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COMMENT View Journal | View Issue

Reply to the ‘Comment on ‘‘CO2 as oxidant:

an unusual light-assisted catalyst free oxidation
Cite this: Chem. Commun., 2023,
59, 14036 of aldehydes to acids under mild conditions’’’
by S. R. Khan, S. Saini, K. Naresh, A. Kumari,
V. Aniya, P. K. Khatri, A. Ray and S. L. Jain, Chem.
Commun., 2022, 58, 2208
Shafiur Rehman Khan,a Sandhya Saini,ab K. Naresh,c Alka Kumari,c Vineet Aniya,c
Praveen K Khatri,a Anjan Ray d and Suman L Jain *a
Received 5th September 2023,
Accepted 24th October 2023 Our recent Communication (S. R. Khan et al., Chem. Commun., 2022, 58, 2208) suggested that CO2 can be
DOI: 10.1039/d3cc04389d used as a potential oxidant under light irradiation without using any catalyst for the oxidation of aldehydes to
acids at room temperature. The Comment based on the published literature on the catalytic oxidation of
rsc.li/chemcomm aromatic aldehydes by CO2 and thermodynamical data argued on the realism of the experimental data.

A recent experimental study1 on the catalyst-free oxidation of concluded that atmospheric O2 improved the product yield,
aldehydes to acids with CO2 reported the potential use of CO2 which speculates the role of CO2 as an actual oxidant. However,
as an oxidant under light irradiation along with the production it was a thermocatalytic reaction and the solvent system was
of CO as the effluent gas. The experimental data suggested the undeniably different from our studies. Another quoted study
crucial role of light in CO2 activation as well as the acetonitrile reported by Kakotos et al.5 demonstrated catalyst-free oxidation
solvent. It also proposed a mechanism elucidating the photo- of aromatic aldehydes to acids in the acetone solvent using
lysis of benzaldehyde to benzoyl radicals (Norish type I) as the 43 W LED 370 nm and O2 as a terminal oxidant. The high-
initial step followed by a solvent-assisted interaction with CO2 lighted conditions are entirely different from our system and a
to give acid and by-product CO. A Comment on this study comparison of these points based on fundamentally different
(A. Favre-Réguillon, Chem. Commun., 2023, submitted) argued reaction conditions seems irrational.
against this interpretation on the basis of the reported litera- In addition, several studies provided evidence that light
ture on the catalytic oxidation of aromatic aldehydes by CO2, could promote radical chemistry under catalyst-free conditions.
photo-activation of aldehydes and thermocatalytic data. The fundamental difference between thermal and light-driven
In this Reply, we would humbly state that despite thermo- reactions lies in the nature of electronic transition. Most
dynamic restrictions imposed on a thermally excited system, thermally catalyzed reactions proceed via electron pair transfer
the reaction is feasible under a light excited system. Indeed, the (ionic), while light driven reactions usually involve free radicals
studies reported by Zhang et al.2 and Nair et al.3 used for the or free radical ions as active intermediates. It is worth reiterat-
comparison were performed at room temperature and in the ing that, many thermocatalytically forbidden reactions can
presence of NHC/base and pressurized CO2. The studies proceed under light irradiation due to a change of the spin
reported by Bode et al.4 investigated the influence of CO2, air state. As an example, the reaction between ground state triplet
and N2 on the reaction product yield using identical conditions O2 and singlet CH4 is highly unfavorable and requires a high
to those mentioned in the studies of Zhang et al.2 They temperature, however under visible light and using a catalyst
the reaction can proceed at room temperature.6 Since, under
a
Chemical & Material Sciences Division, CSIR-Indian Institute of Petroleum, photocatalytic conditions, the reaction proceeds through dif-
Haridwar Road, Mohkampur, Dehradun-248005, India. E-mail: suman@iip.res.in; ferent intermediates, the DFT calculations and the calculated
Tel: +911352525788 energy barrier by Wang et al. are not completely valid for our
b
Academy of Scientific and Innovative Research, Ghaziabad, 201002, India
c
study.7 Even if we consider that the reaction proceeds through
Process Engineering Technology Transfer Division, CSIR-Indian Institute of
Chemical Technology, Hyderabad-500007, India
identical intermediates, the maximum barrier height for alde-
d
Director, CSIR-Indian Institute of Petroleum, Haridwar Road, Mohkampur, hyde conversion is easily surmountable by excitation of visible
Dehradun-248005, India light (510 nm = 2.42 eV = 233 kJ mol1). We agree that CO2 is a

14036 | Chem. Commun., 2023, 59, 14036–14039 This journal is © The Royal Society of Chemistry 2023
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Comment ChemComm

quite stable molecule with a 394 kJ mol1 standard free energy

 
On reported oxidation of aldehydes
of formation DGf , and therefore its direct conversion to CO is using CO2 as the oxidant
challenging. However, a proton-assisted step-wise reduction
requires a much lower value (–0.53 eV = 51.13 kJ mol1). Photo- The Comment argues for the catalytic reduction of carbon
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catalytic CO2 reduction is actually towered on this concept where dioxide to carbon monoxide using aromatic aldehydes as
water oxidation provides electrons and protons for the CO2 reductants under various conditions. In reply to this comment,
reduction to CO/hydrocarbons. we humbly state that the report by Zhang et al.2 and Nair et al.3
We also agree in light of existing isotopic labelling studies utilize NHC/base/pressurized CO2 under thermal/room tem-
using 18O2 and DFT calculations that the CO2-driven oxidation perature conditions for the conversion of aldehydes to acids.
reaction is challenging and therefore should be investigated On the other hand, we have used LED irradiation for the
more intrinsically. activation of CO2. Considering the energy input, the direct
Our study is mainly focused on experimental findings and conversion of CO2 to CO is highly endothermic (free energy of
 
we agree that an isotopic tracing experiment with isotope formation DGf = 394 kJ mol1) and not feasible under
labelled C18O2 would be the most strongest evidence to justify thermal conditions. The photon energy of 510 nm wavelength
this oxidation chemistry. Owing to the unavailability of this light can be translated to 2.43 eV (1238/516) or 239 kJ mol1
isotopic C18O2 and limitations to procure the isotopic com- (1 eV = 96.48 kJ mol1), which is still not enough to activate
pounds on urgent basis we could not perform this experiment; CO2. Indeed CO2 activation by one electron transfer is highly
whereas, to elucidate the reaction mechanism we performed unfavourable and requires 1.9 eV + 0.6 eV (overpotential). On
additional experiments with the available 13CO2. In this regard the other hand, proton- and electron-assisted reduction of
following controlled experiments were carried out: (i) photo- CO2 occurs at much lower energy. For example, CO2 to CO
lysis of benzaldehyde in acetonitrile without adding CO2 under conversion using 2 protons and 2 electrons requires 0.53 eV
visible light irradiation for 4 h to check the possible decarbo- (51.1 kJ mol1). Therefore light-assisted reduction of CO2 is
nylation; (ii) photochemical reaction of benzene with 13CO2 in feasible given protons and electrons are available from external
the acetonitrile solvent under described conditions to check the sources. It is well reported that aldehyde undergoes photolysis
carboxylation; and (iii) addition of TEMPO as a radical trapping under irradiation conditions via the formation of singlet to
agent in the reaction mixture containing benzaldehyde, CO2 triplet states. This triplet state after losing the H atom forms an
and acetonitrile under light irradiation. acyl radical anion (Scheme 2).9,10 Even the studies reported by
In the first reaction unreacted benzaldehyde along with a Kakotos et al.6 mentioned the formation of acyl radicals by
mixture of benzoin and benzil (about 12%) was obtained, suggest- photolysis. This singlet state generates acyl radicals and loses a
ing that decarbonylation did not occur under the experimental H, which might be solvated by polar aprotic acetonitrile. The
conditions. Instead, the formation of benzoin and benzil by-
products supported the generation of intermediate benzoyl radi-
cals, which is in good agreement with existing literature.8 In the
second experiment unreacted benzene was recovered without any
evidence for the formation of a carboxylated product. In the third
experiment, the formation of a quantitative amount of benzoyl-
TEMPO adduct suggested the generation of benzoyl radicals from
photolysis of benzaldehyde that was trapped by TEMPO. These
controlled experiments ruled out the possibility of decarbonyla-
tion followed by the carboxylation reaction. Based on these results
we proposed the mechanism of the reaction as shown in
Scheme 1 and concluded that the desired oxygen for conversion
of aldehyde to acid was derived from CO2 along with the simulta-
neous production of CO in the gaseous phase.

Scheme 2 Proposed mechanism for the hydroacylation of Michael

Scheme 1 Proposed reaction mechanism. acceptors using 4-cyanobenzaldehyde as the photoinitiator.

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ChemComm Comment

formed acyl radical can donate electrons to CO2, while solvated

H is supplied by acetonitrile resulting in the reduction of CO2 to
CO. However, the exact mechanism of the reaction between
CO2 and acyl radicals is not known at this stage. The insertion
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of CO2 can be a leading step. Many metal complex-assisted CO2

reductions also follow similar CO2 insertion steps.11,12 Like the
proposed schemes for metal complexes, CO2 can coordinate
with acyl radicals via electron-deficient C sites followed by Scheme 3 The spectral distribution of sunlight, a white cold LED and a
fluorescent lamp. Source: https://www.lumistrips.com/lumistrips-blog/
abstraction of solvated hydrogen. The formed intermediate cri-explained/.
state, after CO removal will generate formate (benzoic acid).

might help in the H abstraction and solvation during photolysis

followed by a reaction with CO2.
On light-assisted aerobic oxidation of
aldehydes to carboxylic acids
The Comment argues about the aerobic light-promoted oxida-
On thermodynamic stability of CO2
tion of aldehydes to carboxylic acids under photocatalyst-free and feasibility of the reaction
conditions using different light sources and solvents.
The Comment questioned about the thermodynamic feasibility
In reply to this comment, we would like to highlight that the
of the reaction based on the thermodynamic data calculated
study reported by Kakotas et al.6 utilized aerobic conditions for
using the NIST data.15 Here, we fully agree that based on the
the oxidation of benzaldehyde in a different solvent system,
provided calculations, the reaction is nonspontaneous and
while our reactions were performed in CO2 and acetonitrile.
endothermic (+6.4 kJ mol1). However, as we mentioned ear-
The O2-assisted activation of aldehyde to acid involves direct
lier, visible light-irradiation can overcome this barrier. The
reduction of O2 to superoxide radical species, which attacks on
510 nm wavelength can be translated to 2.43 eV (1238/516) or
aldehyde to generate acid. The superoxide anion radicals can be
239 kJ mol1 (1 eV = 96.48 kJ mol1). This energy is enough to
easily quenched by nitrogen in the air and therefore a lower
surmount the calculated energy barrier (+6.4 kJ mol1). Since
population is available for the reaction, which concomitantly
the thermal system loses tremendous energy before reaching a
afforded a lower yield.13,14 It should be noted that N2 is not a
threshold, this barrier is big enough for room temperature
direct scavenger but suppresses the formation of superoxide
transition. Distinctly, under irradiation conditions reaction can
radicals by replacing O2 from the solution. Another element of
proceed theoretically. However, the fact cannot be denied that
variation is the irradiation source. We have used a 20 W white
the reaction requires proton abstraction and CO2 activation,
cold LED light (Model no. HP-FL-20W-F, Hope LED Opto-
which have high energy barriers. Indeed, the reduction of CO2
Electric Co., Ltd. Specification – Chip: KWE, Bridgelux, Epistar
molecules with one electron is highly unfavorable due to
COB LED, 20 W), which has a luminous output of 80–90 lm W1
electronic repulsion between the newly occupied orbital and
(https://hopeled.en.made-in-china.com/product/sMWxzcUHXKRV/
the O 2p orbital in a bent structure. The one electron reduction
China-High-Power-20W-LED-Flood-Light-HP-FL-20W-.html). This
potential for CO2 is 1.9 eV and an over potential of 0.6 eV is
is a street LED with a high intensity compared to household
also required.
LEDs (B5–10 W m2). The calculated power density on the
So total energy required for CO2 reduction is 2.5 eV =
surface of the vessel was 75 W m2, which was significantly
246 kJ mol1.
higher. Contrarily, monochromatic LEDs usually have low
However, proton- and electron-assisted CO2 reduction can
luminescence intensity. The specifications provided by the
occur at much lower energy. As can be seen from Scheme 4 CO2
supplier are wavelength l 4 400–700 nm (maximum at
to CO transformation requires 0.53 eV or 51.1 kJ mol1.
510 nm), which means it is a blend of different wavelengths
This energy can be supplied by visible light. Below, we
of radiation with a maximum wavelength contribution of
have provided the calculation of standard reduction potential
510 nm. For a comparison, we have provided the spectral
(energy in kJ mol1).16
distribution of a cold LED in Scheme 3. Since the intensity of
light was much higher than reported we observed a high
product yield in a short time. Additionally, the presence of
short wavelength light in the spectrum will promote photolysis
of aldehyde to generate acyl radicals, which can react with CO2
to form acid. As explained in the response to the third com-
ment, the energy barrier for the electron- and proton-assisted
CO2 reduction is much lower therefore acyl radicals can activate
CO2 to generate CO and acid. Though at this stage the exact role Scheme 4 Standard CO2 reduction potentials of various products at the
of acetonitrile is not clear, its high polarity and aprotic nature NHE scale and at pH7.

14038 | Chem. Commun., 2023, 59, 14036–14039 This journal is © The Royal Society of Chemistry 2023
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Comment ChemComm

The standard reduction potential for a reaction can be and Industrial Research (CSIR), New Delhi is acknowledged for
 
calculated with the help of the standard free energy DGf of the fellowship of SS and FBR project MLP 1165 scheme.
formation as given below:
Published on 02 November 2023. Downloaded by King Abdullah Univ of Science and Technology on 6/20/2025 6:28:41 AM.

The equation for the CO2 to CO reduction reaction of CO2 +

2H+ + 2e - CO for H2O can be written as:
References
CO2(g) + H2(g) - CO(g) + H2O(l) (1)
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This journal is © The Royal Society of Chemistry 2023 Chem. Commun., 2023, 59, 14036–14039 | 14039