Light-induced carboxylation of aryl derivatives with cooperative COF as an active photocatalyst and Ni(ii) co-catalyst

Article abstract of DOI:10.1039/d0nj05843b

The photocatalytic carboxylation of aryl derivatives was demonstrated under CO₂at atmospheric pressure using a mesoporous covalent organic framework (COF) as the active photocatalyst with triethylamine (TEA) as a sacrificial electron source under visible light. A yield of greater than 91% of the isolated product was achieved with 5 mg of catalyst. The reaction cycle is dependent on the use of the Ni(dmg)₂co-catalyst and the sacrificial electron donor (TEA). The reaction does not occur in the absence of light (445 nm) even at elevated reaction temperature. We have also demonstrated that a yield of 32% of the isolated product could be obtained with the use of sunlight in the catalytic cycle. Additionally, this heterogeneous catalytic system was recyclable and reusable for several cycles.

Full text of DOI:10.1039/d0nj05843b

NJC
View Article Online
View Journal | View Issue
PAPER
Light-induced carboxylation of aryl derivatives
with cooperative COF as an active photocatalyst
and Ni(II) co-catalyst†
Cite this: New J. Chem., 2021,
45, 4738
Pekham Chakrabortty,a Anjan Das,a Arpita Hazra Chowdhury,a Swarbhanu Ghosh,a
b
a
Aslam Khan
and Sk. Manirul Islam
*
The photocatalytic carboxylation of aryl derivatives was demonstrated under CO2 at atmospheric pressure
using a mesoporous covalent organic framework (COF) as the active photocatalyst with triethylamine (TEA)
as a sacrificial electron source under visible light. A yield of greater than 91% of the isolated product was
achieved with 5 mg of catalyst. The reaction cycle is dependent on the use of the Ni(dmg)2 co-catalyst and
the sacrificial electron donor (TEA). The reaction does not occur in the absence of light (445 nm) even at
elevated reaction temperature. We have also demonstrated that a yield of 32% of the isolated product could
be obtained with the use of sunlight in the catalytic cycle. Additionally, this heterogeneous catalytic system
was recyclable and reusable for several cycles.
Received 1st December 2020,
Accepted 1st February 2021
DOI: 10.1039/d0nj05843b
rsc.li/njc
In the last few years, the carboxylation of aryl derivatives with
CO2 using various homogeneous photocatalysts has been
Introduction
Because of its benign properties, such as non-toxicity and non- explored. However, the carboxylation of SP2C–H/X has not yet
flammability, carbon dioxide is an abundant, economical and been widely explored using heterogeneous photocatalytic
renewable C1 building block. Carboxylation of carbon nucleo- systems.15,16 Jain reported the carboxylation of styrene and aryl
philes with CO2 provides a straightforward approach for obtaining halides using a Ru-based metal complex hybridized with Ni/NiO
carboxylic acid functional groups.1–4 Indeed, carboxylic acids and nanoparticles as a heterogeneous photocatalyst (Scheme 1).
their derivatives are utilized as profitable synthetic compounds
and are the most important intermediates in the pharmaceutical
and chemical industries.5–10 The activation of CO2 is highly energy
consuming due to its thermodynamic and kinetic stability.11
However, in the field of photosynthesis, single-electron reduction
of CO2 using light is feasible and has been extensively studied.12
Carboxylation of aryl derivatives with the photocatalytic use of
CO2 has drawn much attention, as carboxylic acid groups can be
directly accessed without the need for multi-step reactions.13 To
avoid the use of traditional organometallic reagents, such as
organolithium or Grignard reagents, aryl halides have been
extensively used as a coupling partner for aryl carboxylation. In
the context of thermal catalysis, Martin and co-workers used
Pd(OAc)2 to carboxylate aryl bromides with CO2. It is worth noting
that all of these processes need metal to reduce CO2.14 Therefore,
an alternative method to carboxylate aryl derivatives is needed.
a Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B.,
India. E-mail: manir65@rediffmail.com; Fax: +91-33-2582-8282;
Tel: +91-33-2582-8750
b King Abdullah Institute for Nanotechnology, King Saud University, Riyadh, 11451,
Saudi Arabia
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
Scheme 1 Carboxylation of C(SP2)–H/X.
d0nj05843b
4738 | New J. Chem., 2021, 45, 4738À4745
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021

View Article Online
Paper
NJC
In this context, covalent organic frameworks (COFs) have Benzoic acid formation process over the porous TpPa-1 COF
recently been shown to be an effective alternative, as a new photocatalyst
group of photoactive heterogeneous materials for light-induced
CO2 reduction was performed photocatalytically in benzoic acid
organic transformations and CO2 reduction.17 Because of their
by the combination of haloarene derivatives (0.1 mmol), 10 mg of
versatile and tunable electronic characteristics, crystallinity,
Ni(dmg)2, triethylamine (TEA, 1 mmol, 0.133 mL) in 5 mL
structure, and porosity, COFs have emerged as a potential
acetonitrile in the presence of 15 mg of COF TpPa-1 in a 25 mL
heterogeneous photocatalyst. Additionally, COFs have effective
round-bottom flask. The reaction was allowed to run under
light harvesting ability and charge transferability, likely
irradiation of blue LED light (445 nm) at room temperature for
because of their p-electron conjugation. In spite of their huge
24 h with nonstop magnetic stirring. After completion of the
reaction, filtration was used to separate COF TpPa-1 and then the
filtrate was dried under vacuum. After evaporation of the solvent,
advantages, COFs have hardly been explored as active photo-
catalysts under visible light for catalytic organic transforma-
tions, aside from CO2 reduction. So, herein, we report the
solid benzoic acid was transferred into a 50 mL two-neck round
carboxylation of aromatic compounds and halides via SP2C–
bottom flask. 1 g of potassium bicarbonate and 20 mL of dry
H/X activation using a suitable COF as the active heterogeneous
acetonitrile were transferred into that round bottom flask; then
photocatalyst with a suitable Ni catalyst under visible light as
methyl iodide was added dropwise over 2 h under continuous
stirring for a further 6 h under an N2 atmosphere. After completion
the energy source.18–21
of the reaction, the product was purified by column chromato-
graphy using 2% ethyl acetate-hexene as the eluent. The formation
of methyl benzoate was confirmed using 1H and 13C nuclear
magnetic resonance (NMR) spectroscopies.
Experimental section
Synthesis of TpPa-1
For the synthesis of TpPa-1, 1.35 mmol (145.8) of para-
phenylenediamine (Pa-1) and 7.5 mmol (1426.5 mg) of para-
toluene sulphonic acid (PTSA) were taken in a mortar and
pestle and evenly grinded for few minutes. After that, 2,4,6-
Results and discussion
Characterization
triformyl phloroglucinol (TFP) (0.9 mmol) was added gradually
Powder X-ray diffraction (PXRD) analysis. The PXRD pattern of
over a period of 15 min, and the reaction mixture was crushed the 2D-COF, namely, TpPa-1, is displayed in Fig. 1. The as-obtained
properly until it turned into a dough-like material. Then 1000– material exhibits two distinct diffraction peaks of moderate inten-
1500 mL of deionized water was mixed in to make the reaction sity, located at diffraction angles of 4.71 and 27.71. Importantly, it
mixture viscous. After that, the paste of COF precursors was can be seen from the PXRD pattern of TpPa-1 that the crystalline
poured into a Teflon-lined steel autoclave and then kept under aspect of the ordered hexagonal COF featuring an intense peak
static conditions in a programmable oven for 6 h at 60 1C and (intensity count of 1409.6) is caused by the (100) facet, located at a
then 10 h at 90 1C. The resulting TpPa-1 COF was transferred diffraction angle of 4.71. It reveals moderate crystallinity owing to
into a succession chamber and washed multiple times with
N,N-dimethylacetamide (DMAc) followed by excess acetone to
remove the unreacted residues. The resulting crude product
was kept under vacuum for 24 h at room temperature to remove
moisture. Finally, the deep-orange TpPa-1 COF was obtained in
85% isolated yield (Scheme 2).
Fig. 1 (a) Small-angle and (b) wide-angle PXRD patterns of the TpPa-1
Scheme 2 Synthesis of TpPa-1.
material.
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
New J. Chem., 2021, 45, 4738À4745 | 4739

View Article Online
NJC
Paper
the decreased rotational freedom of the building blocks. As shown
in Fig. 1b, the obvious hump-shaped peak at a diffraction angle of
26.51 can be ascribed to the existence of p–p stacking between the
aryl groups in the structure of the 2D ordered layered sheets of
COF. This poor peak is caused by the (001) facet. Employing the
Bragg equation (n = 1 for the 100 facets, l = 0.15406 nm and nl =
2dsin y), the measured d spacing value (d100) between the (100)
facets was found to be about 1.87 nm, whereas the interlayer
d-spacing (d001) of the 2D-COF, named TpPa-1, was calculated to be
about 3.20 Å. The determined d spacing between the (001) facets
also corresponds to the p–p stacking distance between the
p-bonded 2D-COF sheets. Intriguingly, the unit cell parameter
determined from the PXRD pattern (a100 = 2.16) is fairly close to
the summation of the wall thickness and pore size, as described in
Fig. 1a.
The poor intensity of the (100) facet of the 2D-COF sheets
may be caused by COF exfoliation.22,23 The breadth of the (001)
facet, owing to stacking between the COF layers, reduces with Fig. 3 (a) FT-IR spectrum of the COF (TpPa-1) material and (b) the
magnified FT-IR spectrum.
an increase in layer number of the obtained COF. The broader
(001) plane of the as-synthesized COF may suggest that the
sample is exfoliated. As described in Fig. 2, PDNLDFT (average
pore diameter) was found to be about 1.9 nm with the help of identical micropores with dimensions of ca. 1.9 nm (inset of
non-local density functional theory (NLDFT). PV (total pore Fig. 2). This outcome is well consistent with previously reported
volume in cm3 gÀ1) was observed to be about 0.278.
work. The as-prepared 2D-COF (TpPa-1) has permanent porosity
with a superior BET surface area and moderate crystallinity.24,25
The decreased surface area can be caused by the partial crystalline
destruction.
WT (wall thickness) = a100 À PDNLDFT
N2 adsorption/desorption isotherm. The N2 isotherm was
obtained at 77 K to gather clear information about the permanent
porosity and BET (Brunauer–Emmett–Teller) surface area of the
synthesized sample. The N2 isotherm of TpPa-1 is presented in
Fig. 2, which represents the combined features of the type I and
type IV patterns. Type I and IV isotherms were fit to this sorption
profile, confirming the microporous and mesoporous features of
the ordered COF. The copious quantity of N2 uptake in the relative
pressure range of 0–0.1 bar indicates that several micropores exist
in the structure of the 2D-COF. Observed from this sorption
profile, the stable pore volume and BET surface area of the 2D-
COF were 0.278 cm3 gÀ1 and 199.83 m2 gÀ1, respectively. The pore
size distribution curve of TpPa-1 was established with the help of
NLDFT to get hidden information about the pattern of pore size
distribution, and the outcome confirms the existence of several
FTIR analysis. The Fourier-transform infrared (FTIR) spectrum
of the synthesized COF material is depicted in Fig. 3. The broad
band at 3420.9 cmÀ1 signifies the N–H bond stretching frequency.
The stretching vibration of hydroxyl groups (O–H) is supposed to
appear at 3200–3600 cmÀ1, which may be overlapped with the
wide N–H band.26 Therefore, the possibility of the presence of
residual –OH groups in the COF framework cannot be ignored.
The sharp peak at 2919 cmÀ1 relates to the C–H stretching
frequency. The intense bands at 1593.1 and 1257.1 cmÀ1 originate
from CQC and CÀN groups, respectively, and this observation
confirms the occurrence of a b-ketoenamine-linked COF structure.
Fig. 2 N2 sorption profile of TpPa-1 material at a specific temperature
Fig. 4 FE-SEM images of the COF (TpPa-1) material at different magni-
(77 K). Pore size distribution curve is displayed in the inset.
fications (a–d).
4740 | New J. Chem., 2021, 45, 4738À4745
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021

View Article Online
Paper
NJC
Fig. 5 Ultra high resolution TEM images of the COF (TpPa-1) material at
different scales: (a) 0.5 mm; (b) 0.1 mm; (c) 20 nm; (d) 0.1 mm; (e) 20 nm; (f) 10 nm.
Fig. 7 Cyclic voltammetry of TpPa-1.
The prominent characterization of the 2D-COF (TpPa-1) was
carried out by XPS, as presented in Fig. 6. Upon deconvolution,
the C 1s spectrum obtained from XPS can be fitted into three
components: the carbon atoms of C–N/C–O (286.3 eV); those of
C–C/CQC (284.6 eV); and those of CQO (289.0 eV) (Fig. 6b). The
N 1s spectrum measured by XPS can be deconvoluted into two
contributions appearing at 403.5 and 400.1 eV, suggesting that
N species exist in the form of C–N linkages (i.e. enamine
nitrogen), as shown in Fig. 6c.27,28 As displayed in Fig. 6d, the
O 1s spectrum suggests that two clearly visible distinct peaks
at binding energies of 531.3 and 533.4 eV can be assigned to the
oxygen atoms of CQO and C–O within the as-prepared 2D-COF,
revealing the existence of keto–enol tautomerism. More intriguingly,
the TpPa-1 material predominantly exists in the keto form. Addi-
tionally, it partially adopts the enol isomer (trace amount).
Microscopic analysis. As observed from the field emission
scanning electron microscopy (FE-SEM) results (Fig. 4), the
micromorphology of TpPa-1 demonstrated that this obtained
COF is made up of multiple asymmetrical rods that are partially
twisted, resulting in the formation of a network structure. The
FE-SEM images of the COF material demonstrate a one-dimen-
sional micro-wire-like morphology of the system. The TEM
images (Fig. 5a and b) suggest that small nano-fibers with
diameters of ca. 0.1–0.16 mm are aggregated together to build
the micro-wire-like network structure. Furthermore, the porous
structure of the material is clearly visible from the high-magnifica-
tion TEM images (Fig. 5c, e and f), which supports the surface area
analysis data.
X-ray photoelectron spectroscopy (XPS) analysis. In order to
find out all the information garnered about the chemical
composition of the obtained samples, XPS was carried out to
prominently characterize the covalently bonded p-conjugated
2D-COF.
Cyclic voltammetry (CV) analysis
CV analysis of the 2D-COF (TpPa-1) was conducted at a scan rate
of 10 mV sÀ1 and domain of À0.3 to 0.4 V in (1 M) sulfuric acid
with the help of a reference electrode (Ag/AgCl) (Fig. 7). The
corresponding reduction potential of the ground state of the
photocatalyst TpPa-1 was estimated (E1/2 = 0.0112 V vs. Ag/AgCl).
Using the ground state reduction potential of COF TpPa-1
(E1/2 = 0.011 V vs. Ag/AgCl), the excited state oxidation potential
Table 1 Deviations from the optimal reaction conditionsa
TpPa-1
(mg)
Co-catalyst
(5 mol%)
Yieldb
(%)
Entry
hv (nm)
Temp. (1C)
1
2
3
4
5
6
7
5
5
—
5
5
2
5
—
455
—
455
455
455
455
Sunlight
25
25
25
60
80
25
25
21
0
0
87
88
56
32
Ni(dmg)2
Ni(dmg)2
Ni(dmg)2
Ni(dmg)2
p-Terphenyl
Ni(dmg)2
a
Fig. 6 XPS survey scan measurement on TpPa-1 (a), C 1s narrow scan (b),
N 1s narrow scan (c) and O 1s narrow scan measurement (d) on the as-
synthesized 2D-COF (TpPa-1).
All reactions were performed with 0.5 mmol (0.056 mL) of the substrate
under 1 atm of CO2. Calculated from 1H NMR spectra using triphenyl-
methane as the internal standard.
b
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
New J. Chem., 2021, 45, 4738À4745 | 4741

View Article Online
NJC
Paper
Table 2 Substrate scope for aryl halidesa
Table 2 (continued)
Yieldb (%)
86
Entry
11
Substrates
Products
Yieldb (%)
Entry
1
Substrates
Products
76
2
3
91
88
12
70
a
All reactions were carried out with 0.5 mmol of substrate, TpPa-1 (5
mg), Ni(dmg)2 (5 mol%), CO2 (1 atm), TEA (1 eq.), MeCN (5 mL).
b
Calculated for the 1H-NMR spectra using triphenylmethane as the
internal reference.
4
5
90
81
for COF TpPa-1 was estimated from the emission maxima of
the normalized emission spectra (581 nm). E1/2(PSꢀ+/PS*) =
À2.114 V vs. Ag/AgCl was also obtained.
Catalysis
The COF TpPa-1 photocatalyst (5 mg), along with the Ni(dmg)2
co-catalyst (5 mol%), was initially investigated for the carboxyl-
ation of iodobenzene (0.5 mmol) with CO2 (1 atm) under visible
light irradiation, by employing 20 W blue light under continuous
stirring for 5 h using acetonitrile as a solvent and triethylamine
(TEA) as a sacrificial electron source. The formation of the
carboxylated product was initially confirmed with 13C NMR by
monitoring the peak at 172 ppm. To determine the yield and to
isolate the product, methyl esterification using K2CO3 and MeI in
the same solution was applied after the catalytic run. The yield of
the products was determined from 1H NMR using triphenyl-
methane as the internal reference. Under this reaction condition,
iodobenzene was converted to benzoic acid with 86% yield
6
7
8
78
75
72
1
calculated from H NMR spectra.
To further improve the yield of the carboxylation product
and determine the role of other reaction parameters, it was
necessary to screen more co-catalysts and reaction conditions.
It was observed that without the use of any co-catalyst, only
21% of the methyl esters of the carboxylated products could be
obtained from iodobenzene (Table 1, entry 1). Without the use
of light, there was no formation of the products, indicating the
exclusive dependency on light for the progress of the reaction
(Table 1, entry 2). Again, the role of the photocatalyst COF,
TpPa-1, was confirmed by carrying out one reaction without it,
in which there was no formation of product (Table 1, entry 3).
9
82
74
10
4742 | New J. Chem., 2021, 45, 4738À4745
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021

View Article Online
Paper
NJC
To improve the reaction yield and to determine the role of and –OCH3 substrates produced the products with slightly
temperature, two reactions were carried out at the elevated reduced yields (Table 2, entries 5 and 6). This catalytic protocol
temperatures of 60 1C and 80 1C (Table 1, entries 4 and 5). works well with other halides such as Cl and Br. Aryl bromides
Surprisingly, upon elevation of temperature, a slight improve- with both electron-withdrawing and donating groups as sub-
ment in the product yield was observed, eliminating the role of stituents produced the corresponding products in good to
temperature. Since p-terphenyl is a commonly used co-catalyst moderate yields (Table 2, entries 7 and 8). Likewise, aryl chlorides
in homogeneous photocatalysis for carboxylation, it was used were also very effective in producing the products in good to
in our reaction too. However, a drop in the yield of the product moderate yields (Table 2, entries 10–12).
was observed (Table 1, entry 6). This could be due to the
Next, we applied our catalytic system to the carboxylation of
mismatch in the redox potential values of p-terphenyl and benzene derivatives by C(SP2)–H activation. Although carboxylation
COF TpPa-1. When the reaction was exposed to sunlight for of the C(SP2)–H bond is difficult compared to the C(SP2)–X bond,
24 h, 32% yield was noticed (Table 1, entry 7). This may be due with this catalytic system the benzene derivatives were able to
to the low intensity of the light. So, from these control experi- produce the corresponding products in good yields. Benzene and
ments, we observed that 5 mg of TpPa-1, along with 5 mol% nitrobenzene produced the corresponding products in 68% and
Ni(dmg)2 at 25 1C using TEA as a sacrificial electron source in 70% yield, respectively (Table 3, entries 1 and 2).
acetonitrile under a 20 W blue LED, are the optimum reaction
conditions.
Mechanism
With the optimized reaction conditions in hand, the substrate
generality of the reaction was examined using various functiona-
A possible mechanism of this light-dependent carboxylation of
lized aryl iodides, bromides and chlorides (Table 2). Aryl iodides
aryl-X/H to form the corresponding carboxylic acids is depicted
bearing electron-withdrawing (–NO2) and electron-donating
in Fig. 8. Upon photo-excitation, TpPa-1 goes into a photo-excited
groups (–CH3, –OCH3) were examined. Substrates containing the
ꢀ
state (EPS
= À2.114 V vs. Ag/AgCl). Upon reducing Ni(II) to
+/PS*
electron-withdrawing group –NO2 produced the corresponding
esters with slightly improved yields (Table 2, entries 2–4). How-
ever, substrates containing the electron-donating groups –CH3
Ni(0), it comes back to the ground state by oxidative quenching.
After relaxation, upon accepting an electron from TEA (E1/2
=
À2.5 V vs. Ag/AgCl) TpPa-1 becomes regenerated. Then, upon
excitation, it undergoes additional reaction cycles. During the Ni
Table 3 Substrate scope for the C–H activation productsa
Entry
1
Substrates
Products
Yieldb (%)
68
2
3
70
62
Fig. 8 Proposed mechanism of photocatalytic carboxylation.
4
60
a
All reactions were performed with 0.5 mmol of the substrates, TpPa-1
(5 mg), Ni(dmg)2 (5 mol%), CO2 (1 atm), TEA (1 eq.), MeCN (5 mL).
b
Calculated for the 1H NMR spectra using triphenylmethane as the
Fig. 9 Recyclability study.
internal reference.
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
New J. Chem., 2021, 45, 4738À4745 | 4743

View Article Online
NJC
Paper
catalytic cycle, the oxidative addition of Ar–X takes place, converting Grant Commission (UGC) New Delhi, India for providing support
Ni(0) to Ni(II). Eliminating XÀ, Ni(II) is restored to Ni(I). Upon further to the Department of Chemistry, the University of Kalyani under
insertion of CO2 into Ni(I) and elimination of ArCOOÀ, the Ni(0) the FIST and SAP programs. P. Chakrabortty is thankful to
catalyst gets regenerated for further cycles. When the reaction was SVMCM, WB GOVT for her fellowship. S. M. I. is thankful to
carried out in presence of TEMPO (radical inhibitor), there was no the University of Kalyani for his personal research grant. A. H.
formation of the product, confirming the radical pathway of the Chowdhury is thankful to the University of Kalyani for her URS
reaction. This could indicate the formation of a complex with fellowship. We are grateful to the Department of Science and
+
TpPa-1ꢀ and TEMPO, deactivating the catalyst.
Technology (DST) New Delhi, India for providing support to the
University of Kalyani under the PURSE program.
Recyclability of the TpPa-1 COF
catalyst
References
To carry out the recycling experiment, iodobenzene was
selected as the model substrate under the optimized reaction
conditions. On completion of the reaction, the COF, TpPa-1,
was isolated and purified by washing it multiple times with
acetonitrile. Surprisingly, we noticed no important alteration in
its activity in terms of isolated yield. Therefore, this recycling
experiment was repeated up to five times without any consider-
able reduction in the activity (Fig. 9). This study demonstrates
the industrial importance of TpPa-1 as a photocatalyst for
carboxylation reactions.
1 P. Braunstein, D. Matt and D. Nobel, Chem. Rev., 1988, 88,
747–764.
2 T. Sakakura, J.-C. Choi and H. Yasuda, Chem. Rev., 2007,
107, 2365–2387.
3 T. Sakakura and K. Kohno, Chem. Commun., 2009, 1312–1330.
4 Q. Liu, L. Wu, R. Jackstell and M. Beller, Nat. Commun.,
2015, 6, 5933–5947.
´
5 A. Correa and R. Martın, Angew. Chem., Int. Ed., 2009, 48,
6201–6204.
6 K. Huang, C.-L. Sun and Z.-J. Shi, Chem. Soc. Rev., 2011, 40,
Conclusions
2435–5224.
´
7 R. Martın and A. W. Kleij, ChemSusChem, 2011, 4,
In summary, the photocatalytic carboxylation of C(SP2)–X/H
with CO2 was demonstrated utilizing the TpPa-1 COF as the
active photocatalyst together with Ni(dmg)2 as a co-catalyst. The
reaction proceeds with excellent yield under 1 atm pressure of
CO2 along with visible light irradiation. Control experiments
demonstrate that the reaction does not progress in the absence
of the co-catalyst. Furthermore, even elevated temperatures
cannot start the reaction under dark conditions. Therefore,
the reaction can be readily controlled by light alteration. A detailed
study for the mechanism of photocatalytic CO2 fixation has been
established with spectroscopic analysis. Furthermore, the photo-
catalyst is also easily recoverable and reusable for up to five cycles
without being deactivated.
1259–1263.
8 Y. Tsuji and T. Fujihara, Chem. Commun., 2012, 48,
9956–9964.
¨
9 M. Borjesson, T. Moragas, D. Gallego and R. Martin, ACS
Catal., 2016, 6, 6739–6749.
10 Y.-Y. Gui, W.-J. Zhou, J.-H. Ye and D.-G. Yu, ChemSusChem,
2017, 10, 1337–1340.
11 S. P. Bew, in Comprehensive Organic Functional Groups
Transformation II, ed. A. R. Katritzky and R. J. K. Taylor,
Elsevier, Oxford, UK, 2005, p. 19.
12 L. J. Goosen, N. Rodriguez and K. Goosen, Angew. Chem., Int.
Ed., 2008, 47, 3100–3120.
13 A. Correa and R. Martin, Angew. Chem., Int. Ed., 2009, 48,
6201–6204.
14 H. Maag, Prodrugs of Carboxylic Acids, Springer, New York,
NY, USA, 2007, pp. 703–729.
15 Q.-Y. Meng, S. Wang and B. Konig, Angew. Chem., 2017, 56,
13426–13430.
Conflicts of interest
There are no conflicts to declare.
16 K. Shimomaki, K. Murata, R. Martin and N. Iwasawa, J. Am.
Chem. Soc., 2017, 139, 9467–9470.
Acknowledgements
S. M. I. acknowledges the Department of Science and Technology, 17 (a) S. Saini, H. Singh, P. K. Prajapati, A. K. Sinhaand and
DST-SERB (project reference no. CRG/2020/000244), New Delhi,
Board of Research in Nuclear Sciences (BRNS), Project reference
no. 37(2)/14/03/2018-BRNS/37003, Govt. of India, for providing
financial support. A. Das is grateful to the University Grants Com-
S. L. Jain, ACS Sustainable Chem. Eng., 2019, 7, 13; (b) A. Das,
R. K. Mondal, P. Chakrabortty, S. Riyajuddin, A. H. Chowdhury,
S. Ghosh, A. Khan, K. Ghosh and S. M. Islam, Mol. Catal., 2021,
499, 111253.
mission for D. S. Kothari’s postdoctoral fellowship (Award letter no. 18 J. Schneider, H. Jia, J. T. Muckerman and E. Fujita, Chem.
F.4-2/2006(BSR)/CH/18-19/0010). A. K. thanks the Researchers Sup- Soc. Rev., 2012, 41, 2036–2051.
porting Project (Grant no. RSP-2021/127), King Saud University, 19 E. B. Cole, P. S. Lakkaraju, D. M. Rampulla, A. J. Morris,
Riyadh, Saudi Arabia for financial support. We acknowledge the
Department of Science and Technology (DST) and the University
E. Abelev and A. B. Bocarsly, J. Am. Chem. Soc., 2010, 132,
11539–11551.
4744 | New J. Chem., 2021, 45, 4738À4745
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021

View Article Online
Paper
NJC
20 J. Low, L. Zhang, B. Zhu, Z. Liu and J. Yu, ACS Sustainable 25 S. Karak, S. Kandambeth, B. P. Biswal, H. S. Sasmal,
Chem. Eng., 2018, 6, 15653–15661.
S. Kumar, P. Pachfule and R. Banerjee, J. Am. Chem. Soc.,
2017, 139, 1856–1862.
21 P. Sarkar, S. Riyajuddin, A. Das, A. H. Chowdhury, K. Ghosh
and S. M. Islam, Mol. Catal., 2020, 484, 110730.
22 H. Wei, S. Chai, N. Hu, Z. Yang, L. Wei and L. Wang, Chem.
Commun., 2015, 51, 12178–12181.
23 X. Mu, J. Zhan, J. Wang, W. Cai, B. Yuan, L. Song and Y. Hu,
J. Colloid Interface Sci., 2019, 539, 609–618.
26 (a) S. Ghosh, T. S. Khan, A. Ghosh, A. H. Chowdhury,
M. A. Haider, A. Khan and S. M. Islam, ACS Sustainable Chem.
Eng., 2020, 8, 5495–5513; (b) M. Sengupta, A. Bag, S. Ghosh,
P. Mondal, A. Bordoloi and S. M. Islam, J. CO2 Util., 2019, 34,
533–542; (c) P. Sarkar, A. H. Chowdhury, S. Riyajuddin, S. Biswas,
K. Ghosh and S. M. Islam, New J. Chem., 2020, 44, 744–752.
24 (a) S. Ghosh, R. A. Molla, U. Kayal, A. Bhaumik and
S. M. Islam, Dalton Trans., 2019, 48, 4657–4666; (b) S. Sarkar, 27 T. I. T. Okpalugo, P. Papakonstantinou, H. Murphy,
S. Ghosh, J. Mondal and S. M. Islam, Chem. Commun., 2020, J. McLaughlin and N. M. D. Brown, Carbon, 2005, 43, 153–161.
56, 12202–12205; (c) R. Khatun, S. Biswas, I. H. Biswas, 28 A. P. Dementjev, A. De Graaf, M. C. M. Van de Sanden,
S. Riyajuddin, N. Haque, K. Ghosh and S. M. Islam, J. CO2
Util., 2020, 40, 101180.
K. I. Maslakov, A. V. Naumkin and A. A. Serov, Diamond
Relat. Mater., 2000, 9, 1904–1907.
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
New J. Chem., 2021, 45, 4738À4745 | 4745