Light-driven carbon dioxide reduction coupled with conversion of acetylenic group to ketone by a functional Janus catalyst based on keplerate {Mo132}

Article abstract of DOI:10.1039/c8ta06243a

Catalysts enabling CO₂ reduction coupled with another organic reaction are rare. In this study, we report such a catalyst keplerate {Mo₁₃₂}, which catalyses photochemical carbon dioxide reduction to formic acid coupled with organic transformation, i.e., hydration of phenylacetylene to acetophenone in visible light. It initially oxidizes water and injects the reducing equivalents for reduction of carbon dioxide at the same time, converting acetylenic group to ketone. Our designed redox Janus catalyst provides an inexpensive pathway to achieve carbon dioxide reduction as well as conversion of phenylacetylene to acetophenone, which is an industrially important precursor.

Full text of DOI:10.1039/c8ta06243a

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Light-driven carbon dioxide reduction coupled
with conversion of acetylenic group to ketone by
a functional Janus catalyst based on keplerate
Cite this: J. Mater. Chem. A, 2018, 6,
20844
{Mo132}†
ab
Joyeeta Lodh,ab Apabrita Mallickab and Soumyajit Roy
*
Catalysts enabling CO2 reduction coupled with another organic reaction are rare. In this study, we report
such a catalyst keplerate {Mo132}, which catalyses photochemical carbon dioxide reduction to formic
acid coupled with organic transformation, i.e., hydration of phenylacetylene to acetophenone in visible
light. It initially oxidizes water and injects the reducing equivalents for reduction of carbon dioxide at the
same time, converting acetylenic group to ketone. Our designed redox Janus catalyst provides an
inexpensive pathway to achieve carbon dioxide reduction as well as conversion of phenylacetylene to
acetophenone, which is an industrially important precursor.
Received 29th June 2018
Accepted 30th September 2018
DOI: 10.1039/c8ta06243a
rsc.li/materials-a
chemicals. Lehn and Sauvage, in 1982 and 1986, conducted
path-breaking studies in the eld of carbon dioxide reduction
using metal-porphyrins,25 Ni-cyclams26 and polyporphyrins.
Introduction
An increase in energy demand and greenhouse gas emission
has called for a need to reduce carbon dioxide1 chemically,
which has been achieved in this study using polyoxometalate
{Mo132}.2–5 It can become an indispensable key technology to
address the global energy and environmental crisis.6 As light is
abundant, it can be harnessed7 to replace the existing use of
fossil fuel reserve if it can valorize CO2. CO2 valorization can be
achieved by its direct reduction8–12 alternatively as a coupled
process, where a sacricial oxidizing agent13,14 is required. In
our laboratory, we have developed pathways for reduction of
CO2 coupled with oxidation of water15,16 using heterogenized
so-oxometalates.17–20 Here, we take the next step and employ
a dual-functional catalyst, a Janus catalyst, synthesized and
Ishitani has reported visible light photocatalytic CO2 reduction
for both carbon nitride nanosheets27 and ytterbium–tantalum28
oxynitride coupled with a binuclear Ru(II) complex. Further-
more, CuGaO2, which is a p-type semi-conductor coupled with
Ru(II)–Re(I) supramolecular catalyst to reduce CO2 to CO pho-
toelectrochemically, has also been reported.29 Yaghi and co-
workers have pioneered the eld of electrocatalytic CO2 reduc-
tion using porphyrin-containing active sites of covalent organic
frameworks.30 They have also pioneered plasmon-enhanced
photocatalytic CO2 reduction under visible light using metal
organic framework-coated nanoparticles, Ag/Re3-MOF.31 Frei's
group has conducted notable research on photoinduced CO2
reduction using Cd and CdSe nanoparticles. Abe et al. have led
the efforts on photoreduction of CO2 to formate using a Cd–Zn
alloy catalyst.32
characterized rst by the Muller group of Germany,2–5 which can
¨
reduce CO2 and convert the acetylenic moiety to ketone. Before
we describe the modus operandi and the design of our catalyst
in detail, we review the literature on CO2 reduction to put our
study in perspective.
The eld of CO2 reduction has been gaining attention for
quite a while21 owing to the prospect of reduction of greenhouse
gases and also for the option to generate high-energy liquid
fuels, such as CH3OH22,23 and HCOOH,16,17 and even higher
carbon containing congeners24 including various ne
In our recent studies, we have approached CO2 reduction
from the perspective of a coupling reaction with water oxida-
tion, where so-oxometalates (SOMs) have been used as pho-
toactive and photosensitizing components. The constituents of
all these SOMs are oxometalates with photo-excitable M]O
units. Here, we take the next step and employ a molecular
VI
(NH4)42[Mo MoV60O372(CH3COOH)30(H2O)72]$hydrate {Mo132} 1
72
as a Janus catalyst and photoexcite it rst using visible light in
the presence of Ru(II)(bpy)3Cl2 to oxidise water. The Janus
function of the catalyst now comes into play. It catalyzes the
reduction of CO2 to formic acid by injecting the generated
electrons and protons. Concomitantly, it can switch to an
organic reaction by the generated protons in the medium along
with oxygen and water. Hence, here, we choose to couple CO2
aEFAML, College of Chemistry, Central China Normal University, 152 Luoyu Road,
Wuhan, P. R. China. E-mail: s.roy@mail.ccnu.edu.cn
bEFAML, Materials Science Centre, Department of Chemical Sciences, Indian Institute
of Science Education & Research, Mohanpur Campus, Kolkata, India. E-mail: s.roy@
iiserkol.ac.in
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c8ta06243a
20844 | J. Mater. Chem. A, 2018, 6, 20844–20851
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reduction with the hydration of an acetylenic bond to synthesize slowly turned brown. The precipitated red brown crystals ob-
a ketone. More specically, we hydrolyze phenylacetylene to tained aer 3–4 days were ltered off through a glass frit,
acetophenone simultaneously while reducing CO2 to formic washed with 90% ethanol and diethyl ether and dried in air.
acid. It might be noted here that organic precursors such as Yield: 3.3 g (52% based on Mo).
acetophenone in particular are vital for pharmaceutical indus-
tries33 for the synthesis of drugs, including pyrrobutamine,34
Synthesis of Ru(bpy)3Cl2
dextropropoxyphene,35 trihexyphenidyl,36 pyridinol,37 and
Reagent grade dimethyl formamide (7 mL) was reuxed with
aspaminol.38 Even though the synthesis of such a vital precursor
2,2-bipyridine (1.195 g, 7.649 mmol), LiCl (1.077 g) and RuCl3-
has been made relatively cheaper, yet, the challenge is to
$3H2O (1 g, 8.824 mmol) for 8 hours. Reagent grade acetone (32
economize an efficient modus operandi for the synthesis of this
mL) was added to the reaction mixture as it cooled down to
precursor. Organic transformation in the presence of visible
room temperature. The reaction mixture was kept overnight at
light39–41 coupled with CO2 reduction is a way forward in that
0
ꢀC. The solution was then ltered, and black crystalline
direction. The reaction is important in the present context as it
is carried out under a mild reaction condition42 as well as atom
economically43 along with a thermodynamically uphill reac-
tion44 such as that of CO2 reduction.
substance was obtained. The crystals were washed thrice with
water and then with diethyl ether and dried by suction.
General reaction procedure for photocatalytic CO2 reduction
We now describe the structure of the catalyst in detail.15–18
VI
The Janus catalyst is (NH4)42[Mo MoV60O372(CH3COOH)30
-
The photocatalytic carbon dioxide reduction was conducted as
72
(H2O)72]$ca. 300H2O.4,45 The molecule has an icosahedral point follows: desired amounts (0.1–0.8 mmol) of {Mo132}, i.e., our
group and consists of 12 [(MoVI)(MoVI)5]46 pentagons disposed catalyst and Ru(bpy)3Cl2 (0.2 mmol) were taken in 10 mL of
at the vertices of the icosahedron. Here, the central pentagonal degassed double distilled water. Furthermore, the reaction
unit is pentagonal bipyramidal [MoO7], which is linked via O mixture was purged with CO2 gas for 2 hours in a sealed reac-
bridging atoms to 5 [MoO5(H2O)] octahedra. We believe that the tion vial. The reaction mixture was kept in blue LED light and
coordinated water molecules in these octahedral sites act as monitored at different time intervals (2–24 hours). A 20 mL
active sites for the hydration of acetylenic groups. Moreover, aliquot of the reaction mixture was taken out and further
there are 30 [MoV2] linkers, each of which connects two diluted with 10 mL of doubly distilled water for monitoring the
[MoO5(H2O)] of two different [(MoVI)(MoVI)5] units forming the products with GC-MS. The presence of formic acid was also
icosahedral cluster. The mixed valent MoV/MoVI centres act as detected using GC-MS. All the quantications of formic acid
the redox centres of the catalyst in the catalytic process, and were performed using GC-MS.
such abundance of mixed valent centres led us to choose this
catalyst for the redox reaction. It may be mentioned that in
recent times, various groups have been involved in exploiting
the alkyne chemistry to generate viable industrially important
chemicals. Recent research includes hydration of alkynes using
systems involving Au salts47–49 and ruthenium-50,51 and
platinum-based catalysts.52 Here, we have taken the next step;
we have coupled alkyne hydroxylation with CO2 reduction. Now,
we describe our experimental design and results.
General procedure for coupling photocatalytic CO2 reduction
with organic hydroxylation reactions
The reaction was conducted photochemically in a 10 mL quartz
tube with phenylacetylene (2 mmol), HCl (12 N, 10 mL), water,
[Mo132] catalyst (0.1–0.8 mmol) and Ru(bpy)3Cl2 (2 mg) kept
under blue LED light. The reaction mixture was sealed in
a reaction vial, and CO2 was purged for 2 hours. The light ux
was measured to be 0.32 W cmꢁ2 (at 475 nm). The reaction was
monitored with thin layer chromatography at different time
intervals and eventually, the product acetophenone was quan-
tied using GC-MS.
Experimental procedure
Materials and reagents
All the materials used for the experiments are available
commercially and have not been puried further. The glass
apparatus used was rst washed in acid bath, followed by water
and nally, it was rinsed with water. All the experiments were
carried out in doubly distilled deionized water.
Characterisation technique
Raman spectroscopy. Raman spectroscopy (Horiba Jobin
Yvon LABRAM HR800) was employed using a He–Ne ion laser of
wavelength 633 nm as the excitation source to analyse the
catalyst before and aer the course of the reaction.
1H NMR spectroscopy. 1H NMR of the isolated products was
recorded on a Jeol 400 MHz Spectrometer.
VI
Synthesis of (NH4)42[Mo MoV60O372(CH3COOH)30(H2O)72]$
72
hydrate (1)
Gas chromatography-mass spectrometry (GC-MS). The
To a solution of (NH4)6Mo7O24$4H2O (5.6 g, 4.5 mmol) and products were identied and analyzed using Trace 1300 GC and
CH3COONH4 (12.5 g, 162.2 mmol) in H2O (250 mL), N2H6$SO4 ISQ qd single quadrupole mass spectrometer with a TG-5MS
(0.8 g, 6.1 mmol) was added and stirred for 10 min. The color capillary column (30 m ꢂ 0.32 mm ꢂ 0.25 mm) supplied by
was observed to change from blue to green. Then, 50% (v/v) Thermo Fisher Scientic, India.
CH3COOH (83 mL) was added. The green solution was stored
Fourier-transform infra-red (FT-IR) spectroscopy. The FT-IR
at 22 ꢀC in an open vessel without further stirring. The color spectra were collected using a PerkinElmer Spectrum RX1
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spectrophotometer. The sample was grounded with KBr and
was recorded within the range of 2000–450 cmꢁ1
.
Results and discussions
About the Janus catalyst
Scheme 1 Schematic representation of the coupling process using
{Mo132} as the catalyst under blue LED light in the presence of
Ru(bpy)3Cl2 as a photosensitizer.
VI
(NH4)42[Mo MoV60O372(CH3COOH)30(H2O)72]$ca. 300H2O (1)
72
The polyoxometalate 1 (Fig. 1) serves as an active catalyst for
photochemical carbon dioxide reduction coupled with organic
transformation of phenylacetylene to acetophenone in water. It
is a keplerate53 anion having a diameter of 2.9 nm. The spherical
cluster consists of 132 molybdenum centres out of which 72 are
MoVI, and the rest 60 are MoV. The purity of the synthesized
{Mo132} was conrmed using FT-IR spectra. The FT-IR spectra of
{Mo132} in the region of 2000–450 cmꢁ1 are shown in Fig. S6.†
The characteristic bands for {Mo132} were found at 968 and 935,
792 and 724 cmꢁ1 due to the presence of Mo]O bond and Mo–
O–Mo bond. The peaks at 1546 and 1404 cmꢁ1 denoted the
presence of COOꢁ and NH4+ groups, respectively (Fig. S6†). Both
the redox activity and photoactivity of the Mo centres in the
cluster facilitated the reaction. We believe that this active
species is responsible for photocatalytic CO2 reduction coupled
with hydration of phenylacetylene.
increased, the activity remains unchanged. The optimised ratio
for maximum activity is achieved with 1 : 1 mole ratio. The
reduction yields formic acid selectively from carbon dioxide,
and the same is detected through cyclic voltammetry (CV) and
gas chromatography MS (GC-MS). We could not trace the
presence of any other liquid or gaseous products other than
formic acid. The peak corresponding to the reduction of carbon
dioxide at around ꢁ0.6 V from the CV experiments vs. the Ag/
AgCl electrode denotes the conversion of CO2 to HCOOH
(Fig. S5†). The formic acid formed is quantied by GC-MS. The
isotopic 13CO2 is used instead of 12CO2 in the photocatalytic
reaction. The products are characterized using gas
chromatography-mass spectrometry (Fig. S7†). Aer the catal-
ysis, the peak appearing at 1.7 min with m/z ¼ 75 corresponds to
ethyl formate formed aer esterication of formic acid found in
the medium with ethanol. This validates the fact that formic
acid is derived from 13CO2. The simultaneously occurring water
oxidation yields oxygen in the reaction medium, which is
detected using a YSI Clark-type electrode (Fig. S1 and S2†). This
is further conrmed from CV experiments. A sharp increase in
current is observed at 1.2 V vs. Ag/AgCl electrode, which is
a characteristic of water oxidation (Fig. S5†). We have later
investigated the effects of catalyst loading, pH and reaction time
on the yield of the reactions depicted in Scheme 1.
Photocatalytic carbon dioxide reduction
The photochemical carbon dioxide reduction was performed
using catalyst 1 under nitrogen atmosphere. On purging CO2, it
gets linked with the Mo2 unit of the catalyst and thus creates
a CO2-absorbed species {Mo132–CO2}.54 Ru(bpy)3Cl2 has been
used as a photosensitizer (PS). On photo-excitation using blue
2+
LED, Ru(bpy)3 transfers its energy to CO2-adsorbed catalyst
species, forming {Mo132–CO2}*.55–58 The water in the reaction
medium acts as a sacricial electron donor to reduce MoVI
centres in excited catalyst species to MoV, thus forming {Mo132
–
CO2}ꢁ.59 This facilitates the reduction of adsorbed carbon
dioxide to formic acid. In the absence of Ru(bpy)3Cl2, formic
acid or acetophenone is not detected in the visible light, indi-
cating the fact that catalytic cycle is initiated by the photosen-
sitizer. The concentration of {Mo132} is kept constant and that of
Ru(bpy)3Cl2 is varied; the activity of the catalyst then increases.
However, when the concentration of Ru(bpy)3Cl2 is further
Coupling organic transformation with CO2 reduction
A more detailed picture leads us to propose a pathway for this
reaction (Fig. 2). On purging CO2 in the reaction medium, peaks
have been observed followed by increase in the current in the
cyclic voltammogram. The peaks correspond to the adsorption
of CO2 on the surface of the catalyst, resulting in the formation
of CO2-adsorbed catalyst species (Fig. 2b). As discussed previ-
ously, while the electrons generated from water oxidation are
utilized for carbon dioxide reaction, the generated protons are
taken up by organic substrates for their oxidation. In this study,
we have used phenylacetylene as the organic moiety. The triple
bonds in phenylacetylene accept the proton and the alkyne
functionality is hydrogenated to form a vinylic carbocation.
Once the proton is bound, the carbocation formed gets attacked
by the water molecules in the reaction medium, and the loss of
proton gives the addition product acetophenone. To probe the
pathway, we have performed the reaction by replacing H2O with
D2O; from the NMR spectra (Fig. 2a), a peak is observed at
3.06 ppm, which corresponds to the D substitution in the
terminal methyl group.
To investigate the dependency of the coupling process of
organic transformation and photochemical carbon dioxide
Fig. 1 Structure of the catalyst {Mo132}.
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Fig. 2 A probable pathway for photocatalytic carbon dioxide reduction and organic reaction using {Mo132} as a catalyst. (a) Cyclic voltammogram
of the reaction mixture showing CO2-adsorbed species (b) 1H NMR showing deuterium substitution in the product obtained from the reaction
mixture in D2O.
with ROS. The same reaction was also performed in the absence
of light to show the effect of light on the reaction. No products
were obtained under this condition, and this implied the fact
that the reaction was dependent on light. Thus, water and light
are integral parts of our reaction. A slight excess acid is needed
to ensure optimum transformation of organic substrates. In the
absence of an acid, phenylacetylene tends to polymerise. The
biphasic solvent systems such as DMSO/H2O allow easy sepa-
ration of the catalyst from the products.
Effect of pH on the reaction
Fig. 3 Plots representing yields of formic acid and acetophenone in
reaction media of water and DMSO.
Now, we investigate the effect of pH on the reaction system. It is
a known fact that carbon dioxide reduction is facilitated by
decrease in pH, whereas water oxidation is characterised by an
increase in pH. This could be well understood by taking into
account these two reaction equilibria:
reduction, we performed the reaction in different kinds of
solvents, such as dry DMF and dry DMSO, keeping the other
conditions constant. In these aprotic solvents, hardly any trace
of formic acid was found. We believe that the trace amount of
water present along with DMF or DMSO led to the formation of
acetophenone. DMSO/water (1 : 1) gave the optimum yield of
the reaction with 0.12 mmol of formic acid and 0.79 mmol of
acetophenone (Fig. 3). DMSO does not play any role other than
solubilising the organic substrate and providing the reaction
2H2O / O2 + 4H+ + 4eꢁ
(1)
(2)
CO2 + 2H+ + 2eꢁ / HCOOH
The carbon dioxide reduction is a proton coupled process;
the reduced product is facilitated by increasing proton
concentration, i.e., with decrease in pH. The water oxidation
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Fig. 4 GC-MS plots of (a) formic acid and (b) acetophenone obtained at various pH. (c) Plot showing yield of formic acid and acetophenone at
different pH.
bonds of the terminal alkynes act as Lewis bases and thus attack
the protons released during water oxidation. This protonates
the carbon with the most number of hydrogen substituents.
Thus, hydration of terminal alkynes could also be stated as
a proton coupled process, wherein the formation of methyl
ketone is favoured by increasing proton concentration in the
reaction medium. Thus, considering the overall mechanism,
the reaction is facilitated by decreasing pH. The maximum yield
of formic acid was observed to be 0.12 mmol at pH 1, whereas
that of acetophenone was 0.79 mmol (Fig. 4).
Effect of catalyst loading on the reaction
The amount of product formation varied with the amount of
catalyst following the kinetics of heterogeneous catalytic reac-
tion. The concentration of products was found to increase with
Fig. 5 Plot showing yield of formic acid and acetophenone for various
loading of {Mo132} catalyst.
the increase in the amount of catalyst only up to a certain limit,
i.e., 0.4 mmol of catalyst 1 (Fig. 5). However, with further
increase in the concentration of catalyst, the concentration of
products becomes almost constant. This is because of the fact
that the reaction is dependent on the active surface area of the
catalyst, which becomes constant aer a certain amount of
catalyst loading. The maximum turnover number (TON) of CO2
reduction reaction is 300 with respect to per mole of catalyst 1,
whereas that of hydration of phenylacetylene is found to be
1975.
Effect of time on the reaction
Next, we performed time-dependent experiments at pH 1 with
0.4 mmol of catalyst 1. The amount of formic acid is found to
increase with increasing time (Fig. 6). The nature of the plot
indicating the formation of products with time is near-
sigmoidal, which implies possibility of operation of heteroge-
neous catalysis in the reaction. Owing to the overlapping nature
Fig. 6 Plots showing yields of formic acid and acetophenone at
different time intervals.
of near-linear and near-sigmoidal nature of the plot, we
envisage molecular and heterogeneous catalysis to be the mode
releases protons into the reaction medium and thus, an
of catalysis. Both the reactions have an initial lag phase of few
increase in pH facilitates water oxidation. The addition of
hours (Fig. 6), which might be the time necessary for the acti-
a proton to the carbon with more number of hydrogen (terminal
vation of the catalyst. The reaction required ca. 24 hours for
carbon atom) suggests the fact that it is a Markovnikov addi-
completion. The maximum turnover frequencies (TOF) for
tion. The Markovnikov additions of hydrogen over terminal
HCOOH and acetophenone at the end of 24 hours of reaction
alkynes result in methyl ketone. The electrons in the triple
are 12.5 hꢁ1 and 82.29 hꢁ1, respectively.
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Table
reaction yield
1 Effects of different substitutions of phenylacetylene on
trimethyl(phenylethynyl)silane, no reactivity was observed
owing to their electron deciency and volatility, respectively.
This observation further indicates that the reaction proceeds via
cation formation. We also observe that the stability of the
intermediate cation plays a predominant role in the product
formation. The reactivity of internal alkynes has been found to
be lower, whereas the use of terminal alkynes as substrates and
0.4 mmol loading of catalyst 1 led to conversions ranging from
79% to 91%. The rate determining step of the organic trans-
formation was marked by the formation of carbonium ion,
which further reacted with water in the medium and tauto-
merized to form ketone. This was proved by performing the
reaction with D2O.
Reagent
Product
Yield
79
83
86
91
8
7
Stability of the catalyst
We further investigated the stability of the catalyst using Raman
spectroscopy (Fig. 7) before and aer the reaction. Raman
spectra of the catalyst were found to be identical in both the
cases. This result highlighted the fact that the cluster remains
intact during the course of the reaction. To conrm the recy-
clability of the catalyst, we have used catalyst 1 up to 10 catalytic
cycles. The catalyst has been found to remain intact even aer
10 cycles, and the yields of the reduction products, i.e., formic
acid and acetophenone remain almost the same. Hence, we
report a stable catalyst, which could be used to catalyse the
reaction under photocatalytic conditions.
No reaction
—
Effect of the substrate
The effect of substitutions on the substrates in hydration of
phenylacetylene to acetophenone could be correlated with the
stability of the carbonium ion formed during the rate deter-
mining step. Solvation plays a signicant role in the carbonium
ions derived from the alkynes and hence, steric hindrance in
such solvation can have a greater impact. As mentioned previ-
ously, substitution greatly alters the reaction rates (Table 1).
It has been observed that para-substituted phenylacetylene
Conclusions
To summarize, herein, we report a simple, effective and green
route to photochemically reduce carbon dioxide to formic acid
and couple it with an organic reaction to produce ketones from
corresponding alkyne substrates. We have used keplerate pol-
yoxometalate – {Mo132} and exploited its photocatalytic activity
to carry out the above reactions as a dual-functional Janus
catalyst. We found that the redox activity of MoV/MoVI centre of
the catalyst drives the whole coupling process. This is important
undergoes
a reaction faster than phenylacetylene itself.
This observation indicates that the presence of electron
donating groups accelerates the reaction, whereas electron
withdrawing groups at the para position decrease the rate
of reaction. Furthermore, for some substituted products,
such as triuoromethyl-substituted phenylacetylene and
Fig. 7 (a) Raman spectra of {Mo132} before and after reaction showing identical peaks. (b) Recyclability of {Mo132} in photochemical CO2
reduction and organic hydroxylation.
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from the perspective of synthetic chemistry as well as green 17 S. Das, S. Biswas, T. Balaraju, S. Barman, R. Pochamoni and
chemistry as the Janus catalyst used here is inexpensive, effi- S. Roy, J. Mater. Chem. A, 2016, 4, 8875–8887.
cient and environmentally friendly. It is also one of the rst 18 S. Biswas, R. Pochamoni and S. Roy, ChemistrySelect, 2018, 3,
examples of how a Janus catalyst can be used in organic 2649–2654.
transformations coupled with carbon dioxide reduction. This 19 S. Roy, CrystEngComm, 2014, 16, 4667–4676.
study can further open up new avenues in the area of catalysis in 20 S. Roy, Comments Inorg. Chem., 2011, 32, 113–126.
the context of CO2 valorization chemistry and organic 21 B. Kumar, M. Llorente, J. Froehlich, T. Dang, A. Sathrum and
syntheses.
C. P. Kubiak, Annu. Rev. Phys. Chem., 2012, 63, 541–569.
22 B. Rungtaweevoranit, J. Baek, J. R. Araujo, B. S. Archanjo,
K. M. Choi, O. M. Yaghi and G. A. Somorjai, Nano Lett.,
2016, 16, 7645–7649.
Conflicts of interest
There are no conicts to declare.
23 F. Studt, I. Sharafutdinov, F. Abild-Pedersen, C. F. Elkjær,
J. S. Hummelshøj, S. Dahl, I. Chorkendorff and
J. K. Nørskov, Nat. Chem., 2014, 6, 320.
24 K. U. D. Calvinho, A. B. Laursen, K. M. K. Yap, T. A. Goetjen,
S. Hwang, B. Mejia-Sosa, A. Lubarski, K. M. Teeluck,
N. Murali, E. S. Hall, E. Garfunkel, M. Greenblatt and
G. C. Dismukes, Energy Environ. Sci., 2018, 11, 2550–2559.
25 J. Hawecker, J.-M. Lehn and R. Ziessel, J. Chem. Soc., Chem.
Commun., 1984, 328–330.
Acknowledgements
SR gratefully acknowledges the start-up and FIRE grants from
IISER-Kolkata. The nancial support from CCNU, China and
NSFC is gratefully acknowledged.
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