pubs.acs.

org/acscatalysis Research Article

Synergistic Effects of Co−Fe Boosts the Transformation of CO2 into

C6+ Dicarboxylic Acids up to Gram-Scale under Mild Conditions
Ying Zhang,*,∇ Junjun Mao,∇ Bo Zhang, Dan Wang, Chenchen Zhang, Yang Lou, Chengsi Pan,
and Yongfa Zhu
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ABSTRACT: Electrochemical carboxylation of 1,3-dienes with

carbon dioxide (CO2) is a feasible method to obtain dicarboxylic
derivatives, which are important synthetic intermediates of
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polymers and pharmaceuticals. However, due to unavoidable

byproducts and unfriendly conditions, the formation of pure
dicarboxylic acids has been limited. In this work, we report that a
bimetallic phosphating CoFeP catalyst on nickel foam (CoFeP/
NF) served as a remarkable electrode, which transforms CO2 into
multicarbon (C6+) dicarboxylic acids. The synergistic effects of
CoFeP catalyst between Co and Fe allow activation of 1,3-dienes
mainly, in which electron transfer easier to the 1,3-dienes
proceeded to afford radical anion of the diene, pursuant
carboxylation with CO2 and further electron transfer formed the ultimate carboxylated products. The reaction can occur in a
commercial flow cell with gram-scale amplification. The dicarboxylic acid obtained was up to 1.08 g at a 5 mmol scale of 1,3-dienes,
illustrating high electrocatalytic activity and practical application of CoFeP/NF.
KEYWORDS: bimetallic catalyst, CO2 conversion, 1,3-dienes carboxylation, organic electrosynthesis, gram-scale amplification

1. INTRODUCTION Electrochemical carboxylation with CO2 has been identified as

CO2 is deemed as the main greenhouse gas in the atmosphere, one of the most sustainable and competent approaches to
and it is also featured as an inexpensive, nontoxic, and access highly value-added carboxylic acids5 from olefins,15
alkynes,16 carbonyl compounds,17 or halogenated com-
attractive one-carbon (C1) building block.1,2 The carboxyla-
pounds.18 Remarkably, the electrocarboxylation of 1,3-dienes
tion of organic compounds using CO2 as a C1 source is a vital
to produce dicarboxylic acids such as adipic acid, which is one
strategy to obtain value-added carboxylic derivatives, which
of the most crucial industrial chemicals, has become a hot topic
exist in natural products and pharmaceuticals.3−6 Nevertheless,
in electrochemical organic synthesis for several decades.19 But
due to the thermodynamic stability and kinetic inertia of CO2,7
1,3-dienes electrocarboxylation still needs high-pressure CO2
numerous transition-metal catalysts and reagents have been
and metal homogeneous catalysts are usually applied to this
applied to catalyze the CO2 carboxylation,8 such as organo-
reaction.20−22 Meanwhile, there are some side products that
metallic nucleophiles,9 and Grignard reagents.10 But those
are obtained during the electrocarboxylation, which include
species are comparatively expensive and usually lead to poor
monocarboxylates and dimers.23 Therefore, exploiting a mild
selectivity of products or low atomic utilization.11 Notably,
route to get ideal diacid products with high selectivity is of
most carboxylation reactions that use transition metals as the
great importance for the electrochemical carboxylation of 1,3-
catalyst, need stoichiometric metal reagents ground on Zn or
dienes with CO2.
Mn as reducing agents, causing the final product separation
Cathode materials play a significant role in this process.24
and environmental concerns.12 From the green chemistry
Recently, nanostructured catalysis has attracted significant
perspective, mild and nontoxic reaction conditions should be interest in highly efficient electrocarboxylation, because of its
developed to replace the use of those metal reducing agents.13
Electrochemical methods allow direct redox reactions to
occur at the electrode surface to avoid the use of noxious and Received: November 9, 2023
pernicious redox reagents and the applied potential could be Revised: November 29, 2023
changed flexibly to active organic chemicals and CO2 required Accepted: December 15, 2023
highly negative reduction potentials; additionally, electricity as
a driving force can improve the sustainability of the reaction,
reproduced via renewable origin, such as solar or wind.14

© XXXX American Chemical Society https://doi.org/10.1021/acscatal.3c05395

1459 ACS Catal. 2024, 14, 1459−1467
ACS Catalysis pubs.acs.org/acscatalysis
microscopic hierarchical structure and surface properties. Lu et
al. prepared Ag NPs as cathode material for electrochemical
carboxylation of 2-phenyl bromide, which could acquire 98%
of 2-phenyl propionic acid.25 In addition, he and his colleagues
also described a bifunctional platinum/nitrogen-doped car-
bon/carbon cloth catalyst for the halide electrochemical
carboxylation with exclusive Faradaic efficiency of producing
2-phenyl propionic acid.26 But those electrocatalysts are mostly
noble metals, which are limited by their exorbitant price and
the scarce reserve.27 Therefore, many low-cost transition-metal
phosphide electrocatalysts afford opportunities.28−31 However,
these electrocatalysts have rarely been reported in the area of
the CO2 electrochemical carboxylation reaction.
In our work, we directly synthesized a bimetallic phosphide
CoFeP on NF using a simple one-step hydrogen bubble
electrodeposition technique. The CoFeP catalyst was demon-
strated as an efficient bimetallic catalytic material for 1,3-dienes
electrocatalytic carboxylation with CO2, and the conversion of
1,3-dienes could be up to 81% with excellent yields (61.9%) of
the dicarboxylic acid products. When the CoFeP catalyst was
used in the system of 1,3-dienes electrocarboxylation with
CO2, it not only significantly achieved the conversion of CO2
to form multicarbon (C6+) dicarboxylic acids, but allowed the
reaction to occur under mild conditions without extra reducing
agents and high pressure. In addition, there are no
homogeneous catalysts required in this method, which
distinguishes our work from most reported works regarding
electrocarboxylation, which could avoid the hard separation
between the product and metal catalysts. More importantly,
there are rarely catalysts that are suitable for the industrial 1,3-
dienes electrocarboxylation process. When the reaction
occurred in a commercial flow cell using the CoFeP catalyst,
the quantity of dicarboxylic acid can reach 1.08 g. This work
presented the first example of applying CoFeP/NF as the
electrocatalyst in the CO2 electrocarboxylation under mild
reaction conditions, producing multicarbon (C6+) dicarboxylic
acids.
2. EXPERIMENTAL SECTION
2.1. Experimental Materials and Reagents. All reagents
are analytically pure and could be used directly without further
purification. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O,
≥99.0%) was obtained from Adamas Reagent Co., Ltd. Ferrous
chloride (FeCl2, 99.5%) was purchased from Shanghai Aladdin
Biochemical Technology Co., Ltd. Besides, anhydrous sodium
dihydrogen phosphate (NaH2PO4, ≥99.0%), ammonium
chloride (NH4Cl, ≥99.5%), sodium acetate (CH3COONa,
99.0%), sodium chloride (NaCl, ≥99.5%), hydrochloric acid
(HCl, AR), acetone (C3H6O, ≥99.5%), absolute ethanol
(C2H5OH, ≥99.7%), and sodium sulfate (Na2SO4, ≥99.0%)
were purchased from Sinopharm Chemical Reagent Co., Ltd.
Trans,trans-1,4-diphenyl-1,3-butadiene (1a) was purchased
from Tokyo Chemical Industry (Shanghai) Development
Co., Ltd. Tetra-n-butylammonium hexafluorophosphate (n-
Bu4NPF6, 98%), N,N-dimethylformamide (DMF, 99.9%, water
≤30 ppm) and ferrocene (99%) were purchased from
Innochem. 1,3,5-Trimethoxybenzene was purchased from
J&K Scientific. CO2 gas (99.999%) was purchased from
Wuxi XinXiYi Technology Co., Ltd. (Methyl sulfoxide)-d6
(DMSO-d6, ≥ 99.8%+TMS) was bought from Shanghai
Titan Technology Co., Ltd. Nickel foam (NF, 99.99%, 0.5
mm thickness, 0.2 mm pore size) was purchased from Kunshan
Luchuang Electronic Technology Co., Ltd. Metal sheets (Co,
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Fe, Ni, 99.99%) were purchased from Anhui Zhengying
Technology Co., Ltd.
2.2. Preparation of Catalytic Electrodes. CoFeP/NF
was synthesized by a constant voltage electrodeposition
process. (See Figure 1.) Before electrodeposition, NF was
Figure 1. Schematic diagram of the synthetic procedure for the
CoFeP/NF.
sequentially ultrasonicated in acetone, pure water, 2 M
hydrochloric acid, and pure water for 10 min, to remove oil
and oxides from its surface. The electrolyte consists of 0.067 M
Co(NO3)2·6H2O, 0.033 M FeCl2, 1.5 M NaH2PO4, 1 M
NH4Cl, 0.5 M NaCl, and 0.02 M CH3COONa. The
electrodeposition was carried out in a three-electrode
configuration with pretreated NF as the working electrode, a
graphite plate as the counter electrode, and a saturated calomel
electrode (SCE) as the reference electrode. The electro-
deposition occurred at room temperature at −1.7 V (vs SCE)
at a constant voltage for 30 min. After electrodeposition, the
NF was washed with pure water and absolute ethanol and then
dried at room temperature. For comparison, CoP/NF or FeP/
NF was fabricated via the same process, but only Co(NO3)2·
6H2O or FeCl2 were added to the electrolyte at a total metal
concentration of 0.1 M.
2.3. Material Characterization. Morphologies of the
catalysts were determined by transmission electron microscopy
(TEM) (Model JEM-2100, JEOL, Tokyo, Japan) and scanning
electron microscopy (SEM) (Model Sigma-300, Zeiss,
Germany). Elemental composition and distribution of the
catalysts were analyzed via scanning electron microscopy
coupled with energy-dispersive X-ray spectroscopy (SEM/
EDS) (Oxford Xplore 30, United Kingdom). X-ray photo-
electron spectroscopy (XPS) measurements, which were
performed on an AXIS Supra system (Kratos, United
Kingdom), using monochromatized Al Kα radiation (hv =
1486.6 eV, 225 W) as the X-ray source, were used to analyze
the chemical composition and surface electronic states of the
samples. All of the binding energies were calibrated with C 1s
(284.8 eV). Inductively coupled plasma−optical emission
spectrometry (ICP-OES) (Agilent, USA) was applied to
analyze the content of metal atoms in the CoFeP catalyst.
Raman spectroscopy (Horiba, Japan), which used a 532 nm
excitation laser, was applied to analyze the interaction of
elements.
2.4. Electrocarboxylation Procedure of 1,3-Dienes
with CO2. The electrocarboxylation process was carried out by
potentiostatic electrolysis with bubbling CO2 (20 mL/min).
Typically, the electrolysis solution included a mixture of 0.5
mM n-Bu4NPF6, and 0.5 mM 1a in 8 mL of DMF in a single
electrochemical cell. The working electrodes were CoFeP/NF
(1 cm × 1 cm), CoP/NF (1 cm × 1 cm), FeP/NF (1 cm × 1
cm), NF (1 cm × 1 cm), Ni plate (1 cm × 1 cm), Fe plate (1
cm × 1 cm) or Co plate (1 cm × 1 cm). The counter electrode
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and quasi-reference electrode were Ni plate (2 cm × 2 cm) and
Ag wire, respectively. −9 V (vs Ag wire) was applied during
each experiment by the CS workstation (CS310H, Wuhan
Corrtest Instruments Corp., Ltd.). This process was con-
tinuously stirring at room temperature until the charge passed
400 C. At the end of each set of experiments, the reaction
mixture was acidified using 2 M HCl, then extracted three
times with ethyl acetate (3 × 8 mL). After that, the organic
phase was washed twice with 5% NaCl solution and then
washed once with saturated NaCl solution and dried with
anhydrous Na2SO4. After suction filtration and evaporation of
ethyl acetate, the yields of obtained products were determined
by 1H NMR spectroscopy, and 1,3,5-trimethoxybenzene was
added as the internal standard substance. Besides, the desired
products were obtained by column chromatography.
2.5. Electrochemical Measurements. The linear sweep
voltammetry (LSV) and cyclic voltammetry (CV) measure-
ments were carried out by using a Model CHI-660E
electrochemical workstation (CHI Instruments) in a standard
three-electrode single cell. Ag wire was used as the quasi-
reference electrode, and the counter electrode was a Ni plate
(2 cm × 2 cm). The catalytic electrodes prepared previously
were directly used as the working electrodes (1 cm × 1 cm).
The same electrolyte was used in the electrocarboxylation
procedure of 1,3-dienes saturated with CO2. The electro-
chemical impedance spectroscopy (EIS) test was measured at
open circuit potential, whose frequency range was 0.01 Hz−
100 kHz, and the AC disturbance amplitude was 5 mV. All
experiments were carried out after bubbling Ar gas to remove
O2 absolutely. We have performed the electrode correction
experiments by using ferrocene (Fc) (see Figure S1 in the
Supporting Information). The quasi-reference potential scale
was transformed to the Fc+/Fc reference potential scale, and all
potentials that have not been mentioned specifically are quoted
against Fc+/Fc.
2.6. Investigation on the Formation of CO2 Radical
Anion. The electrocarboxylation process was carried out by
potentiostatic electrolysis with bubbling CO2 (20 mL/min).
Typically, the electrolysis solution included a mixture of 0.5
mM n-Bu4NPF6, and 0.5 mM 1a in 8 mL of DMF in a
membraneless single electrochemical cell. The working
electrode was CoFeP/NF (1 cm × 1 cm); the counter
electrode and quasi-reference electrode were Ni plate (2 cm ×
2 cm) and Ag wire, respectively. The electrosynthesis was
carried out under continuous stirring at a potential of −9 V (vs
Ag wire) by the CS workstaion (CS310H, Wuhan Correst
Instruments Corp., Ltd.) at room temperature until a charge of
4 F mol−1 had passed. At the end of the experiment, the
reaction mixture was acidified with hydrochloric acid (2 M
HCl), then extracted three times with ethyl acetate (3 × 8 mL)
to get the aqueous phase. After concentration in vacuo
carefully, 1.0 mL of D2O was added to make the mixture
dissolve sufficiently. The aqueous phase was analyzed by crude
1
H NMR and 13C NMR, and formate was observed.
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3. RESULTS AND DISCUSSION
3.1. Structural Characterizations of Catalysts. In this
work, a three-dimensional CoFeP catalyst loaded on NF was
prepared by one-step potentiostatic electrodeposition facilely,
as mentioned in the Experimental Section (recall Figure 1).
The morphologies of CoFeP/NF were identified by SEM and
TEM and are shown in Figure 2. Compared with NF, CoFeP/
NF shows cauliflower-shaped microspheres (Figure 2a). While
CoP/NF (Figures S2a and S2b in the Supporting Information)
presents irregular coralline structure, and the FeP/NF has a
nanosheet morphology (Figures S2d and S2e in the Supporting
Information). The ICP-OES results show that the atomic ratio
of Co, Fe, and P is 6.5:1:0.2 in the CoFeP catalyst (Table S1 in
the Supporting Information). These results illustrate that
CoFeP catalyst was synthesized successfully and the morphol-
ogy of CoFeP catalyst could be significantly changed by adding
a small amount of iron. For further investigation on the
morphology and structure of CoP, FeP, and CoFeP catalysts,
detailed TEM was conducted. The TEM image of CoP (Figure
S2c in the Supporting Information) shows lattice fringes with a
spacing value of 0.223 nm from the (121) crystal plane of the
Co2P. While the TEM image of FeP (Figure S2f in the
Supporting Information) shows that the lattice fringe of the
(002) crystal plane of FeP was 0.294 nm. The lattice fringes of
Co2P and FeP were both found in the TEM image of CoFeP
(Figure 2b), which proves the CoFeP catalyst exhibits
phosphide Co2P and FeP.32,33 In addition, the image shows
a thin nanosheet structure (Figure 2c). EDS analysis of
CoFeP/NF exhibited that the Co, Fe, P, and O elements are
uniformly distributed on the NF substrate (Figure 2d). As for
the EDS mapping results of CoP/NF and FeP/NF (Figures S3
and S4 in the Supporting Information), they reveal an even
distribution of P, O, Co (or Fe) in the corresponding catalytic
electrode.
3.2. Electrocarboxylation Reaction Performance. The
electrochemical carboxylation of 1,3-dienes performances was
evaluated in a traditional three-electrode electrochemical single
cell, which employs trans,trans-1,4-diphenyl-1,3-butadiene
(1a) as the substrate, using Ag as the quasi-reference electrode
(see Section 2.4 in the Experimental Section). A series of
prepared catalysts was applied in the electrocarboxylation of 1a
and CO2 in order to explore electrochemical catalytic
performances. And the yields are obtained in Table 1. First,
we evaluated different types of conventional metal sheets as
cathodes for electrocarboxylation of 1a with CO2 (Table 1,
entries 1−3), which proves that the Co plate and Fe plate have
more effective effects on producing dicarboxylic acid 2a
(Figures S5 and S6 in the Supporting Information) than that of
Ni plate; Co and Fe may promote substrate 1a to transform
into 2a easily. Next, when the NF was used as the cathode
(Table 1, entry 4), the yield of 2a (44.6%) was worse than the
yield of the electrocarboxylation of 1a using Co plate (50.3%)
or Fe plate (54.2%) and the yield of the monocarboxylic acid
2b (Figures S7 and S8 in the Supporting Information) was
increased to 22.9% unexpectedly, compared with that of metal
sheets. However, the conversion rate (yields of 2a + 2b) of 1a
was promoted slightly when the NF was used as the cathode
material due to the porous structure and large specific surface
area. To pursue this advantage, we applied the synthesized
CoP/NF, FeP/NF, and CoFeP/NF as cathodes for electro-
carboxylation of 1a and CO2 (Table 1, entries 5−7).
Compared with CoP/NF, FeP/NF has better catalytic activity
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ACS Catalysis pubs.acs.org/acscatalysis Research Article

Figure 2. (a) SEM image of CoFeP/NF. (b, c) TEM images of CoFeP/NF. (d) SEM image and corresponding EDS mapping results of CoFeP/
NF.

Table 1. Product Selectivity Using Different Cathode Materialsa

entry cathode materials yield of 2ab (%) yield of 2bb (%)

1 Co plate 50.3 ± 1.6 12.0 ± 1.4
2 Fe plate 54.2 ± 2.4 13.1 ± 1.1
3 Ni plate 45.2 ± 1.6 14.1 ± 0.6
4 Ni foam (NF) 44.6 ± 2.3 22.9 ± 1.6
5 CoP/NF 42.4 ± 1.7 26.1 ± 2.4
6 FeP/NF 52.6 ± 1.6 23.0 ± 1.7
7 CoFeP/NF 61.9 ± 1.4 19.1 ± 1.7
a
Standard conditions: 1a (0.5 mmol), n-Bu4NPF6 (1.0 equiv), DMF (8.0 mL), CO2 (1 atm, 20 sccm), −9 V vs Ag wire, Ni plate as the anode,
metal sheets, NF and synthetic materials as the cathode in an undivided cell at room temperature. bYield evaluated by 1H NMR spectroscopy.

for synthesizing 2a. To our delight, using CoFeP/NF as the
cathode material promoted the electrochemical carboxylation
reaction of 1a with CO2 apparently (Table 1, entry 7). And it
not only provided 2a in 61.9% yield but also significantly
decreased the yield of 2b to 19.1%, compared to a 26.1% yield
for 2b in using CoP/NF as the cathode. Compared to
monometallic phosphide CoP/NF and FeP/NF electrodes,
bimetallic phosphating CoFeP/NF catalyst presents the
optimal electrocarboxylation catalytic activity, which added a
small amount of iron according to the results of the ICP-OES
(Table S1 in the Supporting Information). So, we propose that
the synergistic effects between Co and Fe probably existed in
CoFeP/NF catalyst, which could promote the electrocarbox-
ylation of 1a with CO2.
To verify this speculation, Raman spectra of synthesized
catalysts were obtained, which can be seen in Figure 3a. Five
peaks at 188, 466, 509, 606, and 670 cm−1 are observed on
CoP/NF obviously. Compared to CoP/NF, the five peaks in
CoFeP/NF are slightly red-shifted due to Fe doping, which
demonstrates that Fe doping can adjust the electronic structure
1462
of the catalysts and cause interaction between Co and Fe.34−36
Additionally, Figures 3b and 3c show high-resolution XPS
spectra of Co 2p and Fe 2p in synthesized catalysts to probe
elemental interaction. In addition, in the Co 2p spectrum of
CoP/NF, the peaks that are located at ∼781 and 797 eV, can
be ascribed to Co 2p3/2 and Co 2p1/2 respectively, which
indicates that cobalt is mainly present as Co3+ (780.7 and
796.6 eV) with only a small percentage of Co2+ (783.3 and
800.5 eV).36 Meanwhile, in the Fe 2p region of FeP/NF, the
peaks at 708.2 and 722.2 eV can be assigned to Fe2+.37
Interestingly, compared to CoP/NF, it shows a negative shift
of 0.9 eV in the Co2+ peak position of CoFeP/NF. However,
there exists a positive shift of 0.8 eV in the Fe2+ peak position
of CoFeP/NF, which is compared with FeP/NF. Being
consistent with Raman results, these results clearly indicate
the synergistic effects between Co and Fe, which is beneficial
to electron transfer and improves the catalytic activity of
CoFeP/NF.37,38 Moreover, broad features at ∼131 eV are
assigned to oxidized P species due to the synthetic materials
being exposed to air (Figure 3d).
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Figure 3. (a) Raman spectra of CoFeP, CoP, and FeP; (b) high-
resolution XPS of Co 2p performed on CoFeP and CoP; (c) high-
resolution XPS of Fe 2p performed on CoFeP and FeP; and (d) high-
resolution XPS of P 2p performed on CoP, CoFeP, and FeP.
3.3. Electroanalytical Results and Mechanism Dis-
cussion. In order to further discuss the synergistic effects, the
electrochemical behaviors of various kinds of cathode materials
were carried out by linear sweep voltammetry (LSV) and cyclic
voltammetry (CV) (Figures 4a and 4b). The LSV curves for
each electrode material show that CoFeP/NF has the largest
current density and smaller onset potential than other
electrodes, which indicates that the CoFeP/NF electrode has
the optimal and easy electron transfer during the 1a
electrocarboxylation with CO2. CVs were also performed in
the same electrochemical carboxylation conditions (Figure
4b−e).3,39 For the CVs of 1a, (Figure 4b−e, red line) two
obvious reduction peaks are detected by using CoFeP/NF as
Figure 4. (a) Cathodic linear sweep voltammetry data of 0.5 mmol 1a with 0.5 mmol of n-Bu4NPF6 in 8 mL of DMF at 50 mV s−1. CV experiments
of 1a. n-Bu4NPF6 (1.0 equiv) in DMF (8.0 mL) as the electrolyte, at a scan rate of 50 mV/s, using a Ni plate as the anode and Ag wire as the quasi-
reference electrode, cathode using (b) NF, (c) CoFeP/NF, (d) CoP/NF, (e) FeP/NF. (f) Nyquist plots of CoFeP/NF, CoP/NF, FeP/NF and
NF, recorded at open-circuit potential and fitted equivalent circuit.
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the cathode, and a one-electron reduction peak was observed
at the potential of −1.6 V (vs Fc+/Fc) and the second peak was
at −2.1 V (vs Fc+/Fc), which implies the electrochemical
carboxylation of 1a with CO2 may exist as a single electron
transfer process for two times.3,40 Compared with the CVs of
1a at NF and CoP/NF cathodes (Figures 4b and 4d, red line),
the doubled reduction peaks were not detected, which reveals
that NF and CoP/NF cathode materials have bad catalytic
activity for 1a reduction. Meanwhile, at FeP/NF cathode
(Figure 4e), there was only one reduction peak of 1a at −2.3 V
(vs Fc+/Fc), which suggests that the one-electron transfer
process on FeP/NF occurs easier than NF and CoP/NF, but it
is less likely to happen than that of CoFeP/NF. These results
clearly demonstrate that reduction of 1a is most likely to occur
at CoFeP/NF. In addition, at a potential of −1.6 V (vs Fc+/
Fc), the reduction current of CO2 at CoFeP/NF cathode
(Figure 4c, blue line) is expressively lower than that of 1a (0.4
vs 1.0 mA), which pointed out that 1a is easier to be reduced
than CO2. Moreover, when CO2 was bubbled into the
electrolyte with 1a (Figure 4c, green line), only one reduction
peak at −2.1 V (vs Fc+/Fc) was observed, whose peak current
greatly increased to 2.6 mA. It indicates that the one-electron
reduction intermediates reacted with CO2 sharply. However,
while CO2 is being introduced into the electrolyte with 1a at
NF (Figure 4b, green line), the reductive peaks at −2.2 V (vs
Fc+/Fc) were detected, which is more negative potential than
that of CoFeP/NF cathode, with an associated weaker current
(1.7 mA). Also, for the CV of 1a and CO2 (Figure 4d, green
line), there was only one reduction peak at −2.3 V (vs Fc+/Fc)
observed with the peak current of 2.0 mA, whose reduction
potential is more negative and current is lower than that of
CoFeP/NF cathode. When the CO2 was added into the
electrolyte with 1a using FeP/NF (Figure 4e, green line),
which was the only peak that was detected at a potential of
−2.3 V (vs Fc+/Fc). The reduction current is significantly
higher than that of CoFeP/NF (3.9 vs 2.6 mA). But when the
potential is −2.3 V (vs Fc+/Fc) at CoFeP/NF, the current is
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Figure 5. (a) Gram-scale reaction, reaction conditions: 1a (5 mmol), n-Bu4NPF6 (1.0 equiv), DMF (25 mL), CO2 (1 atm, 20 sccm), −9 V vs Ag
wire, Ni plate as the anode, CoFeP/NF as the cathode in a commercial flow cell at room temperature. (b) Investigation on the formation of CO2
radical anion, standard conditions: 1a (0.5 mmol), n-Bu4NPF6 (1.0 equiv), DMF (8.0 mL), CO2 (1 atm, 20 sccm), −9 V vs Ag wire, Ni plate as the
anode, NF as the cathode in an undivided cell at room temperature. (c) Influence of radical inhibitors on electrochemical carboxylation, under
standard conditions with adding 1.0 equiv DMPO or BQ.

slightly higher than that of FeP/NF (4.0 vs 3.9 mA). Those
results proved that CoFeP/NF could promote 1a electro-
carboxylation with CO2 at lower potential and the coexistence
of Co with Fe may be conducive to the 1a electroreduction
reaction. In addition, the Nyquist plot of CoFeP/NF (Figure
4f) proves that there is a semicircle of the smallest diameter,
compared to CoP/NF, FeP/NF, and NF, demonstrating that
faster charge transfer can be accomplished on the surface of the
CoFeP/NF electrode.41 Those electroanalytical results illus-
trate that the synergistic effects of Co and Fe can boost the 1a
electrocarboxylation with CO2.
The stability is a critical parameter in evaluating the
practicability of electrocatalysts. To assess this, the recyclability
of the CoFeP/NF was examined in the 1a electrocarboxylation
with CO2 under the same reaction conditions detailed in Table
1. After each electrolysis, the CoFeP/NF cathode was washed
completely with DMF for the next reaction. As shown in
Figure S9 in the Supporting Information, in a test of four
cycles, the electrocatalytic activity of the CoFeP/NF showed
no palpable decrease, suggesting that the CoFeP/NF is a type
of steady electrocatalyst. The TEM image of the CoFeP/NF
(Figure S10 in the Supporting Information) suggested that the
CoFeP structure was still maintained after the recycling test.
To explore the practical application of the direct electro-
chemical carboxylation of 1a, which used CoFeP/NF as the
cathode, a gram-scale reaction was next certified in a
commercial flow cell instead of the single cell (Figure 5a).
Importantly, the electrochemical carboxylation reaction of 1a
(5 mmol) with CO2 afforded the dicarboxylic acid 2a in 72.9%
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isolated yield (1.08 g) and a small amount of monocarboxylic
acid 2b in 7.5% yield. It illustrates that CoFeP/NF cathode
material can significantly satisfy the diverse equipment and has
the potential for practical application. To obtain insights into
the mechanism of this reaction, several mechanistic experi-
ments were performed. First, we explored the formation of
CO2 radical anions (Figure 5b) and found that formic acid
could be detected in the aqueous phase obtained after
experimental treatment, by 1H NMR spectroscopy under the
standard conditions (Figures S11 and S12 in the Supporting
Information), which illustrated that the CO2 radical anion may
be produced on the cathode.42,43 Next, a radical trapping
experiment was performed where radical inhibitor 5,5-
dimethyl-pyrroline N-oxide (DMPO) was added to the
electrochemical carboxylation reaction to investigate the
existence of radical intermediates. In the presence of DMPO,
the electrocarboxylation of 1a was badly carried out, with the
yield of 2a being 33.8% and that of 2b being 9.2%, compared
with standard conditions (Table 1, entry 4), which indicates
that radical intermediates play a fundamental role and the
radical mechanism happened for this reaction (Figure 5c).44,45
Also, benzoquinone (BQ) was added into the reaction
solution, which can play the role of proton catcher. In
addition, the yield of 2a increased from 44.6% to 64.3%, while
that of 2b decreased from 22.9% to 11.7%. This shows that the
existence of protons impedes the formation of 2a, and also
reveals that 2a is transformed from the further transformation
of 2b.45,46
https://doi.org/10.1021/acscatal.3c05395
ACS Catal. 2024, 14, 1459−1467
ACS Catalysis pubs.acs.org/acscatalysis
Based on the above experimental results, along with previous
literature reports,15,21,45 the reaction pathways for the electro-
chemical carboxylation of 1a were proposed in Figure 6. First,
Figure 6. A plausible mechanism diagram corresponding to
electrochemical carboxylation of 1a with CO2: (Path A, blue line)
1a was first activated; (Path B, black line) CO2 was first activated.
the electrocarboxylation reaction was initiated by the direct
reduction of 1a to give the corresponding radical anion I,
which was formed through a one-electron transfer process on
the cathode. Then, the reaction of I with CO2 produces
monocarboxylic acid radical anion II. Afterward, the
intermediate II is reduced by single electron transfer to give
the intermediate anion III, which could react with CO2 from
the dicarboxylate anion IV, which can get an H+ to form the
final product 2a in the subsequent acidification process. Or the
intermediate III may not be reduced further, which gets an H+
to accomplish hydrocarboxylation to form a monocarboxylic
anion (V) at the end of the reaction (path A). Additionally,
CO2 is also reduced into a CO2 radical anion, and the
formation of II might be generated by the reaction of 1a with a
CO2 radical anion. Next, the dicarboxylate anion IV comes
from the monocarboxylic acid anion II reacting with another
CO2 radical anion on the cathode (path B).
4. CONCLUSION
In summary, a bimetallic phosphating CoFeP catalyst on NF
was demonstrated as the first example of CO2 conversion to
produce multicarbon (C6+) dicarboxylic acids meaningfully
under mild conditions without adding any homogeneous metal
catalysts and stoichiometric metal-reducing agents. This
reaction used CoFeP catalyst as a cathode to achieve the
goal that the yields of the dicarboxylic acid products could be
up to 61.9% with the remarkable conversion (81%) of 1,3-
1465
Research Article
dienes. Compared with CoP/NF and FeP/NF cathode
materials, the synergistic effects between Co and Fe of the
CoFeP/NF electrode promote faster electron transfer to
complete the transformation and activation of substrate
effectively, as proven via the analysis of Raman, XPS, and
electroanalytical experiments. Notably, gram-scale amplifica-
tion reaction by using CoFeP/NF material was tested in a
commercial flow cell, resulting in 72.9% yield (1.08 g) of
dicarboxylic acid 2a and 7.5% yield (0.09 g) of monocarboxylic
acid 2b, which illustrated the potential practical application in
industrial electrocarboxylation of alkenes with CO2 by using
CoFeP/NF material. On the basis of the mechanism study,
there existed two plausible pathways to form the ultimate
carboxylated products, which began with the reduction of 1a or
CO2. Furthermore, we envision that our strategy of designing
cathode material applicable to the electrochemical carbox-
ylation of 1,3-dienes will offer an opportunity for exploiting
promising and new heterogeneous electrocatalysts in hybrid-
izing olefins and CO2 to long-chain acids for electro-
carboxylation.
■ ASSOCIATED CONTENT
Data Availability Statement
The authors declare that the data supporting the findings of
this study are available within the article and its Supporting
Information files. Extra data are available from the author upon
request.
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.3c05395.
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Ying Zhang − School of Chemical and Material Engineering,
Jiangnan University, Wuxi, Jiangsu 214122, China;
orcid.org/0000-0001-6394-3231; Email: ying.zhang@
jiangnan.edu.cn
Authors
Junjun Mao − School of Chemical and Material Engineering,
Jiangnan University, Wuxi, Jiangsu 214122, China
Bo Zhang − School of Physics, Peking University, Beijing
100091, China
Dan Wang − School of Chemical and Material Engineering,
Jiangnan University, Wuxi, Jiangsu 214122, China
Chenchen Zhang − School of Chemical and Material
Engineering, Jiangnan University, Wuxi, Jiangsu 214122,
China
Yang Lou − School of Chemical and Material Engineering,
Jiangnan University, Wuxi, Jiangsu 214122, China;
orcid.org/0000-0002-8310-8150
Chengsi Pan − School of Chemical and Material Engineering,
Jiangnan University, Wuxi, Jiangsu 214122, China;
orcid.org/0000-0002-1624-4259
Yongfa Zhu − Department of Chemistry, Tsinghua University,
Beijing 100084, China; orcid.org/0000-0001-8528-
509X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.3c05395
https://doi.org/10.1021/acscatal.3c05395
ACS Catal. 2024, 14, 1459−1467
ACS Catalysis pubs.acs.org/acscatalysis
Author Contributions
∇ 142 (4), 1780−1785.
These authors contributed equally to this work. Junjun Mao
performed the catalyst preparation, characterizations, and
catalytic tests. Dan Wang and Chenchen Zhang helped with
the catalyst preparation and characterization. Yang Lou,
Chengsi Pan, and Yongfa Zhu helped to discuss the results.
Junjun Mao, Bo Zhang, and Ying Zhang conceived the idea,
designed the study, analyzed the final data, and cowrote the
paper. All authors discussed the results and commented on the
manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (No. 22379054) and Startup Funding at
Jiangnan University.
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