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Presenter : Mohammad Rad
Master : Dr.Vahid SafariFard
5 May 2019
Vo l a t i l e O r g a n i c C o m p o u n d s
b y M e t a l O r g a n i c F r a m e w o r k
Sensing of VOCs by MOFs
IN THE NAME OF GOD
JensMartensson
2
What’s Metal Organic Frameworks?
SensingofVOCsbyMOFsPresenter:MohammadRad
Coordination ChemistryPrussian blue
First study on coordination polymer
New porous material
Metal organic Framework
JensMartensson
3
What’s Metal Organic Frameworks?
Coordination
polymer
an inorganic or
organometallic
polymer
structure
containing metal
cation centers
linked by
ligands.
One Dimension
Two Dimension
Three Dimension
SensingofVOCsbyMOFsPresenter:MohammadRad
JensMartensson
4
What’s Metal Organic Frameworks?
Coordination
polymer
an inorganic or
organometallic
polymer
structure
containing metal
cation centers
linked by
ligands.
Three Dimension
Metal Organic Framework (MOF)
Linker (Organic Compound) Node (Metal Compound)
dative bond
SensingofVOCsbyMOFsPresenter:MohammadRad
JensMartensson
5
What’s Metal Organic Frameworks?
applications in :
catalysis
proton conducting
environmental
storage and separation
drug delivery
gas monitoring
luminescent sensor for detecting
volatile organic compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
JensMartensson
6
What’s volatile organic compounds ?
volatile organic
compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Volatile organic compounds (VOCs) are emitted into the atmosphere from
anthropogenic and biogenic sources, and may also be formed in situ in the
atmosphere as products of the atmospheric transformations of other VOCs
 On a worldwide basis, emission of VOCs from :
1. biogenic sources (mainly vegetation) 1150 Tg per year
2. anthropogenic sources 100 Tg per year
 The major classes of emitted VOCs are :
1. alkanes
2. alkenes
3. aromatic hydrocarbons
4. ethanol
5. oxygenated VOCs ( acetone, methanol and camphor)
6. emissions resulting from vehicle emissions (comprising mainly gasoline constituents)
Ref:Chem.Rev.2003,103,4605-4638
JensMartensson
7
Selective Gas Sorption By MOFs
1. size selective gas sorption
2. selective sorption in flexible and dynamic
framework
3. selectivity apparently independent of size-
SensingofVOCsbyMOFsPresenter:MohammadRad
JensMartensson
8
Selective Gas Sorption By MOFs
[Er2(pda)3]
Free passage smaller than
3 Å
CO2 3.30 Å
Ar 3.40 Å
N2 3.64 Å
Kinetic diameter of :
Kinetic diameter of :
H2 2.89 Å
N2 3.64 Å
SensingofVOCsbyMOFsPresenter:MohammadRad
reported a solvatochromic CuIL-MOF that
can
be a visual color and luminescence
response sensor for small polar VOCs in
the solid state
It might be one of the most sensitive
Copper(I) Metal−Organic Framework: Visual Sensor
for Detecting Small Polar Aliphatic Volatile Organic
Compounds
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
JensMartensson
10
Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
ABSTRACT: A porous Cu-MOF [H2O⊂Cu2(L)2I2; L = 1-benzimidazolyl-3,5-bis(4-pyridyl)benzene], which can be a
visual and luminescent sensor for detecting small polar aliphatic volatile organic compounds (VOCs), such as alcohols,
ketones, and halocarbons, is reported. The nakedeye and luminescent detection limitations for these VOC are 5 and 1
ppm, respectively.
VOC detection methods
gas chromatography (GC)
GC−mass spectrometry
expensive
nonportable
portable sensors
based on metal oxide,
conductive polymers,
and a quartz crystal
microbalance
the selectivity
and sensitivity
are relatively low
Therefor
e
a real need for the development of
performance portable VOC sensors
Solvatochromism
vapochromism
JensMartensson
11
Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
Solvatochromism
vapochromism
The solvatochromic and vapochromic species change color upon exposure to analyte liquid
and vapor phases, and therefore detection of analytes can often occur even by the naked eye.
change colour in response to the vapour of an organic compound or gas.
acts as a sensitive naked-
eye colorimetric sensor to
perceive these VOCs under
ambient conditions.
able to upload various small polar VOCsCu-MOF
such as alcohols, ketones, and halocarbons
JensMartensson
12
1.Absorption on site unsaturated centers (CUS)
Methods of absorbing materials on MOFs :
SensingofVOCsbyMOFsPresenter:MohammadRad
2.Interaction of acid and base
3.Electrostatic interactions
4.Hydrogen bond
5.Complex formation
6.Respiratory properties
JensMartensson
13
Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
guest dimension is the dominating
factor for the color response rate
The analytes with smaller size
would facilitate guest exchange
and, consequently, the color change
smaller analytes could enter the
pores more easily, which would
lead to a faster color response.
JensMartensson
14
Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
 UV−vis diffuse-reflectance spectra of 1−11.
Min Intensity:
2-propanol⊂CuIL
max Intensity:
n-propanol⊂CuIL
Intensity Ref:
H2O⊂CuIL
JensMartensson
15
Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
 PL spectra of H2O⊂CuIL (1) and alcohols⊂CuIL (2−5), ketones⊂CuIL (6−9), and halocarbons⊂CuIL (10 and 11)
Besides a naked-eye color change, VOCs encapsulation mentioned above also
caused a dramatic change in their photoluminescence (PL) spectrum
Compared to H2O⊂CuIL (1),
the emission intensities of
the VOC-loaded samples
from the liquid phase are
much enhanced
enhancement
imposed by the
host−guest
interactions
decreasing solvent polarity
(H2O> VOCs)
Thus, the network is able to detect various
VOCs and differentiate between them (via
either a turn-on or a turn-off interaction).
The network also demonstrates a selective
response toward explosive vapor residues
in an acceptable time frame. This work
reinforces the potential of MOFs to detect
explosive residues and suggests the
potential for further applications in sensing.
Highly Fluorescent Metal−Organic Framework for the
Sensing of Volatile Organic Compounds
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
JensMartensson
17
Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
The drawback of using fluorescence based sensing
aggregation-induced quenching
the emissive properties of the fluorophore are
weakened when it is present in high
concentrations
tetraphenylethene (TPE) was chosen as a fluorophore
as it exhibits aggregation enhanced emission (AIE).
restricted rotation and motion of its central phenyl
groups
this effect can act as a turn-on sensor
by further restricting the movement of the phenyl
groups by “fixing” the orientation and spacing of the
TPE in a MOF
which can activate
fluorescenc
JensMartensson
18
Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
we present a network with superior properties utilizing a pyridyl based ligand, tetrapyridine tetraphenylethene
(Py- TPE) that is more thermally stable, water-stable, and more sensitive. The network can be regenerated and
exhibited enhanced turn-on fluorescence in response volatile organic compounds and quenching in response
to nitro-substituted VOCs.
(Zn2Cl4Py-TPE)·4(TCE)
JensMartensson
19
Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
Like most TPE derivatives,
the Py-TPE ligand exhibits
aggregation induced
emission (AIE) behavior in
the solid and aggregated
states.
In these states
the rotation of the
phenyl rings is
limited
fluorescence is
enhanced
The strong emission of the
ligand ensures :
the network is also
highly luminescent
in the solid-state
at room
temperature.
The fluorescence emission maxima
are 515 and 530 nm (λex = 340 nm)
The AIE-active fluorescence of network has been used for
sensing aromatic compounds bearing electron-donating
or -withdrawing groups, which can quench or enhance the
fluorescence of network.
JensMartensson
20
Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
 Fluorescence intensity changes of 1 when exposed to methyl- and nitro-substituted VOCs.
The expected turn-on fluorescence was
observed for all of the methyl-substituted
derivatives
13 nm red-shift as the degree
of methyl substitution
decreased
JensMartensson
21
Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
 Fluorescence intensity changes of 1 when exposed to nitrobenzene at different time intervals.
The effect was relatively fast, and the fluorescence
quenching efficiency reached its maximum after
approximately 6 h exposure
prepared TPE-based porous MOF
[Zn2(TCPPE)] (1) with a 3D framework and 1D
rhombus channels. Complex 1 exhibits good
luminescence originating from TPE-based
ligands, where the vibrations and 30 rotations of
phenyl rings in TCPPE4‒ are restricted to turn
on luminescence.
A luminescent metal-organic framework constructed
by a tetraphenylethene-based ligand for sensing
volatile organic compounds
Ref : Chem. Commun., 2015,51, 1677-1680
JensMartensson
23
A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Chem. Commun., 2015,51, 1677-1680
tetraphenylethene (TPE)-based ligandZn
tetrakis[4-(4-carboxyphenyl)phenyl]ethene (H4TCPPE),
[Zn2(TCPPE)]
JensMartensson
24
A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Chem. Commun., 2015,51, 1677-1680
employ H4TCPPE as organic linker
and zinc carboxylate chains as SBU
to build a new porous
[Zn2(TCPPE)] with 1D channels.
The vibrations and rotations of
phenyl rings from TCPPE4‒ are
restricted in the rigid framework
complex exhibits
strong blue
luminescence
shows great potential in gas
adsorption, and nitroaromatics and
VOCs sensing.
JensMartensson
25
A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Chem. Commun., 2015,51, 1677-1680
 Solid-state luminescent properties of as synthesized 1 and activated 1 were investigated at room temperature
Ligand [Zn2(TCPPE)] [H4(TCPPE)]
exhibits strongly red-shifted
The fluorescence lifetimes of as-synthesized 1
and activated 1 are 1.5 and 3.0 ns, respectively
JensMartensson
26
A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Chem. Commun., 2015,51, 1677-1680
 Photoluminescence (PL) spectra of as-synthesized 1, activated 1 and activated 1 with selected guest molecules
Ligand
[Zn2(TCPPE)]
efficient solid-state emission of
activated 1 encouraged us to
examine its fluorescent sensing
ability of VOCs
Complex keeps a rigid
and stable framework
after adsorbing various
VOCs, as revealed by the
almost the same PXRD
patterns
The emission of complex is sensitive to different VOCs, and
strongly blue-shifted are recorded after adsorbing VOCs
prepared TPE-based porous MOF
[Zn2(TCPPE)] (1) with a 3D framework and
16666666666666666666666666, where the
vibrations and 30 rotations of phenyl rings in
TCPPE4‒ are restricted to turn on
luminescence.
Ref : Dalton Trans., 2016,45, 14888-14892
A four-fold interpenetrated metal–organic framework
as a fluorescent sensor for volatile organic compounds
JensMartensson
28
SensingofVOCsbyMOFsPresenter:MohammadRad
tetraphenylethene (TPE)-based ligandCd
Cd2(tppe)(bpdc)2(H2O(
1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE)
A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
Ref : Dalton Trans., 2016,45, 14888-14892
This complex
exhibits intense
blue luminescence
and is sensitive to
volatile organic
compounds
JensMartensson
29
A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Dalton Trans., 2016,45, 14888-14892
interpenetrated
JensMartensson
30
Interpenetrating metal–organic frameworks
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : CrystEngComm, 2016,18, 2596-2606
usually refers to two or more individual polymeric networks with the same or different components
catenate with each other, which is a frequently observed phenomenon in metal-organic frameworks
Interpenetration
interpenetrating metal-organic
frameworks (IMOFs) not only show
fascinating architectures and
topologies, but also exhibit improved
functions and applications
1) 1D→2D
2) 1D→3D
3) 2D→2D
4) 2D→3D
5) 3D→3D
five types based on
their interpenetrating
networks
JensMartensson
31
A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Dalton Trans., 2016,45, 14888-14892
Complex possesses a unique four-fold interpenetrated
three dimensional (3D) framework with one-
dimensional (1D) hexagonal channels (12 Å)
which can adsorb various toxic VOCs effectively
The intensive blue luminescence of the MOF
exhibits obvious VOCs dependent wavelength shift originated
from the guest responsive configuration of the TPPE ligand,
which could be utilized for the sensing of VOCs
JensMartensson
32
A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Dalton Trans., 2016,45, 14888-14892
The as-synthesized 1(without M)
underwent a solvent exchange
process with ethanol, (followed by
drying at 80°C under vacuum)
activated 1 (MOF) sample
toyield
Activated 1a maintains its
rigid framework upon
adsorbing various VOCs
 Comparison of PXRD
as revealed by the
similar PXRD patterns
JensMartensson
33
A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Dalton Trans., 2016,45, 14888-14892
 MOF displayed distinct response when encountering different VOCs upon excitation at 380 nm
mesitylene
MOF
WithoutM
toluene
M-xylene
P-xylene
benzene
All MOF+guests show blue-shift
in the MOF the fully coordinated TPPE ligand without
crystalline disorder minimized the rotation/vibration
based nonradiative decay in this complex.
Therefore, the sensing behavior probably correlates with
the conformational changes of phenyl rings of TPPE ligand
reported rapid and sensitive probing of the
adsorption characteristic of VOCs onMOFs by
QCM in combination . The molecular sieve effect
on the adsorption of the studied VOCs can be
excluded because of the kinetic diameters of the
VOCs are all smaller than the smaller windows of
the pores (12 Å) of MIL-101. The high adsorption
capacities and affinity to VOCs, especially
heteroatom VOCs, make MIL-101 very promising
for application in the adsorption and removal of
VOCs.
Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496
Probing the Adsorption Characteristic of Metal-Organic
Framework MIL-101 for Volatile Organic Compounds by
Quartz Crystal Microbalance
JensMartensson
35
Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496
Electromechanics sensing
sensing VOC
luminescent sensor
Electrochemical sensor
Quartz Crystal Microbalance (QCM)
Surface Acoustic Wave (SAW)
JensMartensson
36
Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496
The common methods
for adsorption
alorimetric Measurement
temperature-programmed
desorption (TPD)
gravimetric method
These methods are
time-consuming (several hours or even
days), and require several gram samples
for measurement
requires only a small amount of absorbent (μg
level), offers short response time, and allows
detection of mass change sensitively (ng level).
Quartz Crystal Microbalance (QCM)
Here reported the exploration of QCM for rapidly and sensitively
probing the adsorption characteristic of VOCs on MOFs
JensMartensson
37
Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance
SensingofVOCsbyMOFsPresenter:MohammadRad
Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496
 Biologycal Example of Quartz Crystal Microbalance (QCM)
JensMartensson
38
SensingofVOCsbyMOFsPresenter:MohammadRad
Summary
 Metal Organic Frameworks History
 volatile organic compounds
Coordination polymerapplication
major classes anthropogenic sourcesbiogenic sources
 Selective Gas Sorption By MOFs
Paper 1 Paper 2 Paper 3 Paper 4 Paper 5
2015 2016 2015 2016 2011
JensMartensson
39
SensingofVOCsbyMOFsPresenter:MohammadRad
References (Papers)
Liu, X. G., Wang, H., Chen, B., Zou, Y., Gu, Z. G., Zhao, Z., & Shen, L. (2015). A luminescent metal–organic framework
constructed using a tetraphenylethene-based ligand for sensing volatile organic compounds. Chemical Communications,
51(9), 1677-1680.
Jackson, S. L., Rananaware, A., Rix, C., Bhosale, S. V., & Latham, K. (2016). Highly fluorescent metal–organic framework for
the sensing of volatile organic compounds. Crystal Growth & Design, 16(6), 3067-3071.
Zhao, X., Li, Y., Chang, Z., Chen, L., & Bu, X. H. (2016). A four-fold interpenetrated metal–organic framework as a
fluorescent sensor for volatile organic compounds. Dalton Transactions, 45(38), 14888-14892.
Huang, C. Y., Song, M., Gu, Z. Y., Wang, H. F., & Yan, X. P. (2011). Probing the adsorption characteristic of metal–organic
framework MIL-101 for volatile organic compounds by quartz crystal microbalance. Environmental science & technology,
45(10), 4490-4496.
Yu, Y., Ma, J. P., Zhao, C. W., Yang, J., Zhang, X. M., Liu, Q. K., & Dong, Y. B. (2015). Copper (I) metal–organic framework:
visual sensor for detecting small polar aliphatic volatile organic compounds. Inorganic chemistry, 54(24), 11590-11592.
Atkinson, R., & Arey, J. (2003). Atmospheric degradation of volatile organic compounds. Chemical reviews, 103(12), 4605-
4638.
Liu, B., Tu, M., & Fischer, R. A. (2013). Metal–organic framework thin films: crystallite orientation dependent adsorption.
Angewandte Chemie International Edition, 52(12), 3402-3405.
JensMartensson
40
SensingofVOCsbyMOFsPresenter:MohammadRad
References (Books)
JensMartensson
41
SensingofVOCsbyMOFsPresenter:MohammadRad
There's Plenty of Room at the Bottom
Presenter: Mohammad Rad
Master: Dr.Vahid SafariFard
iran university of science and technology
5 May 2019
December 29th 1959

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Sensing of volatile organic compounds by MOFs

  • 1. Presenter : Mohammad Rad Master : Dr.Vahid SafariFard 5 May 2019 Vo l a t i l e O r g a n i c C o m p o u n d s b y M e t a l O r g a n i c F r a m e w o r k Sensing of VOCs by MOFs IN THE NAME OF GOD
  • 2. JensMartensson 2 What’s Metal Organic Frameworks? SensingofVOCsbyMOFsPresenter:MohammadRad Coordination ChemistryPrussian blue First study on coordination polymer New porous material Metal organic Framework
  • 3. JensMartensson 3 What’s Metal Organic Frameworks? Coordination polymer an inorganic or organometallic polymer structure containing metal cation centers linked by ligands. One Dimension Two Dimension Three Dimension SensingofVOCsbyMOFsPresenter:MohammadRad
  • 4. JensMartensson 4 What’s Metal Organic Frameworks? Coordination polymer an inorganic or organometallic polymer structure containing metal cation centers linked by ligands. Three Dimension Metal Organic Framework (MOF) Linker (Organic Compound) Node (Metal Compound) dative bond SensingofVOCsbyMOFsPresenter:MohammadRad
  • 5. JensMartensson 5 What’s Metal Organic Frameworks? applications in : catalysis proton conducting environmental storage and separation drug delivery gas monitoring luminescent sensor for detecting volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad
  • 6. JensMartensson 6 What’s volatile organic compounds ? volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad Volatile organic compounds (VOCs) are emitted into the atmosphere from anthropogenic and biogenic sources, and may also be formed in situ in the atmosphere as products of the atmospheric transformations of other VOCs  On a worldwide basis, emission of VOCs from : 1. biogenic sources (mainly vegetation) 1150 Tg per year 2. anthropogenic sources 100 Tg per year  The major classes of emitted VOCs are : 1. alkanes 2. alkenes 3. aromatic hydrocarbons 4. ethanol 5. oxygenated VOCs ( acetone, methanol and camphor) 6. emissions resulting from vehicle emissions (comprising mainly gasoline constituents) Ref:Chem.Rev.2003,103,4605-4638
  • 7. JensMartensson 7 Selective Gas Sorption By MOFs 1. size selective gas sorption 2. selective sorption in flexible and dynamic framework 3. selectivity apparently independent of size- SensingofVOCsbyMOFsPresenter:MohammadRad
  • 8. JensMartensson 8 Selective Gas Sorption By MOFs [Er2(pda)3] Free passage smaller than 3 Å CO2 3.30 Å Ar 3.40 Å N2 3.64 Å Kinetic diameter of : Kinetic diameter of : H2 2.89 Å N2 3.64 Å SensingofVOCsbyMOFsPresenter:MohammadRad
  • 9. reported a solvatochromic CuIL-MOF that can be a visual color and luminescence response sensor for small polar VOCs in the solid state It might be one of the most sensitive Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592
  • 10. JensMartensson 10 Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592 ABSTRACT: A porous Cu-MOF [H2O⊂Cu2(L)2I2; L = 1-benzimidazolyl-3,5-bis(4-pyridyl)benzene], which can be a visual and luminescent sensor for detecting small polar aliphatic volatile organic compounds (VOCs), such as alcohols, ketones, and halocarbons, is reported. The nakedeye and luminescent detection limitations for these VOC are 5 and 1 ppm, respectively. VOC detection methods gas chromatography (GC) GC−mass spectrometry expensive nonportable portable sensors based on metal oxide, conductive polymers, and a quartz crystal microbalance the selectivity and sensitivity are relatively low Therefor e a real need for the development of performance portable VOC sensors Solvatochromism vapochromism
  • 11. JensMartensson 11 Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592 Solvatochromism vapochromism The solvatochromic and vapochromic species change color upon exposure to analyte liquid and vapor phases, and therefore detection of analytes can often occur even by the naked eye. change colour in response to the vapour of an organic compound or gas. acts as a sensitive naked- eye colorimetric sensor to perceive these VOCs under ambient conditions. able to upload various small polar VOCsCu-MOF such as alcohols, ketones, and halocarbons
  • 12. JensMartensson 12 1.Absorption on site unsaturated centers (CUS) Methods of absorbing materials on MOFs : SensingofVOCsbyMOFsPresenter:MohammadRad 2.Interaction of acid and base 3.Electrostatic interactions 4.Hydrogen bond 5.Complex formation 6.Respiratory properties
  • 13. JensMartensson 13 Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592 guest dimension is the dominating factor for the color response rate The analytes with smaller size would facilitate guest exchange and, consequently, the color change smaller analytes could enter the pores more easily, which would lead to a faster color response.
  • 14. JensMartensson 14 Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592  UV−vis diffuse-reflectance spectra of 1−11. Min Intensity: 2-propanol⊂CuIL max Intensity: n-propanol⊂CuIL Intensity Ref: H2O⊂CuIL
  • 15. JensMartensson 15 Copper(I) Metal−Organic Framework: Visual Sensor for Detecting Small Polar Aliphatic Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Inorg. Chem., 2015, 54 (24), pp 11590–11592  PL spectra of H2O⊂CuIL (1) and alcohols⊂CuIL (2−5), ketones⊂CuIL (6−9), and halocarbons⊂CuIL (10 and 11) Besides a naked-eye color change, VOCs encapsulation mentioned above also caused a dramatic change in their photoluminescence (PL) spectrum Compared to H2O⊂CuIL (1), the emission intensities of the VOC-loaded samples from the liquid phase are much enhanced enhancement imposed by the host−guest interactions decreasing solvent polarity (H2O> VOCs)
  • 16. Thus, the network is able to detect various VOCs and differentiate between them (via either a turn-on or a turn-off interaction). The network also demonstrates a selective response toward explosive vapor residues in an acceptable time frame. This work reinforces the potential of MOFs to detect explosive residues and suggests the potential for further applications in sensing. Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071
  • 17. JensMartensson 17 Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071 The drawback of using fluorescence based sensing aggregation-induced quenching the emissive properties of the fluorophore are weakened when it is present in high concentrations tetraphenylethene (TPE) was chosen as a fluorophore as it exhibits aggregation enhanced emission (AIE). restricted rotation and motion of its central phenyl groups this effect can act as a turn-on sensor by further restricting the movement of the phenyl groups by “fixing” the orientation and spacing of the TPE in a MOF which can activate fluorescenc
  • 18. JensMartensson 18 Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071 we present a network with superior properties utilizing a pyridyl based ligand, tetrapyridine tetraphenylethene (Py- TPE) that is more thermally stable, water-stable, and more sensitive. The network can be regenerated and exhibited enhanced turn-on fluorescence in response volatile organic compounds and quenching in response to nitro-substituted VOCs. (Zn2Cl4Py-TPE)·4(TCE)
  • 19. JensMartensson 19 Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071 Like most TPE derivatives, the Py-TPE ligand exhibits aggregation induced emission (AIE) behavior in the solid and aggregated states. In these states the rotation of the phenyl rings is limited fluorescence is enhanced The strong emission of the ligand ensures : the network is also highly luminescent in the solid-state at room temperature. The fluorescence emission maxima are 515 and 530 nm (λex = 340 nm) The AIE-active fluorescence of network has been used for sensing aromatic compounds bearing electron-donating or -withdrawing groups, which can quench or enhance the fluorescence of network.
  • 20. JensMartensson 20 Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071  Fluorescence intensity changes of 1 when exposed to methyl- and nitro-substituted VOCs. The expected turn-on fluorescence was observed for all of the methyl-substituted derivatives 13 nm red-shift as the degree of methyl substitution decreased
  • 21. JensMartensson 21 Highly Fluorescent Metal−Organic Framework for the Sensing of Volatile Organic Compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Cryst. Growth Des. 2016, 16, 6, 3067-3071  Fluorescence intensity changes of 1 when exposed to nitrobenzene at different time intervals. The effect was relatively fast, and the fluorescence quenching efficiency reached its maximum after approximately 6 h exposure
  • 22. prepared TPE-based porous MOF [Zn2(TCPPE)] (1) with a 3D framework and 1D rhombus channels. Complex 1 exhibits good luminescence originating from TPE-based ligands, where the vibrations and 30 rotations of phenyl rings in TCPPE4‒ are restricted to turn on luminescence. A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing volatile organic compounds Ref : Chem. Commun., 2015,51, 1677-1680
  • 23. JensMartensson 23 A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Chem. Commun., 2015,51, 1677-1680 tetraphenylethene (TPE)-based ligandZn tetrakis[4-(4-carboxyphenyl)phenyl]ethene (H4TCPPE), [Zn2(TCPPE)]
  • 24. JensMartensson 24 A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Chem. Commun., 2015,51, 1677-1680 employ H4TCPPE as organic linker and zinc carboxylate chains as SBU to build a new porous [Zn2(TCPPE)] with 1D channels. The vibrations and rotations of phenyl rings from TCPPE4‒ are restricted in the rigid framework complex exhibits strong blue luminescence shows great potential in gas adsorption, and nitroaromatics and VOCs sensing.
  • 25. JensMartensson 25 A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Chem. Commun., 2015,51, 1677-1680  Solid-state luminescent properties of as synthesized 1 and activated 1 were investigated at room temperature Ligand [Zn2(TCPPE)] [H4(TCPPE)] exhibits strongly red-shifted The fluorescence lifetimes of as-synthesized 1 and activated 1 are 1.5 and 3.0 ns, respectively
  • 26. JensMartensson 26 A luminescent metal-organic framework constructed by a tetraphenylethene-based ligand for sensing VOCs SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Chem. Commun., 2015,51, 1677-1680  Photoluminescence (PL) spectra of as-synthesized 1, activated 1 and activated 1 with selected guest molecules Ligand [Zn2(TCPPE)] efficient solid-state emission of activated 1 encouraged us to examine its fluorescent sensing ability of VOCs Complex keeps a rigid and stable framework after adsorbing various VOCs, as revealed by the almost the same PXRD patterns The emission of complex is sensitive to different VOCs, and strongly blue-shifted are recorded after adsorbing VOCs
  • 27. prepared TPE-based porous MOF [Zn2(TCPPE)] (1) with a 3D framework and 16666666666666666666666666, where the vibrations and 30 rotations of phenyl rings in TCPPE4‒ are restricted to turn on luminescence. Ref : Dalton Trans., 2016,45, 14888-14892 A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds
  • 28. JensMartensson 28 SensingofVOCsbyMOFsPresenter:MohammadRad tetraphenylethene (TPE)-based ligandCd Cd2(tppe)(bpdc)2(H2O( 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE) A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds Ref : Dalton Trans., 2016,45, 14888-14892 This complex exhibits intense blue luminescence and is sensitive to volatile organic compounds
  • 29. JensMartensson 29 A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Dalton Trans., 2016,45, 14888-14892 interpenetrated
  • 30. JensMartensson 30 Interpenetrating metal–organic frameworks SensingofVOCsbyMOFsPresenter:MohammadRad Ref : CrystEngComm, 2016,18, 2596-2606 usually refers to two or more individual polymeric networks with the same or different components catenate with each other, which is a frequently observed phenomenon in metal-organic frameworks Interpenetration interpenetrating metal-organic frameworks (IMOFs) not only show fascinating architectures and topologies, but also exhibit improved functions and applications 1) 1D→2D 2) 1D→3D 3) 2D→2D 4) 2D→3D 5) 3D→3D five types based on their interpenetrating networks
  • 31. JensMartensson 31 A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Dalton Trans., 2016,45, 14888-14892 Complex possesses a unique four-fold interpenetrated three dimensional (3D) framework with one- dimensional (1D) hexagonal channels (12 Å) which can adsorb various toxic VOCs effectively The intensive blue luminescence of the MOF exhibits obvious VOCs dependent wavelength shift originated from the guest responsive configuration of the TPPE ligand, which could be utilized for the sensing of VOCs
  • 32. JensMartensson 32 A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Dalton Trans., 2016,45, 14888-14892 The as-synthesized 1(without M) underwent a solvent exchange process with ethanol, (followed by drying at 80°C under vacuum) activated 1 (MOF) sample toyield Activated 1a maintains its rigid framework upon adsorbing various VOCs  Comparison of PXRD as revealed by the similar PXRD patterns
  • 33. JensMartensson 33 A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Dalton Trans., 2016,45, 14888-14892  MOF displayed distinct response when encountering different VOCs upon excitation at 380 nm mesitylene MOF WithoutM toluene M-xylene P-xylene benzene All MOF+guests show blue-shift in the MOF the fully coordinated TPPE ligand without crystalline disorder minimized the rotation/vibration based nonradiative decay in this complex. Therefore, the sensing behavior probably correlates with the conformational changes of phenyl rings of TPPE ligand
  • 34. reported rapid and sensitive probing of the adsorption characteristic of VOCs onMOFs by QCM in combination . The molecular sieve effect on the adsorption of the studied VOCs can be excluded because of the kinetic diameters of the VOCs are all smaller than the smaller windows of the pores (12 Å) of MIL-101. The high adsorption capacities and affinity to VOCs, especially heteroatom VOCs, make MIL-101 very promising for application in the adsorption and removal of VOCs. Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496 Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance
  • 35. JensMartensson 35 Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496 Electromechanics sensing sensing VOC luminescent sensor Electrochemical sensor Quartz Crystal Microbalance (QCM) Surface Acoustic Wave (SAW)
  • 36. JensMartensson 36 Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496 The common methods for adsorption alorimetric Measurement temperature-programmed desorption (TPD) gravimetric method These methods are time-consuming (several hours or even days), and require several gram samples for measurement requires only a small amount of absorbent (μg level), offers short response time, and allows detection of mass change sensitively (ng level). Quartz Crystal Microbalance (QCM) Here reported the exploration of QCM for rapidly and sensitively probing the adsorption characteristic of VOCs on MOFs
  • 37. JensMartensson 37 Probing the Adsorption Characteristic of Metal-Organic Framework MIL-101 for Volatile Organic Compounds by Quartz Crystal Microbalance SensingofVOCsbyMOFsPresenter:MohammadRad Ref : Environ. Sci. Technol. 2011, 45, 10, 4490-4496  Biologycal Example of Quartz Crystal Microbalance (QCM)
  • 38. JensMartensson 38 SensingofVOCsbyMOFsPresenter:MohammadRad Summary  Metal Organic Frameworks History  volatile organic compounds Coordination polymerapplication major classes anthropogenic sourcesbiogenic sources  Selective Gas Sorption By MOFs Paper 1 Paper 2 Paper 3 Paper 4 Paper 5 2015 2016 2015 2016 2011
  • 39. JensMartensson 39 SensingofVOCsbyMOFsPresenter:MohammadRad References (Papers) Liu, X. G., Wang, H., Chen, B., Zou, Y., Gu, Z. G., Zhao, Z., & Shen, L. (2015). A luminescent metal–organic framework constructed using a tetraphenylethene-based ligand for sensing volatile organic compounds. Chemical Communications, 51(9), 1677-1680. Jackson, S. L., Rananaware, A., Rix, C., Bhosale, S. V., & Latham, K. (2016). Highly fluorescent metal–organic framework for the sensing of volatile organic compounds. Crystal Growth & Design, 16(6), 3067-3071. Zhao, X., Li, Y., Chang, Z., Chen, L., & Bu, X. H. (2016). A four-fold interpenetrated metal–organic framework as a fluorescent sensor for volatile organic compounds. Dalton Transactions, 45(38), 14888-14892. Huang, C. Y., Song, M., Gu, Z. Y., Wang, H. F., & Yan, X. P. (2011). Probing the adsorption characteristic of metal–organic framework MIL-101 for volatile organic compounds by quartz crystal microbalance. Environmental science & technology, 45(10), 4490-4496. Yu, Y., Ma, J. P., Zhao, C. W., Yang, J., Zhang, X. M., Liu, Q. K., & Dong, Y. B. (2015). Copper (I) metal–organic framework: visual sensor for detecting small polar aliphatic volatile organic compounds. Inorganic chemistry, 54(24), 11590-11592. Atkinson, R., & Arey, J. (2003). Atmospheric degradation of volatile organic compounds. Chemical reviews, 103(12), 4605- 4638. Liu, B., Tu, M., & Fischer, R. A. (2013). Metal–organic framework thin films: crystallite orientation dependent adsorption. Angewandte Chemie International Edition, 52(12), 3402-3405.
  • 41. JensMartensson 41 SensingofVOCsbyMOFsPresenter:MohammadRad There's Plenty of Room at the Bottom Presenter: Mohammad Rad Master: Dr.Vahid SafariFard iran university of science and technology 5 May 2019 December 29th 1959