A facile approach for the synthesis of magnetite microspheres with flower-like morphology is reported
that proceeds via the reduction of iron(III) oxide under a hydrogen atmosphere. The ensuing magnetic
catalyst is well characterized by XRD, FE-SEM, TEM, N2 adsorption-desorption isotherm, and
Mössbauer spectroscopy and explored for a simple yet efficient transfer hydrogenation reduction of a
variety of nitroarenes to respective anilines in good to excellent yields (up to 98%) employing hydrazine
hydrate. The catalyst could be easily separated at the end of a reaction using an external magnet and
can be recycled up to 10 times without any loss in catalytic activity.
Visible light assisted reduction of nitrobenzenes using Fe(bpy)3+2/rGOnanocom...Pawan Kumar
Visible-light-induced photocatalytic reduction of aromatic nitrobenzenes to the corresponding anilinesat room temperature using reduced graphene oxide (rGO) immobilized iron(II) bipyridine complex asphotocatalyst is described. The rGO-immobilized iron catalyst exhibited superior catalytic activity thanhomogeneous iron(II) bipyridine complex and much higher than metal free rGO photocatalysts. Theheterogeneous photocatalyst was found to be robust and could easily be recovered and reused for severalruns without any significant loss in photocatalytic activity.
Heterostructured nanocomposite tin phthalocyanine@mesoporous ceria (SnPc@CeO2...Pawan Kumar
Heterostructured tin phthalocyanine supported to mesoporous ceria was synthesized and used a
photocatalyst for CO2 reduction under visible light. The photoreduction CO2 activities of the
heterostructures were investigated in the presence of triethylamine as sacrificial agent. The developed
photocatalyst exhibited high catalytic activity for photoreduction of CO2 and after 24 hours of visible
light irradiation 2342 mmol g1 cat of methanol (fMeOH ¼ 0.0223 or 2.23%) and 840 mmol g1 cat of CO
(fCO ¼ 0.0026 or 0.26%) were obtained as the major reaction products. The methanol formation rate
(RMeOH) and CO formation rate (RCO) was found to be 97.5 mmol h1 g1 cat and 35.0 mmol h1 g1 cat
respectively. While under the identical experimental conditions mesoporous ceria (meso-CeO2) gave
only 316 mmol g1 cat of methanol (fMeOH ¼ 0.003 or 0.30%) and 126 mmol g1 cat CO (fCO ¼ 0.0004
or 0.04%) with product formation rate RMeOH ¼ 13.2 mmol h1 g1 cat and RCO ¼ 5.3 mmol h1 g1 cat.
Furthermore, the recovered catalyst showed consistent catalytic activity for at least five runs without any
significant loss in product yields
Photo-assisted oxidation of thiols to disulfides using cobalt ‘‘Nanorust’’ un...Pawan Kumar
Heterogeneous ‘‘Nanorust’’ containing cobalt oxide has been developed for the visible light assisted
oxidation of thiols to disulfides using molecular oxygen as an oxidant under alkaline free conditions and
therefore more environmentally friendly. Pyrolysis of heterogenized tetrasulfonated cobalt(II) phthalocyanine
(CoPcS) supported on mesoporous ceria (CeO2) transforms it into a novel heterogeneous ‘‘Nanorust’’
containing CoOx-C,N@CeO2 which exhibited higher catalytic activity than the homogeneous CoPcS as well
as the ceria immobilized CoPcS catalyst. Importantly, these catalysts could easily be recovered and recycled
for several runs, which makes the process greener and cost-effective.
Nanostructured composite materials for CO2 activationPawan Kumar
The increasing energy crisis and the worsening global climate caused by the excessive
utilization of the fossil fuel have boosted tremendous research about CO2 capture, storage and
utilization. Among these approaches, utilization of carbon dioxide to produce valuable chemicals
is preferred than dumping it. Particularly, utilization of CO2 as feedstock for the photocatalytic
conversion into valuable products is a viable approach for harvesting solar radiation as an energy
source and to mitigate increasing CO2 concentration. Artificial photosynthesis by using
nanostructured materials as photocatalyst has immense potential to convert carbon dioxide into
renewable fuels such as methanol/CO etc. The present chapter focuses on the synthesis, characterization and application of various nanostructured materials for CO2 activation including
photoreduction of CO2 to valuable products.
TiO2-HfN Radial Nano-Heterojunction: A Hot Carrier Photoanode for Sunlight-Dr...Pawan Kumar
The lack of active, stable, earth-abundant, and visible-light absorbing materials to replace
plasmonic noble metals is a critical obstacle for researchers in developing highly efficient and costeffective photocatalytic systems. Herein, a core–shell nanotube catalyst was fabricated consisting of
atomic layer deposited HfN shell and anodic TiO2 support layer with full-visible regime photoactivity
for photoelectrochemical water splitting. The HfN active layer has two unique characteristics: (1) a
large bandgap between optical and acoustic phonon modes (2) and no electronic bandgap, which
allows a large population of long life-time hot carriers, which are used to enhance the photoelectrochemical performance. The photocurrent density (≈2.5 mA·cm−2 at 1 V vs. Ag/AgCl) obtained in
this study under AM 1.5G 1 Sun illumination is unprecedented, as it is superior to most existing
plasmonic noble metal-decorated catalysts and surprisingly indicates a photocurrent response that
extends to 730 nm. The result demonstrates the far-reaching application potential of replacing active
HER/HOR noble metals such as Au, Ag, Pt, Pd, etc. with low-cost plasmonic ceramics.
Visible light assisted reduction of nitrobenzenes using Fe(bpy)3+2/rGOnanocom...Pawan Kumar
Visible-light-induced photocatalytic reduction of aromatic nitrobenzenes to the corresponding anilinesat room temperature using reduced graphene oxide (rGO) immobilized iron(II) bipyridine complex asphotocatalyst is described. The rGO-immobilized iron catalyst exhibited superior catalytic activity thanhomogeneous iron(II) bipyridine complex and much higher than metal free rGO photocatalysts. Theheterogeneous photocatalyst was found to be robust and could easily be recovered and reused for severalruns without any significant loss in photocatalytic activity.
Heterostructured nanocomposite tin phthalocyanine@mesoporous ceria (SnPc@CeO2...Pawan Kumar
Heterostructured tin phthalocyanine supported to mesoporous ceria was synthesized and used a
photocatalyst for CO2 reduction under visible light. The photoreduction CO2 activities of the
heterostructures were investigated in the presence of triethylamine as sacrificial agent. The developed
photocatalyst exhibited high catalytic activity for photoreduction of CO2 and after 24 hours of visible
light irradiation 2342 mmol g1 cat of methanol (fMeOH ¼ 0.0223 or 2.23%) and 840 mmol g1 cat of CO
(fCO ¼ 0.0026 or 0.26%) were obtained as the major reaction products. The methanol formation rate
(RMeOH) and CO formation rate (RCO) was found to be 97.5 mmol h1 g1 cat and 35.0 mmol h1 g1 cat
respectively. While under the identical experimental conditions mesoporous ceria (meso-CeO2) gave
only 316 mmol g1 cat of methanol (fMeOH ¼ 0.003 or 0.30%) and 126 mmol g1 cat CO (fCO ¼ 0.0004
or 0.04%) with product formation rate RMeOH ¼ 13.2 mmol h1 g1 cat and RCO ¼ 5.3 mmol h1 g1 cat.
Furthermore, the recovered catalyst showed consistent catalytic activity for at least five runs without any
significant loss in product yields
Photo-assisted oxidation of thiols to disulfides using cobalt ‘‘Nanorust’’ un...Pawan Kumar
Heterogeneous ‘‘Nanorust’’ containing cobalt oxide has been developed for the visible light assisted
oxidation of thiols to disulfides using molecular oxygen as an oxidant under alkaline free conditions and
therefore more environmentally friendly. Pyrolysis of heterogenized tetrasulfonated cobalt(II) phthalocyanine
(CoPcS) supported on mesoporous ceria (CeO2) transforms it into a novel heterogeneous ‘‘Nanorust’’
containing CoOx-C,N@CeO2 which exhibited higher catalytic activity than the homogeneous CoPcS as well
as the ceria immobilized CoPcS catalyst. Importantly, these catalysts could easily be recovered and recycled
for several runs, which makes the process greener and cost-effective.
Nanostructured composite materials for CO2 activationPawan Kumar
The increasing energy crisis and the worsening global climate caused by the excessive
utilization of the fossil fuel have boosted tremendous research about CO2 capture, storage and
utilization. Among these approaches, utilization of carbon dioxide to produce valuable chemicals
is preferred than dumping it. Particularly, utilization of CO2 as feedstock for the photocatalytic
conversion into valuable products is a viable approach for harvesting solar radiation as an energy
source and to mitigate increasing CO2 concentration. Artificial photosynthesis by using
nanostructured materials as photocatalyst has immense potential to convert carbon dioxide into
renewable fuels such as methanol/CO etc. The present chapter focuses on the synthesis, characterization and application of various nanostructured materials for CO2 activation including
photoreduction of CO2 to valuable products.
TiO2-HfN Radial Nano-Heterojunction: A Hot Carrier Photoanode for Sunlight-Dr...Pawan Kumar
The lack of active, stable, earth-abundant, and visible-light absorbing materials to replace
plasmonic noble metals is a critical obstacle for researchers in developing highly efficient and costeffective photocatalytic systems. Herein, a core–shell nanotube catalyst was fabricated consisting of
atomic layer deposited HfN shell and anodic TiO2 support layer with full-visible regime photoactivity
for photoelectrochemical water splitting. The HfN active layer has two unique characteristics: (1) a
large bandgap between optical and acoustic phonon modes (2) and no electronic bandgap, which
allows a large population of long life-time hot carriers, which are used to enhance the photoelectrochemical performance. The photocurrent density (≈2.5 mA·cm−2 at 1 V vs. Ag/AgCl) obtained in
this study under AM 1.5G 1 Sun illumination is unprecedented, as it is superior to most existing
plasmonic noble metal-decorated catalysts and surprisingly indicates a photocurrent response that
extends to 730 nm. The result demonstrates the far-reaching application potential of replacing active
HER/HOR noble metals such as Au, Ag, Pt, Pd, etc. with low-cost plasmonic ceramics.
A ruthenium trinuclear polyazine complex was synthesized and subsequently immobilized through
complexation to a graphene oxide support containing phenanthroline ligands (GO-phen). The developed
photocatalyst was used for the photocatalytic reduction of CO2 to methanol, using a 20 watt white cold
LED flood light, in a dimethyl formamide–water mixture containing triethylamine as a reductive
quencher. After 48 h illumination, the yield of methanol was found to be 3977.57 5.60 mmol gcat
1.
The developed photocatalyst exhibited a higher photocatalytic activity than graphene oxide, which
provided a yield of 2201.40 8.76 mmol gcat
1. After the reaction, the catalyst was easily recovered and
reused for four subsequent runs without a significant loss of catalytic activity and no leaching of the
metal/ligand was detected during the reaction.
Water-splitting photoelectrodes consisting of heterojunctions of carbon nitri...Pawan Kumar
Quinary and senary non-stoichiometric double perovskites such as Ba2Ca0.66Nb1.34-xFexO6-δ (BCNF) have been utilized for gas sensing, solid oxide fuel cells and thermochemical CO2 reduction. Herein, we examined their potential as narrow bandgap semiconductors for use in solar energy harvesting. A cobalt co-doped BCNF, Ba2Ca0.66Nb0.68Fe0.33Co0.33O6-δ (BCNFCo), exhibited an optical absorption edge at ~ 800 nm, p-type conduction and a distinct photoresponse upto 640 nm while demonstrating high thermochemical stability. A nanocomposite of BCNFCo and g-C3N4 (CN) was prepared via a facile solvent assisted exfoliation/blending approach using dichlorobenzene and glycerol at a moderate temperature. The exfoliation of g-C3N4 followed by wrapping on perovskite established an effective heterojunction between the materials for charge separation. The conjugated 2D sheets of CN enabled better charge migration resulting in increased photoelectrochemical performance. A blend composed of 40 wt% perovskite and CN performed optimally, whilst achieving a photocurrent density as high as 1.5 mA cm-2 for sunlight-driven water-splitting with a Faradaic efficiency as high as ~ 88%.
The threat of global warming is high due to the extensive use of fossil fuels.Using non-renewable resources is a viable solution. Sunlight can be converted in two ways - into electrical energy and into chemical energy. Water splitting and CO2 are two important methods which can be used in solar cells.
Carbon Dioxide to Chemicals and Fuels Course Material.
National Centre for Catalysis Research (NCCR, IIT Madras), considered for the first on-line course the topic of Carbon dioxide to Chemicals and Fuels. NCCR has learnt many such lessons which are necessary for the researchers to understand and also have a complete comprehension of the limitations.
The most difficult goal in the next few decades is the replacement of conventional petro-based fuels with more sustainable fuels that can be used in the existing infrastructure. By the use of Renewable energy or nuclear energy, CO2 and H2O can be recycled into liquid hydrocarbon fuels (the reverse of fuel combustion). Capture of CO2 from the atmosphere will form a close carbon-neutral fuel cycle loop. This article also reviews the aspects regarding thermodynamics involved, involved mechanisms and possible technological pathways for recycling CO2 into fuels using renewable energy. These pathways can be broken into three staged- CO2 capture from atmosphere, H2O and CO2 dissociation, and fuel synthesis.
Flexible and Ultrasoft Inorganic 1D Semiconductor and Heterostructure Systems...Pawan Kumar
Low dimensionality and high flexibility are key demands for flexible electronic semiconductor devices. SnIP, the first atomic-scale double helical semiconductor combines structural anisotropy and robustness with exceptional electronic properties. The benefit of the double helix, combined with a diverse structure on the nanoscale, ranging from strong covalent bonding to weak van der Waals interactions, and the large structure and property anisotropy offer substantial potential for applications in energy conversion and water splitting. It represents the next logical step in downscaling the inorganic semiconductors from classical 3D systems, via 2D semiconductors like MXenes or transition metal dichalcogenides, to the first downsizeable, polymer-like atomic-scale 1D semiconductor SnIP. SnIP shows intriguing mechanical properties featuring a bulk modulus three times lower than any IV, III-V, or II-VI semiconductor. In situ bending tests substantiate that pure SnIP fibers can be bent without an effect on their bonding properties. Organic and inorganic hybrids are prepared illustrating that SnIP is a candidate to fabricate flexible 1D composites for energy conversion and water splitting applications. SnIP@C3N4 hybrid forms an unusual soft material core–shell topology with graphenic carbon nitride wrapping around SnIP. A 1D van der Waals heterostructure is formed capable of performing effective water splitting.
Renewable Fuels by Photocatalytic Reduction of carbondioxide (CO2); (Artifici...SAAD ARIF
This presentation contains the enhancement of photocatalytic Titania (TiO2) by Graphene, their synthesis method by solution mixing or in-situ growth and also the application for carbondioxide (CO2) reduction for renewable fuel using solar energy.
Bicrystalline Titania Photocatalyst for Reduction of CO2 to Solar FuelsA'Lester Allen
Degussa P25, a mixture of anatase and rutile crystal structures, is the most commonly used precursor to form the photoactive layer in solar cells; however, the photocatalytic activity of rutile is inferior to brookite. This presentation discusses the enhancement in photocatalytic activity of an antase brookite mixture.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used
for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after
24 h irradiation was 9934 mmol g1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a
sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride
145 mmol g1cat under identical conditions. The presence of triethylamine was found to be vital for the
higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for
subsequent six runs without significant loss in photo activity.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after 24 h irradiation was 9934 μmol g−1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride 145 μmol g−1cat under identical conditions. The presence of triethylamine was found to be vital for the higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for subsequent six runs without significant loss in photo activity.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used
for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after
24 h irradiation was 9934 mmol g1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a
sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride
145 mmol g1cat under identical conditions. The presence of triethylamine was found to be vital for the
higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for
subsequent six runs without significant loss in photo activity.
tA highly efficient, recyclable and magnetically separable core-shell structured CuZnO@Fe3O4microspherewrapped with reduced graphene oxide (rGO@CuZnO@Fe3O4) photocatalyst has been developed and usedfor the photoreduction of carbon dioxide with water to produce methanol under visible light irradiation.Owing to the synergistic effect of the components and to the presence of a thin Fe2O3layer on Fe3O4,rGO@CuZnO@Fe3O44 exhibited higher catalytic activity as compared to the other possible combinationssuch as CuZnO@Fe3O42 and GO@CuZnO@Fe3O43 microspheres. The yield of methanol in case of using2 and 3 as photocatalyst was found to be 858 and 1749 mol g−1cat, respectively. However, the yieldwas increased to 2656 mol g−1cat when rGO@CuZnO@Fe3O44 was used as photocatalyst under sim-ilar experimental conditions. This superior photocatalytic activity of 4 was assumed to be due to therestoration of the sp2hybridized aromatic system in rGO, which facilitated the movement of electronsand resulted in better charge separation. The synthesized heterogeneous photocatalyst could readily berecovered by external magnet and successfully reused for six subsequent cycles without significant loss in the product yield.
Optical Control of Selectivity of High Rate CO2 Photoreduction Via Interband-...Pawan Kumar
Photonic crystals consisting of TiO2 nanotube arrays (PMTiNTs) with periodically modulated diameters were fabricated using a precise charge-controlled pulsed anodization technique. The PMTiNTs were decorated with gold nanoparticles (Au NPs) to form plasmonic photonic crystal photocatalysts (Au-PMTiNTs). A systematic study of CO2 photoreduction performance on as-prepared samples was conducted using different wavelengths and illumination sequences. A remarkable selectivity of the mechanism of CO2 photoreduction could be engineered by merely varying the spectral composition of the illumination sequence. Under AM1.5 G simulated sunlight (pathway#1), the Au-PMTiNTs produced methane (302 µmol h-1) from CO2 with high selectivity (89.3%). When also illuminated by a UV-poor white lamp (pathway#2), the Au-PMTiNTs produced formaldehyde (420 µmol h-1) and carbon monoxide (323 µmol h-1) with almost no methane evolved. We confirmed the photoreduction results by 13C isotope labeling experiments using GC-MS. These results point to optical control of the selectivity of high-rate CO2 photoreduction through selection of one of two different mechanistic pathways. Pathway#1 implicates electron-hole pairs generated through interband transitions in TiO2 and Au as the primary active species responsible for reducing CO2 to methane. Pathway#2 involves excitation of both TiO2 and surface plasmons in Au. Hot electrons produced by plasmon damping and photogenerated holes in TiO2 proceed to reduce CO2 to HCHO and CO through a plasmonic Z-scheme.
Reduced graphene oxide–CuO nanocomposites for photocatalyticconversion of CO2...Pawan Kumar
tReduced graphene oxide (rGO)–copper oxide nanocomposites are prepared by covalent grafting of CuOnanorods on the rGO skeleton. Chemical and structural features of rGO–CuO nanocomposites are probedby FTIR, XPS, XRD and HRTEM analyses. Photocatalytic potential of rGO–CuO nanocomposites is exploredfor reduction of CO2into the methanol under the visible light irradiation. The breadth of CuO nanorods andthe oxidation state of Cu in the rGO–CuO/Cu2O nanocomposites are systematically varied to investigatetheir photocatalytic activities. The pristine CuO nanorods exhibited very low photocatalytic activity owingto fast recombination of charge carriers and yielded 175 mol g−1methanol, whereas rGO–Cu2O andrGO–CuO exhibited significantly improved photocatalytic activities and yielded five (862 mol g−1) andseven (1228 mol g−1) folds methanol, respectively. The superior photocatalytic activity of CuO in therGO–CuO nanocomposites was attributed to slow recombination of charge carriers and efficient transferof photo-generated electrons through the rGO skeleton. This study further excludes the use of scavengingdonor.
A study of micro structural, magnetic and electrical properties of La-Co-Sm n...IJECEIAES
A Lanthanum (La 3+ ) doped Samarium-Cobalt nanoferrites (La_x,Co_0.2,Sm_0.2,Fe_(2-x) O_4, where x=0.0,0.5,1.0) have been synthesized by sol-gel method in citrate media. Obtained spinal ferrites micro structure properties have been investigated by XRD, FTIR, SEM-EDX, and TEM-SAED techniques. All the samples are nano in size with significant hysteresis. Micro structural analysis by XRD confirms the obtained samples showing the single phase cubic spinal structures with an average crystal size found from 12 nm to 25 nm, while the average particles sizes identified from TEM analysis are ranging from 21.5nm-26.8 nm (~23.4nm) and from 20.5 nm to 28(~26.4nm) nm for x=0.5,1.0. The lattice parameter found to be a= 8.402, 8.423, 8.467Å for the respective values of x= 0.0, 0.05, and 1.0. Electrical properties show increase in dc resistivity with increase in La ion concentration. Finally, it was concluded that the doping of Lanthanum ion (La 3+ ) in the ferrites structure is found to influencing the structural and electrical properties without scarifying the ferromagnetic character.
Vapor Deposition of Semiconducting Phosphorus Allotropes into TiO2 Nanotube A...Pawan Kumar
Recent evidence of exponential environmental degradation will demand a drastic shift in research and development toward
exploiting alternative energy resources such as solar energy. Here, we
report the successful low-cost and easily accessible synthesis of hybrid
semiconductor@TiO2 nanotube photocatalysts. In order to realize its
maximum potential in harvesting photons in the visible-light range, TiO2
nanotubes have been loaded with earth-abundant, low-band-gap fibrous
red and black phosphorus (P). Scanning electron microscopy− and
scanning transmission electron microscopy−energy-dispersive X-ray
spectroscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron microscopy, and UV−vis measurements have been performed,
substantiating the deposition of fibrous red and black P on top and
inside the cavities of 100-μm-long electrochemically fabricated nanotubes. The nanotubular morphology of titania and a vapor-transport technique are utilized to form heterojunctions of P and
TiO2. Compared to pristine anatase 3.2 eV TiO2 nanotubes, the creation of heterojunctions in the hybrid material resulted in
1.5−2.1 eV photoelectrocatalysts. An enhanced photoelectrochemical water-splitting performance under visible light compared
with the individual components resulted for the P@TiO2 hybrids. This feature is due to synergistically improved charge
separation in the heterojunction and more effective visible-light absorption. The electronic band structure and charge-carrier
dynamics are investigated in detail using ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy to elucidate
the charge-separation mechanism. A Fermi-level alignment in P@TiO2 heterojunctions leads to a more reductive flat-band
potential and a deeper valence band compared to pristine P and thus facilitates a better water-splitting performance. Our results
demonstrate effective conversion efficiencies for the nanostructured hybrids, which may enable future applications in
optoelectronic applications such as photodetectors, photovoltaics, photoelectrochemical catalysts, and sensors.
A ruthenium trinuclear polyazine complex was synthesized and subsequently immobilized through
complexation to a graphene oxide support containing phenanthroline ligands (GO-phen). The developed
photocatalyst was used for the photocatalytic reduction of CO2 to methanol, using a 20 watt white cold
LED flood light, in a dimethyl formamide–water mixture containing triethylamine as a reductive
quencher. After 48 h illumination, the yield of methanol was found to be 3977.57 5.60 mmol gcat
1.
The developed photocatalyst exhibited a higher photocatalytic activity than graphene oxide, which
provided a yield of 2201.40 8.76 mmol gcat
1. After the reaction, the catalyst was easily recovered and
reused for four subsequent runs without a significant loss of catalytic activity and no leaching of the
metal/ligand was detected during the reaction.
Water-splitting photoelectrodes consisting of heterojunctions of carbon nitri...Pawan Kumar
Quinary and senary non-stoichiometric double perovskites such as Ba2Ca0.66Nb1.34-xFexO6-δ (BCNF) have been utilized for gas sensing, solid oxide fuel cells and thermochemical CO2 reduction. Herein, we examined their potential as narrow bandgap semiconductors for use in solar energy harvesting. A cobalt co-doped BCNF, Ba2Ca0.66Nb0.68Fe0.33Co0.33O6-δ (BCNFCo), exhibited an optical absorption edge at ~ 800 nm, p-type conduction and a distinct photoresponse upto 640 nm while demonstrating high thermochemical stability. A nanocomposite of BCNFCo and g-C3N4 (CN) was prepared via a facile solvent assisted exfoliation/blending approach using dichlorobenzene and glycerol at a moderate temperature. The exfoliation of g-C3N4 followed by wrapping on perovskite established an effective heterojunction between the materials for charge separation. The conjugated 2D sheets of CN enabled better charge migration resulting in increased photoelectrochemical performance. A blend composed of 40 wt% perovskite and CN performed optimally, whilst achieving a photocurrent density as high as 1.5 mA cm-2 for sunlight-driven water-splitting with a Faradaic efficiency as high as ~ 88%.
The threat of global warming is high due to the extensive use of fossil fuels.Using non-renewable resources is a viable solution. Sunlight can be converted in two ways - into electrical energy and into chemical energy. Water splitting and CO2 are two important methods which can be used in solar cells.
Carbon Dioxide to Chemicals and Fuels Course Material.
National Centre for Catalysis Research (NCCR, IIT Madras), considered for the first on-line course the topic of Carbon dioxide to Chemicals and Fuels. NCCR has learnt many such lessons which are necessary for the researchers to understand and also have a complete comprehension of the limitations.
The most difficult goal in the next few decades is the replacement of conventional petro-based fuels with more sustainable fuels that can be used in the existing infrastructure. By the use of Renewable energy or nuclear energy, CO2 and H2O can be recycled into liquid hydrocarbon fuels (the reverse of fuel combustion). Capture of CO2 from the atmosphere will form a close carbon-neutral fuel cycle loop. This article also reviews the aspects regarding thermodynamics involved, involved mechanisms and possible technological pathways for recycling CO2 into fuels using renewable energy. These pathways can be broken into three staged- CO2 capture from atmosphere, H2O and CO2 dissociation, and fuel synthesis.
Flexible and Ultrasoft Inorganic 1D Semiconductor and Heterostructure Systems...Pawan Kumar
Low dimensionality and high flexibility are key demands for flexible electronic semiconductor devices. SnIP, the first atomic-scale double helical semiconductor combines structural anisotropy and robustness with exceptional electronic properties. The benefit of the double helix, combined with a diverse structure on the nanoscale, ranging from strong covalent bonding to weak van der Waals interactions, and the large structure and property anisotropy offer substantial potential for applications in energy conversion and water splitting. It represents the next logical step in downscaling the inorganic semiconductors from classical 3D systems, via 2D semiconductors like MXenes or transition metal dichalcogenides, to the first downsizeable, polymer-like atomic-scale 1D semiconductor SnIP. SnIP shows intriguing mechanical properties featuring a bulk modulus three times lower than any IV, III-V, or II-VI semiconductor. In situ bending tests substantiate that pure SnIP fibers can be bent without an effect on their bonding properties. Organic and inorganic hybrids are prepared illustrating that SnIP is a candidate to fabricate flexible 1D composites for energy conversion and water splitting applications. SnIP@C3N4 hybrid forms an unusual soft material core–shell topology with graphenic carbon nitride wrapping around SnIP. A 1D van der Waals heterostructure is formed capable of performing effective water splitting.
Renewable Fuels by Photocatalytic Reduction of carbondioxide (CO2); (Artifici...SAAD ARIF
This presentation contains the enhancement of photocatalytic Titania (TiO2) by Graphene, their synthesis method by solution mixing or in-situ growth and also the application for carbondioxide (CO2) reduction for renewable fuel using solar energy.
Bicrystalline Titania Photocatalyst for Reduction of CO2 to Solar FuelsA'Lester Allen
Degussa P25, a mixture of anatase and rutile crystal structures, is the most commonly used precursor to form the photoactive layer in solar cells; however, the photocatalytic activity of rutile is inferior to brookite. This presentation discusses the enhancement in photocatalytic activity of an antase brookite mixture.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used
for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after
24 h irradiation was 9934 mmol g1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a
sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride
145 mmol g1cat under identical conditions. The presence of triethylamine was found to be vital for the
higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for
subsequent six runs without significant loss in photo activity.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after 24 h irradiation was 9934 μmol g−1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride 145 μmol g−1cat under identical conditions. The presence of triethylamine was found to be vital for the higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for subsequent six runs without significant loss in photo activity.
Metal-organic hybrid: Photoreduction of CO2 using graphitic carbon nitride su...Pawan Kumar
A novel heteroleptic iridium complex supported on graphitic carbon nitride was synthesized and used
for photoreduction of carbon dioxide under visible light irradiation. The methanol yield obtained after
24 h irradiation was 9934 mmol g1cat (TON 1241 with respect to Ir) by using triethylamine (TEA) as a
sacrificial donor, which was significantly higher as compared to the semiconductor carbon nitride
145 mmol g1cat under identical conditions. The presence of triethylamine was found to be vital for the
higher methanol yield. After the reaction, the photocatalyst could easily be recovered and reused for
subsequent six runs without significant loss in photo activity.
tA highly efficient, recyclable and magnetically separable core-shell structured CuZnO@Fe3O4microspherewrapped with reduced graphene oxide (rGO@CuZnO@Fe3O4) photocatalyst has been developed and usedfor the photoreduction of carbon dioxide with water to produce methanol under visible light irradiation.Owing to the synergistic effect of the components and to the presence of a thin Fe2O3layer on Fe3O4,rGO@CuZnO@Fe3O44 exhibited higher catalytic activity as compared to the other possible combinationssuch as CuZnO@Fe3O42 and GO@CuZnO@Fe3O43 microspheres. The yield of methanol in case of using2 and 3 as photocatalyst was found to be 858 and 1749 mol g−1cat, respectively. However, the yieldwas increased to 2656 mol g−1cat when rGO@CuZnO@Fe3O44 was used as photocatalyst under sim-ilar experimental conditions. This superior photocatalytic activity of 4 was assumed to be due to therestoration of the sp2hybridized aromatic system in rGO, which facilitated the movement of electronsand resulted in better charge separation. The synthesized heterogeneous photocatalyst could readily berecovered by external magnet and successfully reused for six subsequent cycles without significant loss in the product yield.
Optical Control of Selectivity of High Rate CO2 Photoreduction Via Interband-...Pawan Kumar
Photonic crystals consisting of TiO2 nanotube arrays (PMTiNTs) with periodically modulated diameters were fabricated using a precise charge-controlled pulsed anodization technique. The PMTiNTs were decorated with gold nanoparticles (Au NPs) to form plasmonic photonic crystal photocatalysts (Au-PMTiNTs). A systematic study of CO2 photoreduction performance on as-prepared samples was conducted using different wavelengths and illumination sequences. A remarkable selectivity of the mechanism of CO2 photoreduction could be engineered by merely varying the spectral composition of the illumination sequence. Under AM1.5 G simulated sunlight (pathway#1), the Au-PMTiNTs produced methane (302 µmol h-1) from CO2 with high selectivity (89.3%). When also illuminated by a UV-poor white lamp (pathway#2), the Au-PMTiNTs produced formaldehyde (420 µmol h-1) and carbon monoxide (323 µmol h-1) with almost no methane evolved. We confirmed the photoreduction results by 13C isotope labeling experiments using GC-MS. These results point to optical control of the selectivity of high-rate CO2 photoreduction through selection of one of two different mechanistic pathways. Pathway#1 implicates electron-hole pairs generated through interband transitions in TiO2 and Au as the primary active species responsible for reducing CO2 to methane. Pathway#2 involves excitation of both TiO2 and surface plasmons in Au. Hot electrons produced by plasmon damping and photogenerated holes in TiO2 proceed to reduce CO2 to HCHO and CO through a plasmonic Z-scheme.
Reduced graphene oxide–CuO nanocomposites for photocatalyticconversion of CO2...Pawan Kumar
tReduced graphene oxide (rGO)–copper oxide nanocomposites are prepared by covalent grafting of CuOnanorods on the rGO skeleton. Chemical and structural features of rGO–CuO nanocomposites are probedby FTIR, XPS, XRD and HRTEM analyses. Photocatalytic potential of rGO–CuO nanocomposites is exploredfor reduction of CO2into the methanol under the visible light irradiation. The breadth of CuO nanorods andthe oxidation state of Cu in the rGO–CuO/Cu2O nanocomposites are systematically varied to investigatetheir photocatalytic activities. The pristine CuO nanorods exhibited very low photocatalytic activity owingto fast recombination of charge carriers and yielded 175 mol g−1methanol, whereas rGO–Cu2O andrGO–CuO exhibited significantly improved photocatalytic activities and yielded five (862 mol g−1) andseven (1228 mol g−1) folds methanol, respectively. The superior photocatalytic activity of CuO in therGO–CuO nanocomposites was attributed to slow recombination of charge carriers and efficient transferof photo-generated electrons through the rGO skeleton. This study further excludes the use of scavengingdonor.
A study of micro structural, magnetic and electrical properties of La-Co-Sm n...IJECEIAES
A Lanthanum (La 3+ ) doped Samarium-Cobalt nanoferrites (La_x,Co_0.2,Sm_0.2,Fe_(2-x) O_4, where x=0.0,0.5,1.0) have been synthesized by sol-gel method in citrate media. Obtained spinal ferrites micro structure properties have been investigated by XRD, FTIR, SEM-EDX, and TEM-SAED techniques. All the samples are nano in size with significant hysteresis. Micro structural analysis by XRD confirms the obtained samples showing the single phase cubic spinal structures with an average crystal size found from 12 nm to 25 nm, while the average particles sizes identified from TEM analysis are ranging from 21.5nm-26.8 nm (~23.4nm) and from 20.5 nm to 28(~26.4nm) nm for x=0.5,1.0. The lattice parameter found to be a= 8.402, 8.423, 8.467Å for the respective values of x= 0.0, 0.05, and 1.0. Electrical properties show increase in dc resistivity with increase in La ion concentration. Finally, it was concluded that the doping of Lanthanum ion (La 3+ ) in the ferrites structure is found to influencing the structural and electrical properties without scarifying the ferromagnetic character.
Vapor Deposition of Semiconducting Phosphorus Allotropes into TiO2 Nanotube A...Pawan Kumar
Recent evidence of exponential environmental degradation will demand a drastic shift in research and development toward
exploiting alternative energy resources such as solar energy. Here, we
report the successful low-cost and easily accessible synthesis of hybrid
semiconductor@TiO2 nanotube photocatalysts. In order to realize its
maximum potential in harvesting photons in the visible-light range, TiO2
nanotubes have been loaded with earth-abundant, low-band-gap fibrous
red and black phosphorus (P). Scanning electron microscopy− and
scanning transmission electron microscopy−energy-dispersive X-ray
spectroscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron microscopy, and UV−vis measurements have been performed,
substantiating the deposition of fibrous red and black P on top and
inside the cavities of 100-μm-long electrochemically fabricated nanotubes. The nanotubular morphology of titania and a vapor-transport technique are utilized to form heterojunctions of P and
TiO2. Compared to pristine anatase 3.2 eV TiO2 nanotubes, the creation of heterojunctions in the hybrid material resulted in
1.5−2.1 eV photoelectrocatalysts. An enhanced photoelectrochemical water-splitting performance under visible light compared
with the individual components resulted for the P@TiO2 hybrids. This feature is due to synergistically improved charge
separation in the heterojunction and more effective visible-light absorption. The electronic band structure and charge-carrier
dynamics are investigated in detail using ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy to elucidate
the charge-separation mechanism. A Fermi-level alignment in P@TiO2 heterojunctions leads to a more reductive flat-band
potential and a deeper valence band compared to pristine P and thus facilitates a better water-splitting performance. Our results
demonstrate effective conversion efficiencies for the nanostructured hybrids, which may enable future applications in
optoelectronic applications such as photodetectors, photovoltaics, photoelectrochemical catalysts, and sensors.
Vapor Deposition of Semiconducting Phosphorus Allotropes into TiO2 Nanotube A...Pawan Kumar
Recent evidence of exponential environmental degradation will demand a drastic shift in research and development toward exploiting alternative energy resources such as solar energy. Here, we report the successful low-cost and easily accessible synthesis of hybrid semiconductor@TiO2 nanotube photocatalysts. In order to realize its maximum potential in harvesting photons in the visible-light range, TiO2 nanotubes have been loaded with earth-abundant, low-band-gap fibrous red and black phosphorus (P). Scanning electron microscopy– and scanning transmission electron microscopy–energy-dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron microscopy, and UV–vis measurements have been performed, substantiating the deposition of fibrous red and black P on top and inside the cavities of 100-μm-long electrochemically fabricated nanotubes. The nanotubular …
International Journal of Engineering Research and Applications (IJERA) is an open access online peer reviewed international journal that publishes research and review articles in the fields of Computer Science, Neural Networks, Electrical Engineering, Software Engineering, Information Technology, Mechanical Engineering, Chemical Engineering, Plastic Engineering, Food Technology, Textile Engineering, Nano Technology & science, Power Electronics, Electronics & Communication Engineering, Computational mathematics, Image processing, Civil Engineering, Structural Engineering, Environmental Engineering, VLSI Testing & Low Power VLSI Design etc.
Crystal Structure, Topological and Hirshfeld Surface Analysis of a Zn(II) Zwi...Awad Albalwi
Abstract: A mononuclear Zn(II) complex of (Zn(H2L) (CH3OH) Cl2
) (1) has been synthesized by using
a nonlinear optically active Zwitterionic Schiff base which is 4-((2-hydroxy-3-methoxybenzylidene)
amino) benzoic acid (H2L). Complex 1 has been structurally analyzed by FTIR and UV spectroscopy,
TGA, Powder-XRD and single crystal X-ray diffraction. X-Ray crystallographic studies revealed Zn(II)
complex crystallizes in a P21/c space group and exists in a distorted trigonal bipyramidal geometry
(τ = 0.68).
Structure, microstructure and dielectric study of (ba0.6 sr0.4)(zr0.6ti0.4)o3...eSAT Publishing House
IJRET : International Journal of Research in Engineering and Technology is an international peer reviewed, online journal published by eSAT Publishing House for the enhancement of research in various disciplines of Engineering and Technology. The aim and scope of the journal is to provide an academic medium and an important reference for the advancement and dissemination of research results that support high-level learning, teaching and research in the fields of Engineering and Technology. We bring together Scientists, Academician, Field Engineers, Scholars and Students of related fields of Engineering and Technology.
Synthesis of flower-like magnetite nanoassembly: Application in the efficient...Pawan Kumar
A facile approach for the synthesis of magnetite microspheres with flower-like morphology is reported that proceeds via the reduction of iron (III) oxide under hydrogen atmosphere. The ensuing magnetic catalyst is well characterized by XRD, FE-SEM, TEM, N2 adsorption-desorption isotherm and Mössbauer spectroscopy and explored for a simple yetbut efficient transfer hydrogenation reduction of a variety of nitroarenes to respective anilines in good to excellent yields (up to 98%) employing hydrazine hydrate. . The catalyst could be easily separated at the end of reaction using an external magnet and can be recycled up to 10 times without any loss in catalytic activity.
Structural, Electrical and Magnetotransport properties of La0.7Ca0.2Sr0.1MnO3...IOSR Journals
The sample of manganite perovskite oxide La0.7Ca0.2Sr0.1MnO3 has been prepared by solution combustion synthesis. The synthesized sample has been pelletized and further sintered at 8000C for 8 hours. The XRD pattern reveals that the samples are of single phase nature with orthorhombic structure and the diffraction patterns can be indexed with the pbnm space groups. The crystallite sizes calculated from broadening of XRD peaks using Scherrer’s formula were about 18 nm. Resistivity measurements were performed in the temperature range 2K under 3, 5, 10 and 14 T field using PPMS. Magnetoresistance shows a shift in metal-insulator transition temperature from ~213 K at zero field to ~250 K at 14T. MR value decreases as the temperature increases and at 300 K maximum value of MR is found to be ~ 22% for an applied field of 14 T. MR of ~ 28% is observed at 230 K. MR of ~ 35% is observed at 150 K in an applied field of 14 T and MR has negative sign
International Journal of Engineering Research and DevelopmentIJERD Editor
Electrical, Electronics and Computer Engineering,
Information Engineering and Technology,
Mechanical, Industrial and Manufacturing Engineering,
Automation and Mechatronics Engineering,
Material and Chemical Engineering,
Civil and Architecture Engineering,
Biotechnology and Bio Engineering,
Environmental Engineering,
Petroleum and Mining Engineering,
Marine and Agriculture engineering,
Aerospace Engineering.
Facile Synthesis and Characterization of Pyrolusite, β-MnO2, Nano Crystal wit...Editor IJCATR
MnO2 nanoparticles have been synthesized by a simple combustion method using MnSO4.4H2O. The crystalline phase, morphology, optical property and magnetic property of the as prepared nanoparticle were characterized using XRD, FT-IR, FT-Raman, SEM, UV-Vis, PL and VSM respectively. Structural studies by XRD indicate that the synthesized material as tetragonal rutile crystal structure. FT-IR and FT-Raman analysis revealed the stretching vibrations of metal ions in tetrahedral co-ordination confirming the crystal structure. The PL and UV analysis having an emission band at 390 nm, showed a prominent blue peak at 453 nm as well as a green emission lines at 553 nm with band gap energy of 3.2eV. Magnetic measurements indicate that the Néel temperature of the β-MnO2 structures is 92.5K for Hc = 100 Oe which showed antiferromagnetic behaviour.
Facile Synthesis and Characterization of Pyrolusite, β- MnO2, Nano Crystal wi...Editor IJCATR
MnO2 nanoparticles have been synthesized by a simple combustion method using MnSO4.4H2O. The crystalline phase,
morphology, optical property and magnetic property of the as prepared nanoparticle were characterized using XRD, FT-IR, FTRaman,
SEM, UV-Vis, PL and VSM respectively. Structural studies by XRD indicate that the synthesized material as tetragonal rutile
crystal structure. FT-IR and FT-Raman analysis revealed the stretching vibrations of metal ions in tetrahedral co-ordination confirming
the crystal structure. The PL and UV analysis having an emission band at 390 nm, showed a prominent blue peak at 453 nm as well as
a green emission lines at 553 nm with band gap energy of 3.2eV. Magnetic measurements indicate that the Néel temperature of the β-
MnO2 structures is 92.5K for Hc = 100 Oe which showed antiferromagnetic behaviour
Isolated Iridium Sites on Potassium-Doped Carbon-nitride wrapped Tellurium Na...Pawan Kumar
Many industrial processes such transesterification of fatty acid for biodiesel production, soap manufacturing and biosynthesis of ethanol generate glycerol as a major by-product that can be used to produce commodity chemicals. Photocatalytic transformation of glycerol is an enticing approach that can exclude the need of harsh oxidants and extraneous thermal energy. However, the product yield and selectivity remain poor due to low absorption and unsymmetrical site distribution on the catalyst surface. Herein, tellurium (Te) nanorods/nanosheets (TeNRs/NSs) wrapped potassium-doped carbon nitride (KCN) van der Waal (vdW) heterojunction (TeKCN) is designed to enhance charge separation and visible-NIR absorption. The iridium (Ir) single atom sites decoration on the TeKCN core-shell structure (TeKCNIr) promotes selective oxidation of glycerol to glyceraldehyde with a conversion of 45.6% and selectivity of 61.6% under AM1.5G irradiation. The catalytic selectivity can reach up to 88% under 450 nm monochromatic light. X-ray absorption spectroscopy (XAS) demonstrates the presence of undercoordinated IrN2O2 sites which improved catalytic selectivity for glycol oxidation. Band energies and computational calculations reveal faile charge transfer in the TeKCNIr heterostructure. EPR and scavenger tests discern that superoxide (O2•−) and hydroxyl (•OH) radicals are prime components driving glycerol oxidation.
Isolated Iridium Sites on Potassium-Doped Carbon-nitride wrapped Tellurium Na...Pawan Kumar
Many industrial processes such transesterification of fatty acid for biodiesel production, soap manufacturing and biosynthesis of ethanol generate glycerol as a major by-product that can be used to produce commodity chemicals. Photocatalytic transformation of glycerol is an enticing approach that can exclude the need of harsh oxidants and extraneous thermal energy. However, the product yield and selectivity remain poor due to low absorption and unsymmetrical site distribution on the catalyst surface. Herein, tellurium (Te) nanorods/nanosheets (TeNRs/NSs) wrapped potassium-doped carbon nitride (KCN) van der Waal (vdW) heterojunction (TeKCN) is designed to enhance charge separation and visible-NIR absorption. The iridium (Ir) single atom sites decoration on the TeKCN core-shell structure (TeKCNIr) promotes selective oxidation of glycerol to glyceraldehyde with a conversion of 45.6% and selectivity of 61.6% under AM1.5G irradiation. The catalytic selectivity can reach up to 88% under 450 nm monochromatic light. X-ray absorption spectroscopy (XAS) demonstrates the presence of undercoordinated IrN2O2 sites which improved catalytic selectivity for glycol oxidation. Band energies and computational calculations reveal faile charge transfer in the TeKCNIr heterostructure. EPR and scavenger tests discern that superoxide (O2•−) and hydroxyl (•OH) radicals are prime components driving glycerol oxidation.
Isolated Iridium Sites on Potassium-Doped Carbon-nitride wrapped Tellurium Na...Pawan Kumar
Many industrial processes such transesterification of fatty acid for biodiesel production, soap manufacturing and biosynthesis of ethanol generate glycerol as a major by-product that can be used to produce commodity chemicals. Photocatalytic transformation of glycerol is an enticing approach that can exclude the need of harsh oxidants and extraneous thermal energy. However, the product yield and selectivity remain poor due to low absorption and unsymmetrical site distribution on the catalyst surface. Herein, tellurium (Te) nanorods/nanosheets (TeNRs/NSs) wrapped potassium-doped carbon nitride (KCN) van der Waal (vdW) heterojunction (TeKCN) is designed to enhance charge separation and visible-NIR absorption. The iridium (Ir) single atom sites decoration on the TeKCN core-shell structure (TeKCNIr) promotes selective oxidation of glycerol to glyceraldehyde with a conversion of 45.6% and selectivity of 61.6% under AM1.5G irradiation. The catalytic selectivity can reach up to 88% under 450 nm monochromatic light. X-ray absorption spectroscopy (XAS) demonstrates the presence of undercoordinated IrN2O2 sites which improved catalytic selectivity for glycol oxidation. Band energies and computational calculations reveal faile charge transfer in the TeKCNIr heterostructure. EPR and scavenger tests discern that superoxide (O2•−) and hydroxyl (•OH) radicals are prime components driving glycerol oxidation.
Solar-Driven Cellulose Photorefining into Arabinose over Oxygen-Doped Carbon ...Pawan Kumar
Biomass photorefining is a promising strategy to address the energy crisis and transition toward carbon carbon-neutral society. Here, we demonstrate the feasibility of direct cellulose photorefining into arabinose by a rationally designed oxygen-doped polymeric carbon nitride, which generates favorable oxidative species (e.g., O2–, •OH) for selective oxidative reactions at neutral conditions. In addition, we also illustrate the mechanism of the photocatalytic cellulose to arabinose conversion by density functional theory calculations. The oxygen insertion derived from oxidative radicals at the C1 position of glucose within cellulose leads to oxidative cleavage of β-1,4 glycosidic linkages, resulting in the subsequent gluconic acid formation. The following decarboxylation process of gluconic acid via C1–C2 α-scissions, triggered by surface oxygen-doped active sites, generates arabinose and formic acid, respectively. This work not only offers a mechanistic understanding of cellulose photorefining to arabinose but also sets up an example for illuminating the path toward direct cellulose photorefining into value-added bioproducts under mild conditions.
Solar-Driven Cellulose Photorefining into Arabinose over Oxygen-Doped Carbon ...Pawan Kumar
Biomass photorefining is a promising strategy to address the energy crisis and transition toward carbon carbon-neutral society. Here, we demonstrate the feasibility of direct cellulose photorefining into arabinose by a rationally designed oxygen-doped polymeric carbon nitride, which generates favorable oxidative species (e.g., O2–, •OH) for selective oxidative reactions at neutral conditions. In addition, we also illustrate the mechanism of the photocatalytic cellulose to arabinose conversion by density functional theory calculations. The oxygen insertion derived from oxidative radicals at the C1 position of glucose within cellulose leads to oxidative cleavage of β-1,4 glycosidic linkages, resulting in the subsequent gluconic acid formation. The following decarboxylation process of gluconic acid via C1–C2 α-scissions, triggered by surface oxygen-doped active sites, generates arabinose and formic acid, respectively. This work not only offers a mechanistic understanding of cellulose photorefining to arabinose but also sets up an example for illuminating the path toward direct cellulose photorefining into value-added bioproducts under mild conditions.
Solar-Driven Cellulose Photorefining into Arabinose over Oxygen-Doped Carbon ...Pawan Kumar
Biomass photorefining is a promising strategy to address the energy crisis and transition toward carbon carbon-neutral society. Here, we demonstrate the feasibility of direct cellulose photorefining into arabinose by a rationally designed oxygen-doped polymeric carbon nitride, which generates favorable oxidative species (e.g., O2–, •OH) for selective oxidative reactions at neutral conditions. In addition, we also illustrate the mechanism of the photocatalytic cellulose to arabinose conversion by density functional theory calculations. The oxygen insertion derived from oxidative radicals at the C1 position of glucose within cellulose leads to oxidative cleavage of β-1,4 glycosidic linkages, resulting in the subsequent gluconic acid formation. The following decarboxylation process of gluconic acid via C1–C2 α-scissions, triggered by surface oxygen-doped active sites, generates arabinose and formic acid, respectively. This work not only offers a mechanistic understanding of cellulose photorefining to arabinose but also sets up an example for illuminating the path toward direct cellulose photorefining into value-added bioproducts under mild conditions.
Partial Thermal Condensation Mediated Synthesis of High-Density Nickel Single...Pawan Kumar
Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer–Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.
Partial Thermal Condensation Mediated Synthesis of High-Density Nickel Single...Pawan Kumar
Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer–Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.
Selective Cellobiose Photoreforming for Simultaneous Gluconic Acid and Syngas...Pawan Kumar
Here, we demonstrate the selective cellobiose (building block of cellulose) photoreforming for gluconic acid and syngas co-production in acidic conditions by rationally designing a bifunctional polymeric carbon nitride (CN) with potassium/sulfur co-dopant. This heteroatomic doped CN photocatalyst possesses enhanced visible light absorption, higher charge separation efficiency than pristine CN. Under acidic conditions, cellobiose is not only more efficiently hydrolyzed into glucose but also promotes the syngas and gluconic acid production. Density functional theory (DFT) calculations reveal the favorable generation of •O2− during the photocatalytic reaction, which is essential for gluconic acid production. Consequently, the fine-designed photocatalyst presents excellent cellobiose conversion (>80%) and gluconic acid selectivity (>70%) together with the co-production of syngas (~56 μmol g-1 h-1) under light illumination. The current work demonstrates the feasibility of biomass photoreforming with value-added chemicals and syngas co-production under mild condition.
Selective Cellobiose Photoreforming for Simultaneous Gluconic Acid and Syngas...Pawan Kumar
Here, we demonstrate the selective cellobiose (building block of cellulose) photoreforming for gluconic acid and syngas co-production in acidic conditions by rationally designing a bifunctional polymeric carbon nitride (CN) with potassium/sulfur co-dopant. This heteroatomic doped CN photocatalyst possesses enhanced visible light absorption, higher charge separation efficiency than pristine CN. Under acidic conditions, cellobiose is not only more efficiently hydrolyzed into glucose but also promotes the syngas and gluconic acid production. Density functional theory (DFT) calculations reveal the favorable generation of •O2− during the photocatalytic reaction, which is essential for gluconic acid production. Consequently, the fine-designed photocatalyst presents excellent cellobiose conversion (>80%) and gluconic acid selectivity (>70%) together with the co-production of syngas (~56 μmol g-1 h-1) under light illumination. The current work demonstrates the feasibility of biomass photoreforming with value-added chemicals and syngas co-production under mild condition.
Selective Cellobiose Photoreforming for Simultaneous Gluconic Acid and Syngas...Pawan Kumar
Here, we demonstrate the selective cellobiose (building block of cellulose) photoreforming for gluconic acid and syngas co-production in acidic conditions by rationally designing a bifunctional polymeric carbon nitride (CN) with potassium/sulfur co-dopant. This heteroatomic doped CN photocatalyst possesses enhanced visible light absorption, higher charge separation efficiency than pristine CN. Under acidic conditions, cellobiose is not only more efficiently hydrolyzed into glucose but also promotes the syngas and gluconic acid production. Density functional theory (DFT) calculations reveal the favorable generation of •O2− during the photocatalytic reaction, which is essential for gluconic acid production. Consequently, the fine-designed photocatalyst presents excellent cellobiose conversion (>80%) and gluconic acid selectivity (>70%) together with the co-production of syngas (~56 μmol g-1 h-1) under light illumination. The current work demonstrates the feasibility of biomass photoreforming with value-added chemicals and syngas co-production under mild condition.
Partial Thermal Condensation Mediated Synthesis of High-Density Nickel Single...Pawan Kumar
Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer–Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.
Recent advancements in tuning the electronic structures of transitional metal...Pawan Kumar
The smooth transition from finite non-renewables to renewable energy conversion technologies will require efficient electrocatalysts which can harness intermittent energies to store in the form of chemical bonds. The oxygen evolution reaction (OER) impedes the widespread usage of water electrolyzers to convert H2O into H2 and persists as a bottleneck, including other energy conversion devices with sluggish four H+/e− kinetics. In this context, designing highly active and stable catalysts capable of driving a lower overpotential in the OER to produce continuous hydrogen (H2) is a primary demanded. This chapter discussed the mechanism of the OER in conventional adsorbate oxygen and lattice oxygen participation in transition metal oxides (TMOs). Further, the influences of surface engineering, doping, and defects in the TMOs and understanding the electronic structure to screen electrodes towards the structure–activity relationship are highlighted. Specifically, the adsorption strength of O 2p is understood in detail as its binding ability over the surface of TMOs can be correlated directly to the OER activity. The iterative development of TMOs in terms of understanding electronic structural attributes is essential for the commercial deployment of energy conversion technologies. The comprehensive outlook of this chapter investigates thoroughly how TMOs can be used as significant materials for the OER in the near future.
Hole transport materials (HTMs) have a significant impact on the effectiveness of organic electronic devices; therefore, we present a molecular architecture of pyrazino[2,3-g]quinoxaline (PQ10)-based room-temperature organic liquid crystalline semiconductor (OLCS) as an alternative HTM. The PQ10 compound exhibits three different rectangular columnar (Colr) phases offering an impressive hole mobility of 8.8 × 10−3 cm2V−1s−1 which is found to be dexterous than most of existing polymeric hole transport materials. The charge transport mechanism is governed by the hole polarons hopping through H-aggregates of the PQ10 molecules and the hole mobility remains nearly constant throughout the mesophase range, but it decreases with increasing applied electric field. The current-voltage characteristics of the PQ10 have also been investigated in all three Colr phases and explained via the Poole-Frenkel conduction mechanism. The dielectric spectroscopy has been eventually carried out to understand the nature of dielectric permittivity and conductivity as a function of temperature and a correlation is established between the molecular architecture of the Colr phases and aforementioned physical properties. Solar cell simulation has been additionally performed to demonstrate that the PQ10 material can be a better choice as HTM for organic electronics and photovoltaic applications.
Multifunctional carbon nitride nanoarchitectures for catalysisPawan Kumar
Catalysis is at the heart of modern-day chemical and pharmaceutical industries, and there is an urgent demand to develop metal-free, high surface area, and efficient catalysts in a scalable, reproducible and economic manner. Amongst the ever-expanding two-dimensional materials family, carbon nitride (CN) has emerged as the most researched material for catalytic applications due to its unique molecular structure with tunable visible range band gap, surface defects, basic sites, and nitrogen functionalities. These properties also endow it with anchoring capability with a large number of catalytically active sites and provide opportunities for doping, hybridization, sensitization, etc. To make considerable progress in the use of CN as a highly effective catalyst for various applications, it is critical to have an in-depth understanding of its synthesis, structure and surface sites. The present review provides an overview of the recent advances in synthetic approaches of CN, its physicochemical properties, and band gap engineering, with a focus on its exclusive usage in a variety of catalytic reactions, including hydrogen evolution reactions, overall water splitting, water oxidation, CO2 reduction, nitrogen reduction reactions, pollutant degradation, and organocatalysis. While the structural design and band gap engineering of catalysts are elaborated, the surface chemistry is dealt with in detail to demonstrate efficient catalytic performances. Burning challenges in catalytic design and future outlook are elucidated.
Production of Renewable Fuels by the Photocatalytic Reduction of CO2 using Ma...Pawan Kumar
The photo-reductive performance of natural ilmenite was boosted and the production of renewable fuels from the reduction of CO2 was enhanced by doping the natural mineral with magnesium. The doping was achieved by high energy ball milling in the presence of MgO and Mg(NO3)2. The photo-reduction of CO2 in aqueous solution led to the evolution of H2, CH4, C2H4, and C2H6, and the insertion of Mg in the structure of ilmenite enabled increases of up to 1245% in the fuel production yield, reaching total production of 210.9 µmol h-1 gcat-1. Displacements of the conduction band to more negative potentials were evidenced for the samples doped with magnesium. Indirect effects such as increases in the valence band maximum, and the introduction of intermediate energy levels were also evidenced through the measurement of the crystallite size and the determination of the band structure of the materials. Mott-Schottky analyses of the samples showed the n-type nature of the semiconductor materials and enabled the estimation of the density of charge carriers, which strongly influenced the photocatalytic performance. The strong potential of the application of natural ilmenite in gas phase artificial photosynthesis was proved by the evaluation of CO2 reduction in gas conditions, which allowed the enhancement in the selectivity and significantly increased the production of CH4 as compared to aqueous solution, reaching an important yield of CH4 of 16.1 µmol h-1 gcat-1.
Nanoengineered Au-Carbon Nitride Interfaces Enhance PhotoCatalytic Pure Water...Pawan Kumar
Photocatalytic pure water splitting using solar energy is one of the promising routes to produce sustainable green hydrogen (H2). Tuning the interfacial active site density at catalytic heterojunctions and better light management are imperative to steer the structure-activity correlations to enhance the photo-efficiency of nanocomposite photocatalysts. Herein, we report the decoration of nitrogen defects-rich carbon nitride CN(T) with metallic Au nanostructures of different morphologies and sizes to investigate their influence on the photocatalytic hydrogen evolution reactions (HER). The CN(T)-7-NP nano-heterostructure comprises Au nanoparticles (NPs) of ~7 nm and thiourea-derived defective CN exhibits an excellent H2 production rate of 76.8 µmol g–1 h–1 from pure water under simulated AM 1.5 solar irradiation. In contrast to large-size Au nanorods, the high activity of CN(T)-7-NP was attributed to their strong localized surface plasmon resonance (LSPR) mediated visible absorption and interfacial charge separation. The surface ligands used to control Au nanostructures morphology were found to play a major role in the stabilization of NPs and improve interfacial charge transport between Au NPs and CN(T). First-principles calculations revealed that defects in CN and Au-CN interfacial sites in these nanocomposites facilitate the separation of e-/h+ pairs after light excitation and provide lower energy barrier pathways for H2 production by photocatalytic water splitting.
Nanoengineered Au-Carbon Nitride Interfaces Enhance Photo-Catalytic Pure Wate...Pawan Kumar
Photocatalytic pure water splitting using solar energy is one of the promising routes to produce sustainable green hydrogen (H2). Tuning the interfacial active site density at catalytic heterojunctions and better light management are imperative to steer the structure-activity correlations to enhance the photo-efficiency of nanocomposite photocatalysts. Herein, we report the decoration of nitrogen defects-rich carbon nitride CN(T) with metallic Au nanostructures of different morphologies and sizes to investigate their influence on the photocatalytic hydrogen evolution reactions (HER). The CN(T)-7-NP nano-heterostructure comprises Au nanoparticles (NPs) of ~7 nm and thiourea-derived defective CN exhibits an excellent H2 production rate of 76.8 µmol g–1 h–1 from pure water under simulated AM 1.5 solar irradiation. In contrast to large-size Au nanorods, the high activity of CN(T)-7-NP was attributed to their strong localized surface plasmon resonance (LSPR) mediated visible absorption and interfacial charge separation. The surface ligands used to control Au nanostructures morphology were found to play a major role in the stabilization of NPs and improve interfacial charge transport between Au NPs and CN(T). First-principles calculations revealed that defects in CN and Au-CN interfacial sites in these nanocomposites facilitate the separation of e-/h+ pairs after light excitation and provide lower energy barrier pathways for H2 production by photocatalytic water splitting.
Cooperative Copper Single Atom Catalyst in Two-dimensional Carbon Nitride for...Pawan Kumar
Renewable electricity powered carbon dioxide (CO2) reduction (eCO2R) to high-value fuels like methane (CH4) holds the potential to close the carbon cycle at meaningful scales. However, this kinetically staggered 8-electron multistep reduction still suffers from inadequate catalytic efficiency and current density. Atomic Cu-structures can boost eCO2R-to-CH4 selectivity due to enhanced intermediate binding energies (BEs) resulting from favorably shifted d-band centers. Herein, we exploit two-dimensional carbon nitride (CN) matrices, viz. Na-polyheptazine (PHI) and Li-polytriazine imides (PTI), to host Cu-N2 type single atom sites with high density (∼1.5 at%), via a facile metal ion exchange process. Optimized Cu loading in nanocrystalline Cu-PTI maximizes eCO2R-to-CH4 performance with Faradaic efficiency (FECH4) of ≈68% and a high partial current density of 348 mA cm−2 at a low potential of -0.84 V versus RHE, surpassing the state-of-the-art catalysts. Multi-Cu substituted N-appended nanopores in the CN frameworks yield thermodynamically stable quasi-dual/triple sites with large interatomic distances dictated by the pore dimensions. First-principles calculations elucidate the relative Cu-CN cooperative effects between the two matrices and how the Cu-Cu distance and local environment dictate the adsorbate BEs, density of states, and CO2-to-CH4 energy profile landscape. The 9N pores in Cu-PTI yield cooperative Cu-Cu sites that synergistically enhance the kinetics of the rate-limiting steps in the eCO2R-to-CH4 pathway.
Bioinspired multimetal electrocatalyst for selective methane oxidationPawan Kumar
Selective partial electrooxidation of methane (CH4) to liquid oxygenates has been a long-sought goal. However, the high activation energy of C–H bonds and competing oxygen evolution reaction limit product selectivity and reaction rates. Inspired by iron (IV)-oxo containing metalloenzymes’ functionality to activate the C–H bond, here we report on the design of a copper-iron-nickel catalyst for selective oxidation of CH4 to formate via a peroxide-assisted pathway. Each catalyst serves a specific role which is confirmed via electrochemical, in situ, and theoretical studies. A combination of electrochemical and in situ spectroelectrochemical studies revealed that H2O2 oxidation on nickel led to the formation of active oxygen species which trigger the formation of iron (IV) at low voltages. Density functional theory analysis helped reveal the role of iron (IV)-oxo species in reducing the activation energy barrier for CH4 deprotonation and the critical role of copper to suppress overoxidation. Our multimetal catalyst exhibits a formate faradaic efficiency of 42% at an applied potential of 0.9 V versus a reversible hydrogen electrode.
The ability to recreate computational results with minimal effort and actionable metrics provides a solid foundation for scientific research and software development. When people can replicate an analysis at the touch of a button using open-source software, open data, and methods to assess and compare proposals, it significantly eases verification of results, engagement with a diverse range of contributors, and progress. However, we have yet to fully achieve this; there are still many sociotechnical frictions.
Inspired by David Donoho's vision, this talk aims to revisit the three crucial pillars of frictionless reproducibility (data sharing, code sharing, and competitive challenges) with the perspective of deep software variability.
Our observation is that multiple layers — hardware, operating systems, third-party libraries, software versions, input data, compile-time options, and parameters — are subject to variability that exacerbates frictions but is also essential for achieving robust, generalizable results and fostering innovation. I will first review the literature, providing evidence of how the complex variability interactions across these layers affect qualitative and quantitative software properties, thereby complicating the reproduction and replication of scientific studies in various fields.
I will then present some software engineering and AI techniques that can support the strategic exploration of variability spaces. These include the use of abstractions and models (e.g., feature models), sampling strategies (e.g., uniform, random), cost-effective measurements (e.g., incremental build of software configurations), and dimensionality reduction methods (e.g., transfer learning, feature selection, software debloating).
I will finally argue that deep variability is both the problem and solution of frictionless reproducibility, calling the software science community to develop new methods and tools to manage variability and foster reproducibility in software systems.
Exposé invité Journées Nationales du GDR GPL 2024
Slide 1: Title Slide
Extrachromosomal Inheritance
Slide 2: Introduction to Extrachromosomal Inheritance
Definition: Extrachromosomal inheritance refers to the transmission of genetic material that is not found within the nucleus.
Key Components: Involves genes located in mitochondria, chloroplasts, and plasmids.
Slide 3: Mitochondrial Inheritance
Mitochondria: Organelles responsible for energy production.
Mitochondrial DNA (mtDNA): Circular DNA molecule found in mitochondria.
Inheritance Pattern: Maternally inherited, meaning it is passed from mothers to all their offspring.
Diseases: Examples include Leber’s hereditary optic neuropathy (LHON) and mitochondrial myopathy.
Slide 4: Chloroplast Inheritance
Chloroplasts: Organelles responsible for photosynthesis in plants.
Chloroplast DNA (cpDNA): Circular DNA molecule found in chloroplasts.
Inheritance Pattern: Often maternally inherited in most plants, but can vary in some species.
Examples: Variegation in plants, where leaf color patterns are determined by chloroplast DNA.
Slide 5: Plasmid Inheritance
Plasmids: Small, circular DNA molecules found in bacteria and some eukaryotes.
Features: Can carry antibiotic resistance genes and can be transferred between cells through processes like conjugation.
Significance: Important in biotechnology for gene cloning and genetic engineering.
Slide 6: Mechanisms of Extrachromosomal Inheritance
Non-Mendelian Patterns: Do not follow Mendel’s laws of inheritance.
Cytoplasmic Segregation: During cell division, organelles like mitochondria and chloroplasts are randomly distributed to daughter cells.
Heteroplasmy: Presence of more than one type of organellar genome within a cell, leading to variation in expression.
Slide 7: Examples of Extrachromosomal Inheritance
Four O’clock Plant (Mirabilis jalapa): Shows variegated leaves due to different cpDNA in leaf cells.
Petite Mutants in Yeast: Result from mutations in mitochondrial DNA affecting respiration.
Slide 8: Importance of Extrachromosomal Inheritance
Evolution: Provides insight into the evolution of eukaryotic cells.
Medicine: Understanding mitochondrial inheritance helps in diagnosing and treating mitochondrial diseases.
Agriculture: Chloroplast inheritance can be used in plant breeding and genetic modification.
Slide 9: Recent Research and Advances
Gene Editing: Techniques like CRISPR-Cas9 are being used to edit mitochondrial and chloroplast DNA.
Therapies: Development of mitochondrial replacement therapy (MRT) for preventing mitochondrial diseases.
Slide 10: Conclusion
Summary: Extrachromosomal inheritance involves the transmission of genetic material outside the nucleus and plays a crucial role in genetics, medicine, and biotechnology.
Future Directions: Continued research and technological advancements hold promise for new treatments and applications.
Slide 11: Questions and Discussion
Invite Audience: Open the floor for any questions or further discussion on the topic.
Seminar of U.V. Spectroscopy by SAMIR PANDASAMIR PANDA
Spectroscopy is a branch of science dealing the study of interaction of electromagnetic radiation with matter.
Ultraviolet-visible spectroscopy refers to absorption spectroscopy or reflect spectroscopy in the UV-VIS spectral region.
Ultraviolet-visible spectroscopy is an analytical method that can measure the amount of light received by the analyte.
THE IMPORTANCE OF MARTIAN ATMOSPHERE SAMPLE RETURN.Sérgio Sacani
The return of a sample of near-surface atmosphere from Mars would facilitate answers to several first-order science questions surrounding the formation and evolution of the planet. One of the important aspects of terrestrial planet formation in general is the role that primary atmospheres played in influencing the chemistry and structure of the planets and their antecedents. Studies of the martian atmosphere can be used to investigate the role of a primary atmosphere in its history. Atmosphere samples would also inform our understanding of the near-surface chemistry of the planet, and ultimately the prospects for life. High-precision isotopic analyses of constituent gases are needed to address these questions, requiring that the analyses are made on returned samples rather than in situ.
Nutraceutical market, scope and growth: Herbal drug technologyLokesh Patil
As consumer awareness of health and wellness rises, the nutraceutical market—which includes goods like functional meals, drinks, and dietary supplements that provide health advantages beyond basic nutrition—is growing significantly. As healthcare expenses rise, the population ages, and people want natural and preventative health solutions more and more, this industry is increasing quickly. Further driving market expansion are product formulation innovations and the use of cutting-edge technology for customized nutrition. With its worldwide reach, the nutraceutical industry is expected to keep growing and provide significant chances for research and investment in a number of categories, including vitamins, minerals, probiotics, and herbal supplements.
Deep Behavioral Phenotyping in Systems Neuroscience for Functional Atlasing a...Ana Luísa Pinho
Functional Magnetic Resonance Imaging (fMRI) provides means to characterize brain activations in response to behavior. However, cognitive neuroscience has been limited to group-level effects referring to the performance of specific tasks. To obtain the functional profile of elementary cognitive mechanisms, the combination of brain responses to many tasks is required. Yet, to date, both structural atlases and parcellation-based activations do not fully account for cognitive function and still present several limitations. Further, they do not adapt overall to individual characteristics. In this talk, I will give an account of deep-behavioral phenotyping strategies, namely data-driven methods in large task-fMRI datasets, to optimize functional brain-data collection and improve inference of effects-of-interest related to mental processes. Key to this approach is the employment of fast multi-functional paradigms rich on features that can be well parametrized and, consequently, facilitate the creation of psycho-physiological constructs to be modelled with imaging data. Particular emphasis will be given to music stimuli when studying high-order cognitive mechanisms, due to their ecological nature and quality to enable complex behavior compounded by discrete entities. I will also discuss how deep-behavioral phenotyping and individualized models applied to neuroimaging data can better account for the subject-specific organization of domain-general cognitive systems in the human brain. Finally, the accumulation of functional brain signatures brings the possibility to clarify relationships among tasks and create a univocal link between brain systems and mental functions through: (1) the development of ontologies proposing an organization of cognitive processes; and (2) brain-network taxonomies describing functional specialization. To this end, tools to improve commensurability in cognitive science are necessary, such as public repositories, ontology-based platforms and automated meta-analysis tools. I will thus discuss some brain-atlasing resources currently under development, and their applicability in cognitive as well as clinical neuroscience.
Professional air quality monitoring systems provide immediate, on-site data for analysis, compliance, and decision-making.
Monitor common gases, weather parameters, particulates.
Salas, V. (2024) "John of St. Thomas (Poinsot) on the Science of Sacred Theol...Studia Poinsotiana
I Introduction
II Subalternation and Theology
III Theology and Dogmatic Declarations
IV The Mixed Principles of Theology
V Virtual Revelation: The Unity of Theology
VI Theology as a Natural Science
VII Theology’s Certitude
VIII Conclusion
Notes
Bibliography
All the contents are fully attributable to the author, Doctor Victor Salas. Should you wish to get this text republished, get in touch with the author or the editorial committee of the Studia Poinsotiana. Insofar as possible, we will be happy to broker your contact.
Richard's aventures in two entangled wonderlandsRichard Gill
Since the loophole-free Bell experiments of 2020 and the Nobel prizes in physics of 2022, critics of Bell's work have retreated to the fortress of super-determinism. Now, super-determinism is a derogatory word - it just means "determinism". Palmer, Hance and Hossenfelder argue that quantum mechanics and determinism are not incompatible, using a sophisticated mathematical construction based on a subtle thinning of allowed states and measurements in quantum mechanics, such that what is left appears to make Bell's argument fail, without altering the empirical predictions of quantum mechanics. I think however that it is a smoke screen, and the slogan "lost in math" comes to my mind. I will discuss some other recent disproofs of Bell's theorem using the language of causality based on causal graphs. Causal thinking is also central to law and justice. I will mention surprising connections to my work on serial killer nurse cases, in particular the Dutch case of Lucia de Berk and the current UK case of Lucy Letby.
Synthesis of flower-like magnetite nanoassembly: Application in the efficient reduction of nitroarenes
1. 1SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
www.nature.com/scientificreports
Synthesis of flower-like magnetite
nanoassembly:Application in the
efficient reduction of nitroarenes
Kasibhatta J. Datta,Anuj K. Rathi, Pawan Kumar, Josef Kaslik, Ivo Medrik,Vaclav Ranc,
Rajender S.Varma , Radek Zboril & Manoj B.Gawande
A facile approach for the synthesis of magnetite microspheres with flower-like morphology is reported
that proceeds via the reduction of iron(III) oxide under a hydrogen atmosphere.The ensuing magnetic
catalyst is well characterized by XRD, FE-SEM,TEM, N2 adsorption-desorption isotherm, and
Mössbauer spectroscopy and explored for a simple yet efficient transfer hydrogenation reduction of a
variety of nitroarenes to respective anilines in good to excellent yields (up to 98%) employing hydrazine
hydrate.The catalyst could be easily separated at the end of a reaction using an external magnet and
can be recycled up to 10 times without any loss in catalytic activity.
The selective reduction of nitroarenes has attracted a great deal of attention as the resulting anilines are impor-
tant intermediates for the manufacture of pharmaceuticals, dyes, polymers, and fine chemicals1–3
. Generally,
the synthesis of anilines entails catalytic4–6
and non-catalytic methods employing different reducing agents7–9
.
The non-catalytic processes use either Bechamp or sulphide reduction technology which generates large
amounts of undesirable waste that is detrimental to the environment10
. On the other hand, catalytic process is a
well-established technology but relies on mainly expensive precious metal catalysts, namely Pd, Pt, and Ru which
lack chemoselectivity in the presence of other common reducible functional groups6, 11–14
. Furthermore, when
hydrogen is used as the reducing agent, high temperature and pressure are usually needed with requirement of
the specialized equipment. These limitations can be circumvented using various hydrogen donors such as formic
acid4, 5
, hydrazine hydrate9, 15–19
, ammonium salts20
, and sodium borohydride21
, among others, in presence of
various metal catalysts.
Amongst hydrogen donors, hydrazine monohydrate is particularly noteworthy as it produces only harmless
by-products, such as nitrogen gas and water, and is relatively safe and easy to handle compared to its anhydrous
form. From a sustainability perspective, substitution of precious metals by earth-abundant base metals is a highly
desirable pursuit for heterogeneous catalysis. In this aspect, magnetic materials especially iron-based catalysts in
organic synthesis have received significant attention, as iron is plentiful, cost effective, and relatively environmen-
tally benign element22–27
. Consequently, it is not surprising that the reduction of nitroarenes has been reported uti-
lizing a combination of hydrazine and iron catalysts namely various iron salts, its complexes, and oxide forms and
as a supported catalysts9, 15, 17–19, 28, 29
. The readily available magnetic iron oxide nanoparticles stand out to be very
attractive candidates as they are cost-effective nanocatalysts;30–36
being recoverable effortlessly with an external
magnet due to the paramagnetic behaviour thus avoiding cumbersome filtration/separation processes12, 29, 37–39
.
This strategy could significantly improve the catalytic efficiency and decrease the operational cost which is crucial
for practical applications.
Herein, we report a simple approach for the synthesis of magnetite via thermally induced solid state reaction
of iron (III) oxide under hydrogen a atmosphere (Fig. 1). It is interesting to note that the flower/rod like mor-
phology of the precursor is well preserved even after the hydrogen treatment. The as-prepared magnetite catalyst
is characterized by several techniques, namely XRD, FE-SEM, TEM, nitrogen adsorption-desorption isotherm
and Mössbauer spectroscopy. The magnetite acts as a catalyst for the transfer hydrogenation of nitroarenes with
hydrazine hydrate as the reducing agent in a microwave reactor affording nearly quantitative yields. The salient
features of this work are the excellent catalytic performance, simple procedure, easy separation, and the excellent
reusability of the catalyst.
Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science,
Palacký University, Šlechtitelů 27, 783 71, Olomouc, Czech Republic. Kasibhatta J. Datta and Anuj K. Rathi
contributed equally to this work. Correspondence and requests for materials should be addressed to R.Z. (email:
radek.zboril@upol.cz) or M.B.G. (email: manoj.gawande@upol.cz)
Received: 12 June 2017
Accepted: 26 July 2017
Published: xx xx xxxx
OPEN
2. www.nature.com/scientificreports/
2SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
Results and Discussion
The preparation of magnetite microspheres by reduction of iron(III) oxide under a hydrogen atmosphere has been
well investigated40, 41
. Herein, we report a novel method for the synthesis of magnetite with a unique flower-like
morphology from iron(III) oxalate via a simple two-step approach. Firstly, thermally induced solid state decom-
position of iron oxalate was used to produce iron(III) oxide (Fe2O3) with ultra-small nanostructured particles;
and secondly, the subsequent thermally induced reduction of the prepared iron(III) oxide under a hydrogen
atmosphere afforded magnetite (Fe3O4). Figure 2 depicts the stepwise transformation of iron(III) oxide to mag-
netite by hydrogen reduction process via in situ monitoring by XRD. The two shoulders (around 40° and 74° of
2θ) are clearly visible in the diffraction patterns up to 210 °C confirming that the material is iron(III) oxide with
ultra-small particles. At 220 °C, the diffraction lines belonging to fcc structure of magnetite/maghemite start to
Figure 1. Schematic illustration of the synthesis of Fe3O4 nanoflower.
Figure 2. Evolution of X-ray diffraction patterns during in situ monitored thermally induced transformation of
iron(III) oxide with ultra-small particles to magnetite in hydrogen gas atmosphere.
3. www.nature.com/scientificreports/
3SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
emerge and their intensities gradually increased during the 60 min period of isothermal treatment. Thus, we
choose temperature 220 °C for 2 hours as the optimum condition for the preparation of magnetite from iron(III)
oxide with ultra-small particles using a tube furnace under a hydrogen atmosphere.
Figure 3a depicts XRD pattern of magnetite sample. All of the diffraction lines can be clearly ascribed to
standard face-centered cubic (fcc) structure of Fe3O4 (space group: Fd3m (227), JCPDS card No. 01-089-3854).
Although the isostructural character of magnetite and maghemite cause difficulties in direct and precise iden-
tification of these phases by XRD point of view, the cell parameter indicates correct suggestion; it varies from
0.8351 nm for maghemite and 0.8396 nm for stoichiometric magnetite42, 43
. The cell parameter of cubic structure
in the prepared sample is a = 0.8394 nm, which is in good agreement with values described for magnetite in
the literature44
. Nevertheless, the Mössbauer spectroscopy is a powerful experimental technique which provides
precise identification of valence state of iron atoms and cations distribution and more specifically, for the iden-
tification of iron compounds. Consequently, Mössbauer spectroscopy was used for direct identification of iron
oxide’s state (Fig. 2b). The acquired spectrum is composed of two magnetically split subspectra (i.e., sextets). The
first sextet component with an isomer shift (δ) value of 0.27 mm s−1
, quadrupole shift (εQ) value of −0.01 mm/s
and hyperfine magnetic field (Bhf) value of 49.0 T corresponds to Fe3+
ions occupying all the tetrahedral positions
in the Fe3O4 crystal structure and with a contribution from Fe3+
ions sitting in the octahedral sites having Fe3+
ions as the nearest neighbours (i.e. Fe3+
–O–Fe3+
pathway). On the other hand, the second sextet with δ = 0.67
mm/s, εQ = 0.00 mm/s, and Bhf = 46.0 T is ascribed to Fe2+
and Fe3+
ions occupying the octahedral positions in
the Fe3O4 crystal structure among which the electron hopping occurs (i.e., an Fe2+
ion with a neighbouring Fe3+
ion and vice versa; Fe2+
–O–Fe3+
pathway) with a frequency faster than the characteristic time of the Mössbauer
technique and thus manifested as a component with δ value lying in the range typical of an average valence state
of + 2.545
. Relative spectral area of Fe3+
and Fe2.5+
sextet is 41 and 59%, respectively. This difference from ideal
spectral area of 33 (Fe3+
sextet) and 67% (Fe2.5+
sextet) for stoichiometric magnetite indicates a nonstoichiometry
in magnetite. In particular, Fe3+
ions having Fe3+
as the nearest neighbours in the octahedral sites, which thus do
not participate in the electron hopping process, forms their own subspectrum with hyperfine parameters values
very close to those of the subspectrum representing Fe3+
in the tetrahedral sites. Therefore, these two subspectra
with nearly identical parameters are fitted as one and its relative area is increased to the detriment of subspectra
representing mixed valence Fe2.5+
in octahedral sites.
Figure 3. (a) XRD pattern and (b) Mössbauer spectrum of magnetite.
4. www.nature.com/scientificreports/
4SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
The morphology of the prepared samples was obtained using scanning electron microscope (SEM) and trans-
mission electron microscope (TEM). The SEM image (Fig. 4a) of magnetite revealed the retention of rod/flower
like pattern as found in the case of iron(III) oxide46
. From the TEM image (Fig. 4b), it can be seen that the indi-
vidual nanorods possess an average breadth of size 300 nm while the self-assembled floral pattern has a diameter
of about 3 μm.
TEM image (Fig. 4b) also showed the porous nature of the rods composed of interconnected microspheres.
The sharp diffraction spot due to various planes of Fe3O4 in selected area electron diffraction (SAED) pattern
(Fig. 4b inset) of the particles reveals well crystalline nature of materials. The width of the nanorods forming rod/
flower like pattern was found to be uniform along its entire length as evidenced from the TEM image. The pores
might be formed during recrystallization process or from the elimination of water during the reduction process.
The N2 adsorption–desorption isotherms show Type II isotherm for the magnetite with a small hysteresis
(Fig. 5) which reveal macroporous nature with cylindrical pores. The specific surface area obtained from BET
method is 20 m2
/g.
Furthermore to examine the efficiency of the catalyst, we evaluated its reduction prowess for a variety of nitro
compounds to their corresponding industrially important amine derivatives in ethanol under microwave (MW)
irradiation. Initially, to optimize the reaction conditions, various parameters such as effect of temperature, cata-
lyst loading, solvent, and different hydrogen source including the amount of hydrazine hydrate were studied by
choosing nitrobenzene as a model substrate. As expected, no reaction occurred in the absence of magnetite and
hydrazine hydrate (Table 1, entries 1–3). Firstly, the reaction was carried out under conventional heating condi-
tion using magnetite (30 mg) as a catalyst and 150 μL hydrazine hydrate as hydrogen source in ethanol at 90 °C;
complete conversion occurred in 3 h (Table 1, entry 14). Interestingly, when the reaction was performed under
MW irradiation condition, the complete conversion could be achieved within 15 min (Table 1, entry 7) and no
trace of substrate, intermediates or side product was evident by GC analysis. To explore the optimum amount of
needed catalyst, different catalyst loadings (10, 20, and 30 mg) were investigated which revealed that 30 mg cata-
lyst was the optimum loading that afforded > 99% conversion of nitrobenzene (Table 1, entry 5). The quantity of
hydrazine hydrate did impact the conversion rate; reaction using 60 μL resulted in only 90% conversion (Table 1,
entry 9), while 100 μL delivered quantitative conversion (Table 1, entry 7).
Figure 4. (a) SEM and (b) TEM image of magnetite.
5. www.nature.com/scientificreports/
5SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
Next, the effect of temperature on reduction reactions was determined and at 50 °C, 35% conversion and at
70 °C, 72% conversion was observed (Table 1, entries 10, and 11); increasing the temperature to 90 °C, however,
afforded quantitative conversion within 15 min (Table 1, entry 7). Time variation, a crucial factor, was investigated
next for complete conversion; 10 minutes delivered 94% conversion and 91% yield (Table 1, entry 12). Notably,
with isopropyl alcohol as a hydrogen donor, no reaction occurred (Table 1, entry 13). The catalyst could catalyse
the reaction under conventional heating conditions as well; however, an extended reaction time was required
up to 240 min (Table 1, entry 14). Further, we observed that the reaction did not occur at room temperature and
heating was essential for accomplishing this reaction (Table 1, entry 15).
The effect of different solvents on the reduction of nitrobenzene was also investigated and it was discerned that
ethanol, 2-propanol, and acetonitrile afforded good conversion and yields (Table 2, entries 1, 3, and 5). For THF,
the efficiency of the reduction significantly decreased and only 4% conversion was obtained while a mixture of
EtOH:H2O (1:1) showed moderate conversion (Table 2, entry 2).
Assorted iron catalysts for the reduction of nitrobenzene with hydrazine hydrate were also examined under
the optimized conditions. Notably, commercial Fe powder, FeSO4.7H2O, FeCl3.6H2O (Table 3, entries 1, 2 and 4)
Figure 5. N2 adsorption-desorption isotherm of magnetite.
Entry Catalyst
Amount
of catalyst
(mg)
Hydrazine
hydrate (μL)
Temp.
(˚C)
Time
(Min)
b
Conversion
(%)
b
Yield
(%)
1 ---- ---- ----- 90 30 0 0
2 ----- ---- 150 90 30 0 0
3 Fe3O4 30 ---- 90 30 0 0
4 Fe3O4 10 150 90 30 >97 95
5 Fe3O4 30 150 90 30 >99 98
6 Fe3O4 30 150 90 15 >99 98
7 Fe3O4 30 100 90 15 >99 98
8 Fe3O4 20 100 90 15 93 89
9 Fe3O4 30 60 90 15 >90 87
10 Fe3O4 30 100 50 15 35 25
11 Fe3O4 30 100 70 15 72 66
12 Fe3O4 30 100 90 10 >94 91
13 Fe3O4 30 -----c
90 15 0 ---- c
14 Fe3O4 30 100 90 180 99 97d
15 Fe3O4 30 100 rt 360 ---- ----
Table 1. Magnetite catalyzed catalytic reduction of nitrobenzene under microwave irradiationa
. a
Reaction
conditions: Nitrobenzene (0.5 mmol), Hydrazine hydrate (100 µL), Fe3O4 (30 mg), EtOH (1.5 mL), Temp 90°C.
b
Determined by GC using dodecane as an internal standard, c
Isopropyl alcohol, d
Conventional heating.
6. www.nature.com/scientificreports/
6SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
did not show any activity under these conditions, while FeCl3.4H2O, Fe(acac)3 and magnetite exhibited
18%, > 99%, and > 99% conversion, respectively (Table 3, entries 3, 5, and 6). Although, as-prepared magnetite
and Fe(acac)3 have the same conversion and selectivity, but due to the homogeneous nature of Fe(acac)3, it cannot
be recycled which limits its applications. In contrast, magnetite is a heterogeneous catalyst and has shown superi-
ority due to its magnetic separation property and importantly, the ease of recyclability.
These optimized reaction conditions were then applied to an array of selected substituted nitroarenes bearing
additional reducible groups to ascertain the chemoselectivity aspect and wider scope of the catalyst (Table 4). In
most of the cases, quantitative ( > 99%) conversion of the substrates to the desired amine derivatives occurred
within 15 min.
It was observed that for 5-nitro-1H-indole, sterically hindered 1-methyl-2-nitrobenzene and
6-nitro-2,3-dihydrobenzo[1,4]dioxine, the reactions were completed in 25 min (Table 4, entries 4, 9, and 15),
while 3-fluoro nitrobenzene 4-methoxy nitrobenzene, and 4-methyl nitrobenzene exhibited 99% conversion in
22 min (Table 4, entries 10, 13 and 14). The sole exception was 4-nitrobenzamide which showed 42% conver-
sion in 25 min (Table 4, entry 7) presumably due to the polar nature of the amidic compound. Interestingly,
halogenated nitroarenes such as 2-chloro-4-iodo-1-nitrobenzene, 3-fluoro nitrobenzene, 4-bromo nitroben-
zene, and 4-chloro nitrobenzene showed excellent conversions (Table 4, entries 1, 10, 11, and 12) without any
dehalogenated product being observed. Easily reducible ester groups were well accommodated in this catalytic
system (Table 4, entries 5 and 6). The catalytic prowess became apparent in the reduction of 4-nitrobenzonitrile,
6-nitroquinoline, and methyl (4-nitrophenyl)sulfane with excellent yield of the corresponding desired products
(Table 4, entries 2, 3, and 8).
The catalyst recycling is certainly very essential in heterogeneous catalytic reactions. Therefore, we examined
the recyclability of our developed catalyst for reduction reaction by using nitrobenzene as a model substrate
under the optimized conditions. After completion of the reaction, the catalyst could be easily separated using an
external magnet. The separated spent catalyst was then washed with ethanol and dried before reuse. This process
was repeated 10 times successfully without any noticeable decrease in catalytic activity (Fig. 6) suggesting that the
catalyst could find application in the practical reduction of nitroarenes on industrial scale. The leaching aspect of
any iron after recycling was examined by determining the metal content of reaction solution using AAS (atomic
Entry Solvents b
Conversion (%) b
Yield (%)
1 Ethanol >99 98
2 EtOH:H2O 80 74
3 ACN 95 92
4 THF 4 -
5 2-propanol 95 91
Table 2. Evaluation of different solvents for the reduction of nitrobenzenea
. a
Reaction conditions:
Nitrobenzene (0.5 mmol), Hydrazine hydrate (100 μL), Fe3O4 (30 mg), solvent (1.5 mL), temperature (90 °C),
time (15 min). b
Determined by GC using dodecane as an internal standard.
Entry Catalyst b
Conversion (%) b
Yield (%)
1 Fe powder 0 0
2 FeSO4.7H2O 0 0
3 Fe(acac)3 >99 98
4 FeCl3.6H2O 0 0
5 FeCl3.4H2O 18 14
6 Fe3O4 >99 98
Table 3. Comparative evaluation of different iron species for the reduction of nitrobenzenea
. a
Reaction
conditions: Nitrobenzene (0.5 mmol), Hydrazine hydrate (100 μL), catalyst (30 mg), EtOH (1.5 mL),
temperature (90 °C), time (15 min). b
Determined by GC using dodecane as an internal standard.
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8SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
absorption spectroscopy) after removing of the catalyst; metal content was found to be 0.0735 ± 20% mg/L, which
shows negligible leaching of iron from the catalyst which bodes well for its robustness and reusability.
As mentioned in previous reports, that reduction of nitroarenes can proceed via two common routes10, 47, 48
.
The first direct route proceeds via nitrosobenzene and N-phenylhydroxylamine intermediates, (Fig. 7a). In con-
trast, the second route involves the condensation of nitrosobenzene and N-phenylhydroxylamine which advances
Entry Nitro compound Product
a
Conversion
% b
Yield %
12 99 96
13 99 96e
14 99 95f
15 99 95c
Table 4. Catalytic reduction of nitro compoundsa
. a
Reaction conditions: Nitrobenzene (0.5 mmol),
Hydrazine hydrate (100 μL), Fe3O4 (30 mg), EtOH (1.5 mL), temperature (90 °C), time (15 min).
b
Determined by GC using dodecane as an internal standard. c
reaction time (25 min), d
reaction time
(20 min), e
reaction time (22 min), f
isolated yield.
Figure 6. Reaction conditions: Nitrobenzene (1 mmol), Hydrazine hydrate (200 µL), Fe3O4 (60 mg), EtOH
(3 mL), temperature (90 °C), MW. Determined by GC using dodecane as an internal standard.
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9SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
through the intermediacy of azoxybenzene, azobenzene, and hydrazobenzene. In order to determine the exact
route for this reduction of nitrobenzene, a reaction under identical reaction conditions was conducted for
azobenzene. At the end of reaction, only hydroazobenzene could be isolated and no trace of aniline was detected
which confirmed that reduction of nitroarene proceeded via first direct route.
In view of experimental validation of the direct route and on the basis of previous literature reports, a plausible
mechanism is proposed49–52
. The reaction initiates with the adsorption of hydrazine on the surface of magnet-
ite nanoflowers followed by bond dissociation which produces nitrogen and surface-bound hydrogen as metal
hydride. The nitroarenes adsorbed on the surface of magnetite thus get transformed to nitrosoarenes after reac-
tion with surface adsorbed hydrogen. These highly active nitroso moieties further react with hydrogen to form
stable hydroxylamine; hydrogenation of hydroxylamine is slow and the rate determining step. In the next step,
two proton transfers produce the desired aniline derivatives (Fig. 7).
Conclusion
In summary, we have established a robust, chemoselective and magnetically reusable catalyst for the reduction
of industrially valuable nitroarenes substrates in the presence of other sensitive reducible functional groups. A
diverse range of amines derivatives could be obtained expeditiously (15 min) in excellent yields under the MW
heating conditions at 90 °C using hydrazine hydrate as a hydrogen source which precludes the use of a precious
metal catalysts and hydrogen gas in the preparation of amines derivatives. The magnetite with a unique morphol-
ogy prepared by our method was found to be very stable and could be used ten times successfully with minor
decrease in its catalytic activity. The excellent catalytic performance, simple and a safe procedure, easy separation,
and the recyclability make this environmentally benign catalytic system a remarkable and useful alternative to
other Fe-based catalytic systems.
Methods
Materials. All solvents, hydrazine hydrate (50–60%), iron (II) chloride tetrahydrate (99.99%), oxalic acid
(98%), N,N-dimethylacetamide (DMA) ( ≥ 99%), were purchased from Aldrich as analytical grade and were used
without further purification.
Preparation of the magnetite catalyst. In a typical synthesis protocol, 1 mmol (0.126 g) of oxalic acid
(H2C2O4.2H2O) was dissolved in 10 mL of DMA under continuous magnetic stirring and admixed with an equal
mole ratio (0.198 g) of aqueous iron chloride (FeCl2.4H2O) followed by addition of 12 mL deionised water. After
stirring for 10 min, the as-obtained yellow coloured product (iron oxalate) was separated by centrifugation and
Figure 7. Schematics of (a) direct reaction route for reduction of nitroarene to anilines and (b) mechanism of
nitroarenes reduction over the surface of magnetite via direct route using hydrazine hydrate as hydrogen source.
10. www.nature.com/scientificreports/
10SCienTiFiC Reports | 7: 11585 | DOI:10.1038/s41598-017-09477-7
washed with ethanol several times and dried at 333 K for 12 h. The as-prepared iron oxalate was thermally treated
in air at the conversion temperature of 448 K for 12 h to obtain mesoporous iron(III) oxide (Fe2O3)46
. Further,
magnetite (Fe3O4) was prepared by thermally induced solid state reaction of iron(III) oxide in hydrogen gas at
220 °C for 2 h.
General procedure for the reduction of nitrobenzene. Into a 10 mL microwave vial equipped with
a magnetic stir bar, was placed 0.5 mmol of nitro compound in ethanol (1.5 mL), 100 μL of hydrazine hydrate
followed by 30 mg catalyst. The vial was sealed with a Teflon-lined septum and irradiated with microwaves in a
Monowave 300 single-mode MW reactor (Anton Paar GmbH, Graz, Austria) at 90 °C for 15 min. Progress of the
reaction was monitored by TLC (silica gel; hexane/ethyl acetate) and the conversion and yield were determined
by GC (gas chromatography) using n-hexadecane as an internal standard.
Characterization. XRD patterns of materials were recorded on an X’Pert PRO diffractometer
(PANanalytical) in Bragg-Brentano geometry with iron-filtered Co-Kα radiation (λ = 1.7903 Å) equipped
with fast X’celerator detector. The reaction chamber XRK900 (Anton Paar) mounted to the diffractometer was
employed for in situ monitoring of the preparation of the magnetite sample. Data were processed in High Score
Plus Software in conjunction with PDF-4 + and ICSD databases.
The 57
Fe Mössbauer Spectroscopy measurements were carried out to investigate iron-bearing phase compo-
sitions in the studied samples. Mössbauer spectra were recorded with 1024 channels and measured at room tem-
perature employing MS2006 Mössbauer spectrometer based on virtual instrumentation technique53, 54
, operating
at a constant acceleration mode and equipped with a 57
Co(Rh) source. The acquired Mössbauer spectra were
processed (i.e., noise filtering and fitting) using the MossWinn software program55
. The isomer shift values were
referred against α-Fe foil sample at room temperature.
FESEM images were recorded on a Hitachi 6600 FEG microscope operating in the secondary electron mode
and using an accelerating voltage of 5 kV. Detailed particle size and morphological studies of solid samples were
performed by TEM on a JEOL JEM-2010 instrument equipped by a LaB6 cathode (accelerating voltage of 160 kV;
point-to-point resolution of 0.194 nm). A drop of high-purity ethanol was placed onto a holey carbon film sup-
ported by a copper-mesh TEM grid (SPI Supplies, USA) and air-dried at room temperature. The dimensions of
the microspheres were measured using ITEM software.
Nitrogen adsorption-desorption isotherms at 77.4 K were measured up to the saturation pressure of
nitrogen (molecular cross-sectional area 0.162 nm2
), and obtained by the static volumetric technique on an
Autosorb-iQ-C analyzer (Quantachrome). Prior to the measurements, samples were degassed at room temper-
ature for 12 h to reach pressure below 0.001 torr. Specific surface areas were calculated using the multipoint
BET (Brunauer-Emmett-Teller) model. The best fits were obtained using adsorption data in the relative pres-
sures of 0.08/0.25 (P/P0). The analysis and evaluations were performed with the ASiQwin 2.0 software package
(Quantachrome). For the reaction, 10 mL glass vial equipped with Teflon-lined cap was irradiated in a Monowave
300 single-mode microwave reactor (Anton Paar GmbH, Graz, Austria) having auto adjusting MW power to
maintain the reaction temperature.
The nitroarenes reduction products were analyzed using an Agilent 6820 GC equipped with an Agilent DB-5
capillary column (30 m × 0.32 mm, 0.5 m) under the operation parameters: inlet temperature of 100 °C, temper-
ature of flame ionization detector of 250 °C, temperature ramp of the oven from 100 to 250 °C at a rate of 10 °C
min−1
.
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Acknowledgements
The authors acknowledge the support of the Ministry of Education, Youth and Sports of the Czech Republic
(Project No. LO1305), and the Internal Grant of the Palacký University, Olomouc, Czech Republic (IGA_
PrF_2016_010). The authors also thank Ondrej Tomanec for FE-SEM and Ms. J. Straska for TEM analysis.