The document describes experiments on dehydrogenation of methylcyclohexane over Pt supported catalysts. Among Pt supported on various metal oxides (Pt/MO), Pt supported on lanthanum oxide (Pt/La2O3) showed the highest activity with a hydrogen evolution rate of 21.1 mmol/gmet/min. Pt supported on perovskites exhibited even higher activity and selectivity than Pt/MO catalysts. In particular, Pt supported on lanthanum-yttrium nickelate (Pt/La0.7Y0.3NiO3) gave the best performance with a hydrogen evolution rate of 45 mmol/gmet/min and nearly 100% selectivity towards dehydrogenation. The catalysts were
Magnetic Fe3O4@MgAl–LDH composite grafted with cobalt phthalocyanine as an ef...Pawan Kumar
Magnetically separable layered double hydroxide MgAl–LDH@Fe3O4 composite supported cobalt
phthalocyanine catalyst was synthesized and used for the aerobic oxidation of mercaptans to corresponding
disulfides under alkali free conditions. The catalyst exhibited excellent activity for the oxidation of
mercaptans using molecular oxygen as an oxidant which can be effectively recovered by using an external
magnetic field. In addition, the covalent immobilization of cobalt phthalocyanine to MgAl–LDH@Fe3O4
support prevents the leaching of the catalyst and improves its activity and stability
International Journal of Engineering and Science Invention (IJESI)inventionjournals
International Journal of Engineering and Science Invention (IJESI) is an international journal intended for professionals and researchers in all fields of computer science and electronics. IJESI publishes research articles and reviews within the whole field Engineering Science and Technology, new teaching methods, assessment, validation and the impact of new technologies and it will continue to provide information on the latest trends and developments in this ever-expanding subject. The publications of papers are selected through double peer reviewed to ensure originality, relevance, and readability. The articles published in our journal can be accessed online.
Using Tunisian Phosphate Rock and Her Converted Hydroxyapatite for Lead Remov...IJERA Editor
Natural and synthesis apatites represent a cost effective soil amendment, which can be used for in situ reduction of lead bioavailability and mobility. In our previous work, we selected Tunisian Phosphate Rock (TPR) and Hydroxyapatite (CaHAp) as promising minerals for the removal of lead from aqueous solutions. X-ray powder diffraction patterns (DRX), Infra Red (IR), Thermogravimetric analysis (TGA) and Scanning Electron Microscopy (SEM) were used to characterize TPR and CaHAp. CaHAp was prepared from TPR and employed for the removal of Pb2+ ions at different concentrations from aqueous solution to determine the adsorption properties of CaHAp and compare them with those of a TPR. The kinetic data obtained indicated that the adsorption performances of the adsorbents depended both on their specific surface area and crystallinity. Complexation of lead ion on the adsorbent surface favoured the dissolution of hydroxyapatites characterized by a Ca/Pb molar ratio of 1.69. The maximum adsorption capacity of CaHAp for Pb2+ ions at 25 °C was 1.806 mmol /g relative to 1.035 mmol /g for TPR at the same temperature. The higher capacity of CaHAp was explained in terms of its porosity and crystallinity. The Pb2+ ions sorption results could be modelled by the Langmuir and Freundlich isotherms. The simulations of adsorption isotherms of Pb2+ on CaHAp allow us to conclude that there is a good correlation between the experimental data and the Langmuir model. On TPR, we show a good correlation between the experimental data and the Langmuir and Freundlich model.
V mn-mcm-41 catalyst for the vapor phase oxidation of o-xylenesunitha81
The role of V and Mn incorporated mesoporous molecular sieves was
investigated for the vapor phase oxidation of o-xylene. Mesoporous monometallic
V-MCM-41 (Si/V = 25, 50, 75 and 100), Mn-MCM-41 (Si/Mn = 50) and bimetallic
V-Mn-MCM-41 (Si/(V ? Mn) = 100) molecular sieves were synthesized by
a direct hydrothermal (DHT) process and characterized by various techniques such
as X-ray diffraction, DRUV-Vis spectroscopy, EPR, and transmission electron
microscopy (TEM). From the DRUV-Vis and EPR spectral study, it was found that
most of the V species are present as vanadyl ions (VO2?) in the as-synthesized
catalysts and as highly dispersed V5? ions in tetrahedral coordination in the calcined
catalysts. The activity of the catalysts was measured and compared with each other
for the gas phase oxidation of o-xylene in the presence of atmospheric air as an
oxidant at 573 K. Among the various catalysts, V-MCM-41 with Si/V = 50
exhibited high activity towards production of phthalic anhydride under the experimental
condition. The correlation between the phthalic anhydride selectivity and
the physico-chemical characteristics of the catalyst was found. It is concluded that
V5? species present in the MCM-41 silica matrix are the active sites responsible for
the selective formation of phthalic anhydride during the vapor phase oxidation of
o-xylene.
Magnetic Fe3O4@MgAl–LDH composite grafted with cobalt phthalocyanine as an ef...Pawan Kumar
Magnetically separable layered double hydroxide MgAl–LDH@Fe3O4 composite supported cobalt
phthalocyanine catalyst was synthesized and used for the aerobic oxidation of mercaptans to corresponding
disulfides under alkali free conditions. The catalyst exhibited excellent activity for the oxidation of
mercaptans using molecular oxygen as an oxidant which can be effectively recovered by using an external
magnetic field. In addition, the covalent immobilization of cobalt phthalocyanine to MgAl–LDH@Fe3O4
support prevents the leaching of the catalyst and improves its activity and stability
International Journal of Engineering and Science Invention (IJESI)inventionjournals
International Journal of Engineering and Science Invention (IJESI) is an international journal intended for professionals and researchers in all fields of computer science and electronics. IJESI publishes research articles and reviews within the whole field Engineering Science and Technology, new teaching methods, assessment, validation and the impact of new technologies and it will continue to provide information on the latest trends and developments in this ever-expanding subject. The publications of papers are selected through double peer reviewed to ensure originality, relevance, and readability. The articles published in our journal can be accessed online.
Using Tunisian Phosphate Rock and Her Converted Hydroxyapatite for Lead Remov...IJERA Editor
Natural and synthesis apatites represent a cost effective soil amendment, which can be used for in situ reduction of lead bioavailability and mobility. In our previous work, we selected Tunisian Phosphate Rock (TPR) and Hydroxyapatite (CaHAp) as promising minerals for the removal of lead from aqueous solutions. X-ray powder diffraction patterns (DRX), Infra Red (IR), Thermogravimetric analysis (TGA) and Scanning Electron Microscopy (SEM) were used to characterize TPR and CaHAp. CaHAp was prepared from TPR and employed for the removal of Pb2+ ions at different concentrations from aqueous solution to determine the adsorption properties of CaHAp and compare them with those of a TPR. The kinetic data obtained indicated that the adsorption performances of the adsorbents depended both on their specific surface area and crystallinity. Complexation of lead ion on the adsorbent surface favoured the dissolution of hydroxyapatites characterized by a Ca/Pb molar ratio of 1.69. The maximum adsorption capacity of CaHAp for Pb2+ ions at 25 °C was 1.806 mmol /g relative to 1.035 mmol /g for TPR at the same temperature. The higher capacity of CaHAp was explained in terms of its porosity and crystallinity. The Pb2+ ions sorption results could be modelled by the Langmuir and Freundlich isotherms. The simulations of adsorption isotherms of Pb2+ on CaHAp allow us to conclude that there is a good correlation between the experimental data and the Langmuir model. On TPR, we show a good correlation between the experimental data and the Langmuir and Freundlich model.
V mn-mcm-41 catalyst for the vapor phase oxidation of o-xylenesunitha81
The role of V and Mn incorporated mesoporous molecular sieves was
investigated for the vapor phase oxidation of o-xylene. Mesoporous monometallic
V-MCM-41 (Si/V = 25, 50, 75 and 100), Mn-MCM-41 (Si/Mn = 50) and bimetallic
V-Mn-MCM-41 (Si/(V ? Mn) = 100) molecular sieves were synthesized by
a direct hydrothermal (DHT) process and characterized by various techniques such
as X-ray diffraction, DRUV-Vis spectroscopy, EPR, and transmission electron
microscopy (TEM). From the DRUV-Vis and EPR spectral study, it was found that
most of the V species are present as vanadyl ions (VO2?) in the as-synthesized
catalysts and as highly dispersed V5? ions in tetrahedral coordination in the calcined
catalysts. The activity of the catalysts was measured and compared with each other
for the gas phase oxidation of o-xylene in the presence of atmospheric air as an
oxidant at 573 K. Among the various catalysts, V-MCM-41 with Si/V = 50
exhibited high activity towards production of phthalic anhydride under the experimental
condition. The correlation between the phthalic anhydride selectivity and
the physico-chemical characteristics of the catalyst was found. It is concluded that
V5? species present in the MCM-41 silica matrix are the active sites responsible for
the selective formation of phthalic anhydride during the vapor phase oxidation of
o-xylene.
KINETICS, EQUILIBRIUM AND THERMODYNAMICS STUDIES ON BIOSORPTION OF HEAVY META...Drm Kapoor
Batch studies were conducted to assess biosorption potential of Aspergillus niger and Aspergillus flavus dead biomass, operated under various pH (5, 6 and 7), temperature (20, 30 and 40ºC) and initial metal concentration (300, 600 and 900ppm) conditions. The maximum sorption by A. flavus being a better adsorbent showed to be 257mg/g for Cr (III) at 40C leading to 85.6% biosorption. Metal uptake was preeminent at pH 6 and decreased at pH 7. Results revealed amplifying uptake in biosorption with the increase in temperature and initial metal concentration. Kinetics and equilibrium studies were carried out in which pseudo-second-order kinetic model and Langmuir adsorption isotherm best represented the biosorption with regression coefficient values > 0.982 respectively. The calculated thermodynamic parameters (∆G, ∆H and ∆S) showed that the biosorption of each of the metal ions on A. flavus was spontaneous, feasible and endothermic. A. flavus was efficient for removal of toxic metals.
Inhibitive properties, thermodynamic, kinetics and quantumAl Baha University
Inhibitive properties, thermodynamic, kinetics and quantum
chemical calculations of polydentate Schiff base compounds
as corrosion inhibitors for iron in acidic and alkaline media
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...IOSR Journals
Some transition metal ions Complexes with 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino]
pyrimidin-5-yl} methyl)-2,3,4-trimethoxybenzene were prepared and characterized by elemental analyses,
Infrared , magnetic moment, electronic spectra , mass spectra, X-ray powder diffraction, molar conductance
and thermal analysis (TGA). The complexes have general formulae [ML2.2H2O] {where M = Mn (II), Co (II), Ni
(II), Cu (II), Zn (II), Pd (II) and Pt (II). The coordination behavior of the metal ions towards to the investigated
Schiff base takes place through –C=N,-NH2 and –OH groups. The obtained C, H and N elemental analysis data
showed the Metal: Ligand ratio is 1:2 [M: L] ratio. The molar conductance data reveal that all the metal
complexes are non-electrolytic in nature. From the magnetic moments the complexes are paramagnetic except
Zn metal ion complexes have octahedral geometry with coordination number eight. The thermal behavior of
these complexes shows that, the hydrated complexes have loses two water molecules and immediately followed
by decomposition of the anions and ligand molecules in the second and third stage. The Schiff bases and metal
complexes show good activity against some bacteria. The antimicrobial results indicate that, the metal
complexes have better antimicrobial activity as compared to the prepared Schiff base.
Iron Doped Titania Nanostructures Synthesis, DFT modelling and Photocatalysisioneec
In this work, Fe-doped TiO2 nanoparticles ranging from a 0.2 to 1 weight % were grown from
the surface of graphene sheet templates containing –COOH functionalities using sol–gel
chemistry in a green solvent, a mixture of water/ethanol. The assemblies were characterized by a
variety of analytical techniques, with the coordination mechanism examined theoretically using
the density functional theory (DFT). Scanning electron microscopy and transmission electron
microscopy images showed excellent decoration of the Fe-doped TiO2 nanoparticles on the
surface of the graphene sheets >5 nm in diameter. The surface area and optical properties of the
Fe-doped photocatalysts were measured by BET, UV and PL spectrometry and compared to
non-graphene and pure TiO2 analogs, showing a plateau at 0.6% Fe. Interactions between
graphene and Fe-doped anatase TiO2 were also studied theoretically using the Vienna ab initio
Simulation Package based on DFT. Our first-principles theoretical investigations validated the
experimental findings, showing the strength in the physical and chemical adsorption between the
graphene and Fe-doped TiO2. The resulting assemblies were tested for photodegradation under
visible light using 17β-estradiol (E2) as a model compound, with all investigated catalysts
showing significant enhancements in photocatalytic activity in the degradation of E2.
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFE...Premier Publishers
In this paper, a novel copper oxide coated kaolinite was prepared as an adsorbent of Hg(II) ions from aqueous media. The materials used for this study were synthesized, characterised and the product tested for mercury ion removal using standard laboratory procedures. Reactivity and removal kinetic models derived from Freundlich isotherm were used to investigate contact time and pH effects on the coefficient of protonation and rate of mass transfer of Hg(II) ions to the reactive sites, Proton coefficient of 0.89 indicated a decrease in proton consumption function when compared with uncoated kaolinite. At the 12th h reaction time, a maximum adsorption capacity of 85% was achieved. Mass transfer rates of 0.9359h-1 and 0.0748h-1 for the first and second reaction phases indicated a reduction when compared with uncoated kaolinite. These changes may be ascribed to masking of reaction sites and exposed surface area of the Cu-Oxide coated kaolinite.
SYNTHESIS, SPECTRAL AND ANTIMICROBIAL ACTIVITY OF MIXED LIGAND COMPLEXES OFCo(II), Ni(II), Cu(II) and Zn(II) WITH 4-AMINOANTIPYRINE AND TRIBUTYLPHOSPHINE
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.
Synthesis and Crystal Structure of Anickel (II) and Zinc (II) Complex From 1,...IOSRJAC
:The title mononuclear nickel and zinc complexes, Ni(C11H9N4S3)2andZn(C11H9N4S3)2 .2(C3H7NO), were prepared by the reaction of Nickel(II) or Zinc(II)acetate with 1,5-bis[(2- thiophenyl)methylidene]thiocarbonohydrazide in a methanol solution. It features mono-deprotonated bisbidentate ligands, which coordinate to metal (II) ions by hydrazylN and thiocarbony lS atoms, yielding a tetracoordinated metal ions complexes. In Ni(II) complex the geometry around the metal ion is described as square planar. In the Zn(II) the metal atom shows severely tetrahedral distortion from anideal square-planar coordination geometry, as reflected by the dihedral angle between ZnN2and ZnS2 planes of 73.03(13)°. Two intramolecular hydrogen bonds are observed between the solvate dmf molecules and the coordinated ligands:N2—H2N…O1i and N6—H6N…O2 ii in this complex
The types of tissue culture can be grouped by the structures formed in culture.
Plantlets
Seedlings
Callus
Somatic EmbryogenesisPlantlet formationThis is the most common form of micropropagation. Uses a portion of the stem with one to several nodes
1. Axillary shoot formation Meristem culture Shoot culture
2. Adventitious shoot formation Diploid plant regenerationPseudocorms
Pseudocorms are the structures initiated after seed germination in orchids Haploid and triploid regeneration
Callus cultures are initiated from a small part of an organ or tissue segment called the explants on a growth supporting solidified nutrient medium under sterile conditions. Any part of the plant organ or tissues may be used as the explants.Plant tissue culture is a collection of techniques used to maintain or grow plant cells, tissues or organs under sterile conditions on a nutrient culture medium of known composition. Plant tissue culture is widely used to produce clones of a plant in a method known as micropropagation.Tissue culture commonly refers to the culture of animal cells and tissues, with the more specific term plant tissue culture being used for plants.Plant Tissue Culture products include Murashige and Skoog media, plant growth regulators, plant growth hormones, plant transformation systems,
KINETICS, EQUILIBRIUM AND THERMODYNAMICS STUDIES ON BIOSORPTION OF HEAVY META...Drm Kapoor
Batch studies were conducted to assess biosorption potential of Aspergillus niger and Aspergillus flavus dead biomass, operated under various pH (5, 6 and 7), temperature (20, 30 and 40ºC) and initial metal concentration (300, 600 and 900ppm) conditions. The maximum sorption by A. flavus being a better adsorbent showed to be 257mg/g for Cr (III) at 40C leading to 85.6% biosorption. Metal uptake was preeminent at pH 6 and decreased at pH 7. Results revealed amplifying uptake in biosorption with the increase in temperature and initial metal concentration. Kinetics and equilibrium studies were carried out in which pseudo-second-order kinetic model and Langmuir adsorption isotherm best represented the biosorption with regression coefficient values > 0.982 respectively. The calculated thermodynamic parameters (∆G, ∆H and ∆S) showed that the biosorption of each of the metal ions on A. flavus was spontaneous, feasible and endothermic. A. flavus was efficient for removal of toxic metals.
Inhibitive properties, thermodynamic, kinetics and quantumAl Baha University
Inhibitive properties, thermodynamic, kinetics and quantum
chemical calculations of polydentate Schiff base compounds
as corrosion inhibitors for iron in acidic and alkaline media
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...IOSR Journals
Some transition metal ions Complexes with 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino]
pyrimidin-5-yl} methyl)-2,3,4-trimethoxybenzene were prepared and characterized by elemental analyses,
Infrared , magnetic moment, electronic spectra , mass spectra, X-ray powder diffraction, molar conductance
and thermal analysis (TGA). The complexes have general formulae [ML2.2H2O] {where M = Mn (II), Co (II), Ni
(II), Cu (II), Zn (II), Pd (II) and Pt (II). The coordination behavior of the metal ions towards to the investigated
Schiff base takes place through –C=N,-NH2 and –OH groups. The obtained C, H and N elemental analysis data
showed the Metal: Ligand ratio is 1:2 [M: L] ratio. The molar conductance data reveal that all the metal
complexes are non-electrolytic in nature. From the magnetic moments the complexes are paramagnetic except
Zn metal ion complexes have octahedral geometry with coordination number eight. The thermal behavior of
these complexes shows that, the hydrated complexes have loses two water molecules and immediately followed
by decomposition of the anions and ligand molecules in the second and third stage. The Schiff bases and metal
complexes show good activity against some bacteria. The antimicrobial results indicate that, the metal
complexes have better antimicrobial activity as compared to the prepared Schiff base.
Iron Doped Titania Nanostructures Synthesis, DFT modelling and Photocatalysisioneec
In this work, Fe-doped TiO2 nanoparticles ranging from a 0.2 to 1 weight % were grown from
the surface of graphene sheet templates containing –COOH functionalities using sol–gel
chemistry in a green solvent, a mixture of water/ethanol. The assemblies were characterized by a
variety of analytical techniques, with the coordination mechanism examined theoretically using
the density functional theory (DFT). Scanning electron microscopy and transmission electron
microscopy images showed excellent decoration of the Fe-doped TiO2 nanoparticles on the
surface of the graphene sheets >5 nm in diameter. The surface area and optical properties of the
Fe-doped photocatalysts were measured by BET, UV and PL spectrometry and compared to
non-graphene and pure TiO2 analogs, showing a plateau at 0.6% Fe. Interactions between
graphene and Fe-doped anatase TiO2 were also studied theoretically using the Vienna ab initio
Simulation Package based on DFT. Our first-principles theoretical investigations validated the
experimental findings, showing the strength in the physical and chemical adsorption between the
graphene and Fe-doped TiO2. The resulting assemblies were tested for photodegradation under
visible light using 17β-estradiol (E2) as a model compound, with all investigated catalysts
showing significant enhancements in photocatalytic activity in the degradation of E2.
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFE...Premier Publishers
In this paper, a novel copper oxide coated kaolinite was prepared as an adsorbent of Hg(II) ions from aqueous media. The materials used for this study were synthesized, characterised and the product tested for mercury ion removal using standard laboratory procedures. Reactivity and removal kinetic models derived from Freundlich isotherm were used to investigate contact time and pH effects on the coefficient of protonation and rate of mass transfer of Hg(II) ions to the reactive sites, Proton coefficient of 0.89 indicated a decrease in proton consumption function when compared with uncoated kaolinite. At the 12th h reaction time, a maximum adsorption capacity of 85% was achieved. Mass transfer rates of 0.9359h-1 and 0.0748h-1 for the first and second reaction phases indicated a reduction when compared with uncoated kaolinite. These changes may be ascribed to masking of reaction sites and exposed surface area of the Cu-Oxide coated kaolinite.
SYNTHESIS, SPECTRAL AND ANTIMICROBIAL ACTIVITY OF MIXED LIGAND COMPLEXES OFCo(II), Ni(II), Cu(II) and Zn(II) WITH 4-AMINOANTIPYRINE AND TRIBUTYLPHOSPHINE
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.
Synthesis and Crystal Structure of Anickel (II) and Zinc (II) Complex From 1,...IOSRJAC
:The title mononuclear nickel and zinc complexes, Ni(C11H9N4S3)2andZn(C11H9N4S3)2 .2(C3H7NO), were prepared by the reaction of Nickel(II) or Zinc(II)acetate with 1,5-bis[(2- thiophenyl)methylidene]thiocarbonohydrazide in a methanol solution. It features mono-deprotonated bisbidentate ligands, which coordinate to metal (II) ions by hydrazylN and thiocarbony lS atoms, yielding a tetracoordinated metal ions complexes. In Ni(II) complex the geometry around the metal ion is described as square planar. In the Zn(II) the metal atom shows severely tetrahedral distortion from anideal square-planar coordination geometry, as reflected by the dihedral angle between ZnN2and ZnS2 planes of 73.03(13)°. Two intramolecular hydrogen bonds are observed between the solvate dmf molecules and the coordinated ligands:N2—H2N…O1i and N6—H6N…O2 ii in this complex
The types of tissue culture can be grouped by the structures formed in culture.
Plantlets
Seedlings
Callus
Somatic EmbryogenesisPlantlet formationThis is the most common form of micropropagation. Uses a portion of the stem with one to several nodes
1. Axillary shoot formation Meristem culture Shoot culture
2. Adventitious shoot formation Diploid plant regenerationPseudocorms
Pseudocorms are the structures initiated after seed germination in orchids Haploid and triploid regeneration
Callus cultures are initiated from a small part of an organ or tissue segment called the explants on a growth supporting solidified nutrient medium under sterile conditions. Any part of the plant organ or tissues may be used as the explants.Plant tissue culture is a collection of techniques used to maintain or grow plant cells, tissues or organs under sterile conditions on a nutrient culture medium of known composition. Plant tissue culture is widely used to produce clones of a plant in a method known as micropropagation.Tissue culture commonly refers to the culture of animal cells and tissues, with the more specific term plant tissue culture being used for plants.Plant Tissue Culture products include Murashige and Skoog media, plant growth regulators, plant growth hormones, plant transformation systems,
unani or Unani medicine (Urdu: طب یونانی tibb yūnānī) is the term for Perso-Arabic traditional medicine, practiced in Mughal India and in Muslim culture in South Asia and modern day Central Asia. The term is derived from Arabic Yūnānī "Greek", as the Perso-Arabic system of medicine was in turn based on the teachings of the Greek physicians Hippocrates and Galen.The medical tradition of medieval Islam was introduced to India by the 13th century with the establishment of the Delhi Sultanate and it took its own course of development during the Mughal Empire , influenced by Indian medical teachings of Sushruta and Charaka.
Electrooxidation of methanol on carbon supported pt ru nanocatalysts prepared...suresh899
Carbon Supported PtRu nanocatalysts have been prepared by simple impregnation reduction method in which Pt and Ru precursors are reduced by ethanol under reflux conditions for different reaction times. The prepared nanocatalysts were characterized by means of XRD, EDAX, ICP-AAS, FESEM and TEM. XRD analyses showed that all nanocatalysts exhibited f.c.c crystal structure, the structure characteristic for pure Pt, except for that reduced at prolonged reaction time of 4h which showed the presence of characteristic peak for Ru metal. The lattice constant calculations indicate that all catalysts are present in unalloyed phase and the average particle size as determined by TEM was in the range of 3.7 nm. The electrocatalytic activities and stability for the prepared nanocatalysts methanol electro-oxidation reaction (MOR) were studied by cyclic voltammetry. The catalysts prepared at 2h reduction time showed higher electrocatalytic activity in terms of mass specific activity and good stability over potential sweep for 100 cycles for methanol electro-oxidation. The results showed that the prepared nanocatalysts are considered as promising electrode catalyst (anode catalyst) for electro-oxidation of methanol in direct methanol fuel cells.
Nickel and cobalt transfigured natural clay: a green catalyst for low-tempera...Devika Laishram
Soot particulates in engine exhausts pose a severe threat to the environment and human health – causing cancer, affecting the heart and lungs and drives metal processes. This study proposes a practical,
real-world application of transition metal modified natural clay as an environmentally benign, low-cost,
green catalyst for soot oxidation. Ni and Co (NC-Clay) incorporated natural clay catalysts were prepared
by a simple wet impregnation method and meticulously characterized by different characterization
techniques. The catalyst exhibited higher H2 absorption at a lower temperature with similar trends as
observed in O2 TPD that indicated a remarkable redox property, which is useful for applications as a
catalyst in soot oxidation. Excellent catalytic activity with a very low T50 of 358 1C was observed and can
be accredited to the improved surface oxygen vacancies and thermal stability by the metal modification
of clay
Electrochemical study of anatase TiO2 in aqueous sodium-ion electrolytesRatnakaram Venkata Nadh
In this paper, a basic electro-analytical study on the behavior of anatase TiO2 in aqueous NaOH has been presented using cyclic voltammetry technique (CV). The study has explored the possibility of using TiO2 as anode material for ARSBs in presence of 5 M NaOH aqueous electrolyte. CV profiles show that anatase TiO2 exhibits reversible sodium ion insertion/de-insertion reactions. CV studies of TiO2 anode in aqueous sodium electrolytes at different scan rate shows that the Na+ ion insertion reaction at the electrode is diffusion controlled with a resistive behavior. Proton insertion from aqueous sodium electrolytes into TiO2 cannot be ruled out. To confirm the ion inserted and de-inserted, CV studies are done at different concentration of NaOH and it is found that at lower concentrations of NaOH, proton insertion process competes with Na+ ion insertion process and as the concentration increases, the Na+ ion insertion process becomes the predominant electrode reaction making it suitable anode materials for aqueous sodium batteries in 5 M NaOH.
Study of the Influence of Nickel Content and Reaction Temperature on Glycerol...IJRESJOURNAL
ABSTRACT: La2O3-SiO2-supported nickel catalysts were evaluated in glycerol steam reforming. The samples (30wt% La and 5, 10 and 15wt% of Ni on 70wt% commercial SiO2), prepared by the simultaneous impregnation method, were characterized by EDX, nitrogen physisorption, XRD, in-situ XRD, XANES and TPR. The analyses revealed NiO species weakly interact with the support and the different metallic surface areas of the catalysts. Catalytic tests were performed in a fixed bed reactor at 600oC and 15Ni catalyst, which showed the best performance, was also evaluated at 500oC and 700oC. According to the results, the Ni content on the catalyst surface interferes in the distribution of gaseous products H2, CO, CO2 and CH4. The increase in the Ni content increases the carbon formation during reaction. The reaction temperature affected the catalytic performance and the best results were obtained with the 15Ni catalyst at 600oC, which was also tested for 20 hours for the analysis of its stability.
Calix Assisted Palladium Nanocatalyst: A Reviewijtsrd
The article reviews recent advances in c c cross coupling area as calix protected palladium nanocatalyst. The extensive use of palladium complex as catalyst in the calix chemistry is newly emerging field which deals with Suzuki, Heck, Stille and Sonogashira cross coupling reactions. The brief survey of cross coupling reactions also includes yield, catalyst loading, Recyclability. Keyur D. Bhatt | Krunal Modi "Calix Assisted Palladium Nanocatalyst: A Review" Published in International Journal of Trend in Scientific Research and Development (ijtsrd), ISSN: 2456-6470, Volume-4 | Issue-1 , December 2019, URL: https://www.ijtsrd.com/papers/ijtsrd29654.pdf Paper URL: https://www.ijtsrd.com/chemistry/other/29654/calix-assisted-palladium-nanocatalyst-a-review/keyur-d-bhatt
Nanocomposite ion exchanger, poly-o-toluidine/Multiwalled Carbon Nanotubes/Sn(IV)
tungstate (POT/MWCNT/ST) was chemically synthesized by mixing of organic polymers i.e. o-toluidine into
inorganic gels of Sn(IV) tungstate (ST) and Multiwalled Carbon Nanotubes (MWCNT) with different mixing
volume ratios. Ion-exchange kinetics for few divalent metal ions was evaluated by particle diffusion-controlled
and ion-exchange phenomenon at four different temperatures. The particle diffusion mechanism is confirmed by
the linear τ (dimensionless time parameter) Vs t (time) plots. The exchange processes were controlled by the
diffusion within the exchanger particle for the systems studies. Some physical parameters like self-diffusion
coefficient (D0), energy of activation (Ea) and entropy of activation (ΔS0) have been evaluated under conditions
favouring a particle diffusion-controlled mechanism.
1. Efficient hydrogen supply through catalytic dehydrogenation
of methylcyclohexane over Pt/metal oxide catalysts
Anshu A. Shukla a
, Priti V. Gosavi a
, Jayshri V. Pande a
, Vanama P. Kumar b
,
Komandur V.R. Chary b
, Rajesh B. Biniwale a,
*
a
Environmental Materials Unit, National Environmental Engineering Research Institute (NEERI), Council of Scientific and Industrial Research,
Nehru Marg, Nagpur 440020, India
b
Indian Institute of Chemical Technology (IICT), Council of Scientific and Industrial Research, Hyderabad 500 607, India
a r t i c l e i n f o
Article history:
Received 14 October 2009
Received in revised form
1 February 2010
Accepted 2 February 2010
Available online 19 March 2010
Keywords:
Hydrogen delivery
Dehydrogenation
Pt over metal oxide
Perovskite
Methylcyclohexane
Pulse spray reactor
a b s t r a c t
This paper describes the results of experiments on dehydrogenation of methylcyclohexane
over Pt supported on metal oxides (Pt/MO) and Pt supported on perovskite (Pt/Per) catalysts.
The reaction is being considered as a means for delivery of hydrogen to fueling stations in
the form of more easily transportable methylcyclohexane. Among Pt/MO catalysts, the best
activity as determined by the hydrogen evolution rate was observed over Pt/La2O3 catalyst
at 21.1 mmol/gmet/min. Perovskite-supported catalysts exhibited relatively higher activity
and selectivity, with Pt/La0.7Y0.3NiO3 giving the best performance. This Pt/Per catalyst had
an activity of ca 45 mmol/gmet/min with nearly 100% selectivity towards dehydrogenation.
The catalysts were characterized using XRD, CO-chemisorption and SEM-EDXA techniques.
The present study reports catalysts that minimize the use of Pt and explores tailoring the
properties of the perovskite structure.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
1. Introduction
Developing hydrogen storage media having relatively high
capacity on weight and volume basis is one of the major
challenges as the hydrogen economy is facing today for its
real launch. The various materials being pursued for
hydrogen storage include metal hydrides, alanates, boranes,
carbon nano-tubes and chemical hydrides. Organic liquid
hydrides such as cyclohexane, methylcylohexane and dec-
alin have relatively high hydrogen content, 6–8% on weight
basis and ca. 60–62 kg/m3
on volume basis [1–4]. Due to
high boiling points, liquid organic hydrides provide poten-
tial media for transport of hydrogen using simple transport
equipment such as Lorries [1,5–10]. Additionally, the
advantages of using the cycloalkanes as a hydrogen carrier
include the supply of hydrogen without carbon-monoxide
and the recyclable aromatic products [1–3,5–7,11–15].
Accordingly, catalytic dehydrogenation of cycloalkanes has
been reported in several studies as an option for delivery of
hydrogen [1–3,16].
Pt based catalysts are the most widely reported catalysts
for dehydrogenation of cycloalkanes [1–3,13]. However, from
economic point of view there is a specific interest to minimize
the use of Pt [1–3,17]. We have earlier reported Ni/C as efficient
catalysts for dehydrogenation of cyclohexane and discussed
synergistic effect of addition of a small amount of Pt to Ni–Pt/C
* Corresponding author. Tel.: þ91 712 2249885x410, þ91 9822745768 (mobile); fax: þ91 712 2249900.
E-mail address: rb_biniwale@neeri.res.in (R.B. Biniwale).
Available at www.sciencedirect.com
journal homepage: www.elsevier.com/locate/he
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 6
0360-3199/$ – see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.02.014
2. catalysts [2]. It has been reported in the literature that addition
of metal oxide results in promoting activity of Pt catalysts [13].
Metal oxides promote the activity and selectivity of Pt cata-
lysts through strong metal–support interaction [17].
Mixed metal oxides such as perovskites, having definite
chemical structure, could be good candidates for supporting
Pt. The ABO3 type perovskite oxides are being used in various
applications due to its tailoring properties. The substitution at
A or B site with various elements creates valences and
vacancies, which are responsible for activity in different
applications [13]. For example, ferromagnetic nature of Ni
enhances magnetic moment at surface of its bulk which helps
to reduce magnetic ordering of Ni. This helps in dehydroge-
nation reaction mechanism [18]. It is reported by Pernifguez
et al. [17] that when a perovskite LaNiO3 is used in reducing
atmosphere the Ni migrate from LaNiO3 and forms Ni metallic
particles resulting in Ni/La2O3 phase. Re-oxidation results into
recuperation of the LaNiO3 Qiao and Bi [20] also reported using
XPS analysis of LaNiO3 and Pt/LaNiO3 that Ni exists in two
oxidation states Ni3þ
and Ni2þ
. They have further investigated
the effect of presence of Pt on reducibility of Ni in perovskite
and concluded that the Pt do not interfere with reducibility of
Ni. The presence of Ni along with Pt on the surface of catalyst
promotes formation of more active sites for dehydrogenation.
The presence of small amount of Pt inside the perovskite
structure or as co-catalyst, promotes the activity of
perovskite.
In this work, platinum promoted metal oxides were
studied as catalysts for dehydrogenation of methylcyclohex-
ane. The aim of this study is to find better support for plat-
inum in terms of improved catalytic activity and selectivity of
the catalyst. Selected metal oxides from transition, lantha-
nides, and metalloids series were used to support Pt. With
a view to improve activity, we have used perovskite with La at
A-site and Ni at B-site as support for Pt. Further, the perovskite
was modified by partial substitution of Y to La at A-site.
2. Materials and methods
2.1. Synthesis and characterization
Commercial metal-oxides namely La2O3, ZrO2, TiO2, CeO2,
Fe2O3, Al2O3 and MnO2 were used as supports for Pt catalyst.
Platinum was loaded by wet impregnation method using PtCl4
solution.
Perovskites, LaNiO3 and La0.7Y0.3NiO3 were synthesized
using co-precipitation method. In synthesis of LaNiO3,
lanthanum nitrate hexa hydrate solution (HIMEDIA, India)
was added to nickel nitrate solution (MERCK, India) in stoi-
chiometric ratio. The mixed nitrate solution was precipitated
in 50% ammonia solution. Resultant solution was stirred for
1 h and complete precipitation of nitrate solution was ensured
by adding excess of ammonia. Precipitate was allowed to
stand for 24 h, filtered and dried in oven at 110
C for 6 h. The
resultant hydroxide precursor was calcined at 800
C for 12 h
following a specific heating cycle. Similarly, La0.7Y0.3NiO3 was
synthesized using respective nitrates in required stoichio-
metric proportion. Further, Pt/Per catalysts were prepared by
wet impregnation method.
The catalysts were characterized using powder X-ray
diffraction (XRD, make RIGAKU, Miniflex II X-RAY Diffrac-
tometer), scanning electron microscopy-electron diffraction
X-ray analysis (SEM/EDXA, make JEOL 2300) and CO-
chemisorption techniques.
2.2. Experimental methods
The details of experimental setup are depicted in Fig. 1. The
experiments for catalytic dehydrogenation of methyl-
cyclohexane were carried out using a spray-pulsed reactor.
Atomized spray of reactant was fed to the reactor in pulsed
injection mode using a fine nozzle fitted at the top of the
reactor. A frequency generator was used to control the pulse
injection frequency and pulse width. The pre-treatment of
catalyst surface was performed using nitrogen flow at 300
C
with flow rate of 100 mL/min. The catalyst activation was
performed in the flow of hydrogen with the flow rate of
75 mL/min at 400
C following a defined heating cycle. All the
reactions were performed at atmospheric pressure under
nitrogen flow. In each experiment about 0.3 g of catalyst was
used. Pulse injection frequency and pulse width was kept
constant as 0.33 Hz (pulse injection of methylcyclohexane at
every 3 s) and 10 ms respectively. The temperature of the
surface of the catalyst was maintained at 350
C by a PID
temperature controller. The product from the reaction was
separated using a condenser to condense toluene and
unreacted methylcyclohexane. The gaseous products from
reactor were continuously monitored by using a TCD-GC
(SHIMADZU, with porapak-Q column, 3 m).
3. Results and discussion
3.1. Characterization of catalyst
All the catalysts were characterized using XRD method. The
commercial metal oxides (La2O3, Al2O3, CeO2, MnO2, TiO2,
Fe2O3 and ZrO2) were found to be crystalline in nature. The
XRD patterns for 1 wt% Pt/LaNiO3, LaNiO3, 1 wt% Pt/La0.7Y0.3-
NiO3 and La0.7Y0.3NiO3 catalysts are depicted in Fig. 2. Presence
of platinum in case of 1 wt% Pt/LaNiO3 and 1 wt% Pt/
La0.7Y0.3NiO3 was confirmed by XRD peak corresponding to Pt
(JCPDS card no. 87-0640). The elemental composition of the
catalyst was confirmed by SEM/EDXA analysis (Figs. 3 and 4).
In addition to XRD, EDXA data also confirms the presence of Pt
on supports. The elemental compositions of 1 wt% Pt/LaNiO3
and 1 wt% Pt/La0.7Y0.3NiO3 are reported in Table 1.
3.2. Dehydrogenation of methylcyclohexane over
different Pt/MO catalysts
The rates of hydrogen evolution observed during dehydroge-
nation of methylcyclohexane over various Pt/MO type cata-
lysts are depicted in Fig. 5. Although, Pt loading was equal i.e.
3 wt% on each metal oxide support namely, La2O3, Al2O3,
CeO2, MnO2, TiO2, Fe2O3 and ZrO2 the catalysts exhibited
different catalytic activity in terms of hydrogen evolution
rates. This may be because of difference in their surface area
and platinum dispersion over the supports. The supports used
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 6 4021
3. for Pt can be ranked according to hydrogen evolution rate
(at 90 min) observed for each Pt/MO catalysts as follows;
La2O3 TiO2 Al2O3 MnO2 Fe2O3 ZrO2 CeO2
At 90 min from the start of the reaction, the rate of hydrogen
evolution during dehydrogenation of methylcyclohexane over
3 wt% Pt/La2O3 catalyst was 21.1 mmol/gmet/min. The reaction
over two catalysts 3 wt% Pt/TiO2 and 3 wt% Pt/Al2O3 exhibited
nearly the same hydrogen evolution rates of 9.7 and 7.6 mmol/
gmet/min respectively at 90 min. However, the trend for
hydrogen evolution rates in case of 3 wt% Pt/La2O3 and 3 wt%
Pt/Al2O3 catalysts was similar. The catalytic activity as
20 40 60 80
2θ
Intensity(a.u)
(d)
(c)
(b)
(a)
Fig. 2 – XRD patterns for various catalysts (a) 1 wt%
Pt/LaNiO3, (b) LaNiO3, (c) 1 wt% Pt/La0.7Y0.3NiO3 and
(d) La0.7Y0.3NiO3.
Fig. 3 – SEM and EDXA pattern of catalyst 1 wt% Pt/LaNiO3
(a) Scanning Electron Micrographs for 1 wt% Pt/LaNiO3
catalysts and (b) EDXA pattern for 1 wt% Pt/LaNiO3
catalysts.
0-200 cc/min
12MPa
N2
C7H14
Nozzle
MFC
Condenser
GC
(TCD)
Reactant
Spray
Catalyst TC 1
Fig. 1 – Schematic of experimental setup with spray-pulsed reactor.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 64022
4. determined by hydrogen evolution rates using 3 wt% Pt/MnO2,
3 wt% Pt/Fe2O3, 3 wt% Pt/ZrO2 and 3 wt% Pt/CeO2 catalysts was
observed as 3.7, 3.97, 1.5 and 0.89 mmol/gmet/min respectively
at 90 min. During first 5 min from the start of the reaction
hydrogen evolution rates using 3 wt% Pt/La2O3 and 3 wt% Pt/
TiO2 catalysts were similar. While the hydrogen evolution rate
over 3 wt% Pt/Al2O3 was relatively low.
Accordingly, among the various Pt/MO catalysts used in
this study, 3 wt% Pt/La2O3 was found to be most active for
dehydrogenation of methylcyclohexane. Therefore, La2O3
may be the best support for Pt under the conditions used in
this study.
The trends of activity observed for different catalysts can
be explained based on active particle diameter of Pt and ability
of support to keep Pt in reduced state. The active particle
diameter of Pt supported on various metal oxides was
estimated by CO-chemisorption method. Table 2 lists the
hydrogen evolution rates and particle diameters of Pt for
various Pt/MO catalysts. The active particle diameters of Pt in
case of 3 wt% Pt/La2O3 and 3 wt% Pt/MnO2 were estimated as
9.8 and 9.2 nm respectively. The activity of 3 wt% Pt/MnO2
catalyst in terms of hydrogen evolution rate was less than the
former. This indicates that in addition to the active particle
diameter of Pt, metal–support interaction has an effect on
catalytic activity. In the case of catalysts namely 3 wt% Pt/
Fe2O3, 3 wt% Pt/CeO2 and 3 wt% Pt/ZrO2 the lower catalytic
activity may be due to weak metal–support interaction
wherein Pt may be in higher oxidation state [12]. When elec-
tronic configuration of La (5d1
6s2
) is considered, in La2O3, one
electron from 5d1
orbital is available for reducing Pt. This leads
to more active sites on the catalyst surface. Moreover, the
dehydrogenation reaction is a reversible reaction wherein it is
important to desorb hydrogen and limit the reverse rate of
reaction. Reduced state of Pt may favor hydrogen spillover
phenomena over catalyst surface. The role of the support for
metal catalysts has been explained in the literature for
hydrogen spillover with migration of hydrogen atom over
supports such as carbon and metal oxides. A hydrogen spill-
over phenomenon in metal oxides is well studied with mate-
rials such as MoO3 and WO3 [19]. According to a report, in
metal oxides hydrogen spillover is favorable because of the
thermodynamic and small energy barrier [18]. This can be
attributed to easy migration of H atoms from catalyst to
support and subsequent proton diffusion in the bulk. In case
of carbon based materials energy barrier is low however,
Fig. 4 – SEM and EDXA pattern of catalyst 1 wt% Pt/
La0.7Y0.3NiO3 (a) Scanning Electron Micrographs 1 wt%
Pt/La0.7Y0.3NiO3 and (b) EDXA pattern for 1 wt% Pt/
La0.7Y0.3NiO3.
Table 1 – Elemental analysis of catalysts using SEM-EDXA.
Composition Mass% Atomic%
Catalyst La Ni O Pt Y La Ni O Pt Y
1 wt% Pt/LaNiO3 84.6 7.47 7.24 0.64 – 51.16 10.62 37.95 0.27 –
1 wt% Pt/La0.7Y0.3NiO3 72.3 6.16 8.83 1.33 11.3 39.73 8.0 42.03 0.52 9.72
0
5
10
15
20
30 60 90
Time (min)
Hydrogenevolution(mmol/gmet/min)
(a)
(f)
(g)
(e)
(d)
(c)
(b)
Fig. 5 – Hydrogen evolution rates over various catalysts at
350 8C. (a) 3 wt% Pt/La2O3, (b) 3 wt% Pt/TiO2, (c) 3 wt% Pt/
Al2O3, (d) 3 wt% Pt/MnO2, (e) 3 wt% Pt/Fe2O3, (f) 3 wt% Pt/
ZrO2 and (g) 3 wt% Pt/CeO2.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 6 4023
5. proton diffusion would be energetically difficult if H atoms get
chemisorbed. The role of metal oxide support and hydrogen
spillover effect is also evident form improved kinetic rate
constant for Pt/La2O3 as compared to Pt/AC. The reported
value for kinetic rate constant for dehydrogenation of meth-
ylcyclohexane over Pt/AC [6] is 1.16 per min (k ¼ 6.5 mmol/
min, volume of reactant 0.7 mL) at 300
C using alternate wet-
dry conditions. The Pt/La2O3 catalyst in the present study has
exhibited better rate constant of 6.3 per min indicating better
hydrogen spillover and strong role of support.
The active particle diameters of Pt in case of 3 wt% Pt/Al2O3
and 3 wt% Pt/TiO2 catalysts were estimated as 4.81 nm and
2.07 nm respectively. The active particle diameter of Pt in
3 wt% Pt/Al2O3 was larger but the catalyst exhibited lower
activity with relatively low hydrogen evolution rates. As
reported for TiO2, when it interacts with noble metals such as
Rh and Pt, It has tendency to reduce Ti4þ
to Ti3þ
[1,5,12,13]. Ti3þ
ions are fixed in surface of lattices of anatase titania.
A temperature of 400
C maintained during pre-treatment of
catalysts was favorable for anatase form of titania [15]. Thus,
the hydrogen evolution rate was found to be relatively better
with 3 wt% Pt/TiO2 than 3 wt% Pt/Al2O3.
Accordingly, choice of support, due to difference in metal–
support interaction, has effect on dehydrogenation of meth-
ylcyclohexane. Fig. 5 amply depicts the stability of catalyst up
to 90 min; leading to the conclusion that 3 wt% Pt/La2O3 has
relatively better stability compared to other Pt/MO catalysts in
this study.
The kinetics of reaction can be well explained by differ-
ential equation, in terms of rate law as follows:
ln
À
dCA
dt
¼ klnCn
A
where, CA is the concentration of hydrogen (mmol/min), k is
rate constant (per min). The reaction of dehydrogenation of
methylcyclohexane is of zero order with rate constants as 6.3
per min for 1 wt% Pt/La2O3. Thus, reactions are not concen-
tration dependant.
3.3. Selectivity towards hydrogen formation
The mechanism of dehydrogenation of methylcyclohexane
may be similar to reported mechanism for dehydrogenation of
cyclohexane. This involves the adsorption of methyl-
cyclohexane, with either simultaneous or rapid subsequent
dissociation of hydrogen atoms. The aromatic structure
formed is bonded through pi–electron interaction with metal
d-orbitals. The adsorbed hydrogen atoms then form mole-
cules and desorbs from the surface [9]. Toluene if not desorbed
Table 2 – Hydrogen evolution rate of all catalysts and their particle size.
Sr No. Catalysts Particle size (nm) Metallic surface area
as estimated by
CO-chemisorption
(m2
/g)
Hydrogen Evolution
rate at 350
C at
90 min in
(mmol/gmet/min)
1 3 wt% Pt/La2O3 9.81 0.85 21.11
2 3 wt% Pt/TiO2 2.07 4.04 9.7
3 3 wt% Pt/Al2O3 4.84 1.74 7.6
4 3 wt% Pt/Fe2O3 3.36 2.49 3.97
5 3 wt% Pt/MnO2 9.23 0.90 3.7
6 3 wt% Pt/ZrO2 2.87 2.91 1.5
7 3 wt% Pt/CeO2 2.67 3.13 0.8
8 1 wt% Pt/La2O3 9.94a
– 24.08
9 1 wt% Pt/LaNiO3 5.15a
– 17.79
10 1 wt% Pt/La0.7Y0.3NiO3 2.53a
– 45.76
a The particle size have been calculated using Scherer’s formula from XRD pattern.
Table 3 – Catalytic activity of various catalysts for
dehydrogenation of methylcyclohexane at 350 8C at
150 min.
Sr
No.
Catalysts H2 evolution
(mmol/gmet/min)
Methane formation
(mmol/min)
1. 1 wt% Pt/
La2O3
12.47 0.0009
2. 1 wt% Pt/
LaNiO3
30.30 0.0020
3. 1 wt% Pt/
La0.7Y0.3NiO3
45.26 BDLa
a BDL ¼ Beyond detectable limit by gas chromatograph.
0.00
0.01
0.01
0.02
0.02
0.03
0.03
0.04
0.04
0.05
A B C D
Catalysts
Products(mmol/min)
CH4
C7H8
C6H6
Fig. 6 – Rate of various products at 90 min over different
catalysts (A) 1 wt% Pt/La2O3, (B) 1 wt% Pt/LaNiO3, (C)
La0.7Y0.3NiO3, (D) 1 wt% Pt/La0.7Y0.3NiO3. Rate of hydrogen
production is not shown.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 64024
6. quickly then undergoes further dissociation. Although the
various metal oxides as discussed above are good supports for
Pt to design dehydrogenation catalysts, selectivity towards
hydrogen formation is an important issue. Along with
hydrogen, methane was observed in the product gas during
reaction over a few catalysts, indicating hydrogenolysis
reaction. It is reported that on well dispersed Pt catalysts
dehydrogenation reaction prevails whereas relatively higher
grain size leads to hydrogenolysis reaction. Methane forma-
tion was observed for catalysts, 3 wt% Pt/Al2O3, 3 wt% Pt/
MnO2, 3 wt% Pt/Fe2O3 and 3 wt% Pt/La2O3. No methane
formation was observed over 3 wt% Pt/TiO2, 3 wt% Pt/ZrO2 and
3 wt% Pt/CeO2 catalysts. It is evident that the La2O3 exhibits
higher activity and stability; however, it has relatively low
selectivity towards dehydrogenation reaction. In this study
when metal surface areas for various catalysts were compared
no direct correlation was found with catalytic activity. This
indicates that metal support interaction has major effect on
catalytic activity. When considering same support (same
metal oxide) higher dispersion may result into better activity.
3.4. Improving selectivity towards dehydrogenation
reaction
In order to improve the selectivity and stability of Pt/La2O3 we
have used two different approaches namely, reducing the Pt
loading from 3 wt% to 1 wt% over La2O3 and use of LaNiO3
perovskite instead of La2O3 as a support. Reducing Pt loading
may improve the dispersion of Pt on support and therefore
may exhibit better selectivity towards dehydrogenation reac-
tion. In another approach the addition of second active metal
to oxides or using perovskite was expected to have synergistic
effect on activity. Further, partial substitution of La by Y in
LaNiO3 perovskites has been explored for designing active and
selective catalysts for dehydrogenation.
The methylcyclohexane was dehydrogenated over 1 wt%
Pt/La2O3. The feed rate of the reactant was kept constant as
3.38 mmol/min with pulse injection frequency of 0.33 Hz and
pulse width of 10 ms. The experiments were carried out for
a period of 150 min to observe stability of the catalyst.The
temperature of the catalyst surface was kept constant at
350
C. As listed in Table 3, the hydrogen evolution rate over
1 wt% Pt/La2O3 was 12.47 mmol/gmet/min at 150 min. In terms
of hydrogen evolution rate at 90 min (Table 2), the perfor-
mance of 1 wt% Pt/La2O3 is relatively better than 3 wt% Pt/
La2O3. The catalyst was modified using LaNiO3 perovskite as
support for Pt, to increase the efficiency and stability of the
catalyst. Hydrogen evolution rate over 1 wt% Pt/LaNiO3 was
observed as 30.3 mmol/gmet/min at 150 min, however,
formation of methane was also observed with 1 wt% Pt/LaNiO3
as listed in Table 3. Yttrium was used for the partial substi-
tution of La in LaNiO3. Hydrogen evolution rate of about
45.3 mmol/gmet/min at 150 min was observed using 1 wt% Pt/
La0.7Y0.3NiO3 with no methane formation.
From the above discussions, it can be observed that there
is a role of support in catalytic activity and using a mixed
metal oxide can be an option for supporting Pt. Perovskite
type mixed metal oxides having a definite structure and
excellent tailoring possibilities have been reported for many
catalytic reactions. While selecting perovskites composition,
we selected La at A-site and Ni at B-site in ABO3 structure,
since Ni is reported as a good reforming catalyst. In fact, as
reported for perovskite, B-site is catalytically active site. In
order to compare the catalytic activity of only perovskite with
Pt/Per catalysts the dehydrogenation of methylcyclohexane
was carried out over catalyst LaNiO3 and 1 wt% Pt/LaNiO3.
Only LaNiO3 catalysts did not exhibit activity for dehydroge-
nation. As reported by Pernifguez et al. [17], using XPS anal-
ysis of LaNiO3 and reduced LaNiO3, the reduced sample shows
a profile characteristics of a La2O3 phase indicated by
a doublet at 833.2 eV (3d5/2) and 850.0 eV (3d3/2). This report
suggests that the Ni migrate from LaNiO3 and forms Ni
metallic particles resulting in Ni/La2O3 phase. Re-oxidation
results into recuperation of the LaNiO3. Accordingly, Ni
migrates on the surface from the perovskite. Qiao and Bi [20]
also reported using XPS analysis of LaNiO3 and Pt/LaNiO3 that
Ni exists in two oxidation states Ni3þ
and Ni2þ
. They have
further investigated the effect of presence of Pt on reducibility
of Ni in perovskite and concluded that the Pt do not interfere
with reducibility of Ni. Similar effect is expected in our cata-
lysts wherein Ni migrates on the surface and provides more
active sites by co-existence of Pt and Ni under the reducing
conditions [19]. From above results, it can be observed that
there is a role of support in this reaction either for dispersion
of Pt or as a co-catalyst. In the case of perovskite, it is widely
reported that activity of B-site element can be improved with
partial substitution at A-site to create defects in the structure.
In-fact this is generally achieved by partial substitution
at A-site or B-site with metal having different valences such
as 2þ
or 4þ
. Nevertheless, partial substitution at A-site with
different metal loading leads to higher catalytic activity. We
have used La0.7Y0.3NiO3 catalyst that exhibited a comparable
activity with 1 wt% Pt/La2O3 and 1 wt% Pt/LaNiO3. Also
selectivity was observed to be enhanced as there was no
formation of by products like CH4 and C6H6 with La0.7Y0.3NiO3
(Fig. 6). In order to examine effect of co-existing Pt and
perovskite, we have used 1 wt% Pt with La0.7Y0.3NiO3. The
catalyst exhibited highest activity as compared to other
catalysts in this study.
It is evident that the use of perovskite La0.7Y0.3NiO3 in place
of La2O3 as support for Pt resulted in the improved catalytic
activity. This may be attributed to possible migration of Ni
from perovskite and then exhibiting behavior of Ni–Pt bime-
tallic catalyst as explained in above discussions. When Y is
substituted at La site of the perovskite it provides low energy
sites due to difference in electronic configurations of La and Y.
The lower energy sites of outer most orbital of 4d1
of Y
provides more access for Pt loading. This is evident from the
SEM-EDXA data in Table 1, wherein higher loading of Pt was
observed in case of Pt/La0.7Y0.3NiO3 as compared to Pt/LaNiO3.
With improved loading of Pt, the activity of the catalysts Pt/
La0.7Y0.3NiO3 was relatively higher.
In the case of the catalysts, wherein, Pt is supported on
La2O3, and LaNiO3 side reaction of hydrogenolysis of methyl-
cyclohexane was observed in addition to dehydrogenation
with formation of methane. It is important to avoid side
reaction to maintain the quality of hydrogen to be supplied to
fuel cell applications. Thus, 1 wt% Pt/La0.7Y0.3NiO3 which
found to be highly selective towards the dehydrogenation may
be the most promising catalyst.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 4 0 2 0 – 4 0 2 6 4025
7. The catalytic activity for dehydrogenation of methyl-
cyclohexane is reported in the literature for different reaction
conditions. Dehydrogenation using a fixed bed reactor over
0.1 wt% K þ 0.6 wt% Pt/Al2O3 is reported with hydrogen
evolution rate as 744 mmol/Lcat/min (equivalent to 132 mmol/
gmet/min) [21]. However, the reaction was carried out with co-
feed of H2 to keep the catalyst under reduced conditions. In
the present study without co-feed of hydrogen the activity over
1 wt% Pt/La0.7Y0.3NiO3 is ca 45 mmol/gmet/min with nearly 100%
selectivity. Under the conditions, the catalyst is a potential
candidate for the dehydrogenation of methylcyclohexane.
The rate constants were estimated as 8.3 per min for both
1 wt% Pt/LaNiO3 and 1 wt% Pt/La0.7Y0.3NiO3 catalysts. The
similar values of rate constants for 1 wt% Pt/LaNiO3 and 1 wt%
Pt/La0.7Y0.3NiO3 explain that partial substitution of La by Y has
no effect on the kinetics. Nevertheless, substitution has
significant impact on selectivity of hydrogen evolution. Rela-
tively higher rate constant for 1 wt% Pt/LaNiO3 and 1 wt% Pt/
La0.7Y0.3NiO3 catalysts as compared to Pt/La2O3 may be
attributed to contribution of Ni as active sites supporting
better hydrogen spillover phenomena.
4. Conclusions
The dehydrogenation of methylcyclohexane was successfully
carried out over Pt supported on metal oxides and Pt sup-
ported on perovskites. It was demonstrated that the selec-
tivity towards the dehydrogenation reaction can be achieved
by proper design of perovskite composition by substitution at
La-site. The loading of Pt on supports in this study was ca
1 wt%, which is promising to minimize the use of Pt in catalyst
compositions. With a cost-effective, active and selective
dehydrogenation catalyst available, the dehydrogenation of
methylcyclohaxane could be a potential option for hydrogen
transportation in future.
Acknowledgments
Financial support received from Ministry of New and Renew-
able Energy, New Delhi is acknowledged.
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