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org/JACS Article

Electrocatalytic Interconversions of CO2 and Formate on a Versatile

Iron-Thiolate Platform
Yongxian Li, Jia-Yi Chen, Xinchao Zhang, Zhiqiang Peng, Qiyi Miao, Wang Chen, Fei Xie,
Rong-Zhen Liao,* Shengfa Ye,* Chen-Ho Tung, and Wenguang Wang*
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ABSTRACT: Exploring bidirectional CO2/HCO2− catalysis holds

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significant potential in constructing integrated (photo)-

electrochemical formate fuel cells for energy storage and
applications. Herein, we report selective CO2/HCO2− electro-
chemical interconversion by exploiting the flexible coordination
modes and rich redox properties of a versatile iron-thiolate
platform, Cp*Fe(II)L (L = 1,2-Ph2PC6H4S−). Upon oxidation,
this iron complex undergoes formate binding to generate a diferric
formate complex, [(L−)2Fe(III)(μ-HCO2)Fe(III)]+, which exhibits
remarkable electrocatalytic performance for the HCO2−-to-CO2
transformation with a maximum turnover frequency (TOFmax)
∼103 s−1 and a Faraday efficiency (FE) ∼92(±4)%. Conversely, this iron system also allows for reduction at −1.85 V (vs Fc+/0) and
exhibits an impressive FE ∼93 (±3)% for the CO2-to-HCO2− conversion. Mechanism studies revealed that the HCO2−-to-CO2
electrocatalysis passes through dicationic [(L2)−•Fe(III)(μ-HCO2)Fe(III)]2+ generated by unconventional oxidation of the diferric
formate species taking place at ligand L, while the CO2-to-HCO2− reduction involves a critical intermediate of [Fe(II)-H]− that was
independently synthesized and structurally characterized.

■ INTRODUCTION
Metalloenzymes set high standards for synthetic catalysts to
perform green energy conversion by utilizing atmospheric gas
molecules as sustainable feedstocks.1−3 For instance, metal-
dependent formate dehydrogenases (FDHs) containing either
molybdenum or tungsten can efficiently catalyze both formate
oxidation and CO2 reduction, both having impressive reaction
rates, i.e., 3400 s−1 at pH 7.5 for the former process and 280 s−1
for the latter.4,5 The microscopic CO2/HCO2− interconversions
inspire research into coupling electricity production with CO2
reduction to store the energy into formic acid as a renewable
feedstock for fuel cells (eq 1).6−8 This approach holds great
promise for constructing integrated photoelectrochemical
devices that harness solar energy to drive CO2 reduction and
subsequently release electrical energy via oxidation of formate to
CO2 with the same device.7,9−11 Therefore, the exploration of
catalytic systems capable of performing electrochemical CO2/
HCO2− interconversion is of crucial importance and scientific
intrigue.12−14
Eox
HCO2 XoooooooooY CO2 + 2e + H+
Ered
(singlecatalyst)
Inspired by Nature’s strategy using FDHs, the straightforward
route to achieve electrocatalytic CO2/HCO2− interconversion is
to invoke reversible catalysis with a single metal complex.
Regarding the concepts of “bidirectional catalysis” and
“reversible catalysis” defined by Fourmond and Léger,15,16
electrocatalysts capable of performing both reduction and
oxidation reactions are considered bidirectional, but they are
considerably reversible when they operate within a small
departure from the equilibrium potential in both directions.17,18
Yang presented an exemplary reversible catalyst, [Pt(depe)2]2+,
which functions both CO2-to-HCO2− reduction and HCO2−-to-
CO2 oxidation through sharing a common Pt−H intermediate
(Figure 1a).17,18 In principle, the facile occurrence of such
catalytic processes requires that each elementary step thereof
should have a minimum free energy change and should not
entail a high barrier.16,17 Apparently, it is difficult to design
systems to meet these requirements. As a consequence, only two
molecular bidirectional catalytic systems have been published
thus far, i.e., [Pt(depe)2]2+17 and (PONOP)Ir(H)3,19 whereas
numerous catalysts have already been reported for each
individual transformation.12,20−25 It should be noted that for
both CO2 reduction and formate oxidation, the vast majority of
catalysts are noble metal complexes that are typically superior to
Received: September 7, 2023
(1) Revised: November 15, 2023
Accepted: November 16, 2023
Published: November 29, 2023

© 2023 American Chemical Society https://doi.org/10.1021/jacs.3c09824

26915 J. Am. Chem. Soc. 2023, 145, 26915−26924
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Figure 1. (a) Proposed catalytic cycle for reversible transformations of CO2/HCO2− by [Pt(depe)2](PF6)2. Reproduced with permission from ref 17.
Copyright 2020 John Wiley and Sons. (b) Hypothesized electrochemical CO2/HCO2− interconversions using a single catalyst. (c) Present versatile
iron-thiolate platform for the CO2/HCO2− interconversions.

Figure 2. Electrochemical analysis of (a) formate oxidation and (b) CO2 reduction by using 1-N2 as a catalyst in the THF solution. For (a), CVs of
n
Bu4NHCO2·HCO2H (gray line), 1-N2 (1 mM) (red line), and 1-N2 with nBu4NHCO2·HCO2H (blue line); for (b), CVs of 1-N2 (1 mM) under N2
(red line), under N2 with TFE (violet line), under CO2 (green line), and under CO2 with TFE (orange line). Conditions: 1 mM sample in 0.3 M
n
Bu4NPF6-THF, scan rate 0.1 V/s; glassy carbon working electrode, Ag wire reference electrode, and Pt wire counter electrode.

their 3d counterparts.20,25 More critically, the catalytic activities
of the artificial systems in both directions are far below those of
FDHs. This reflects the challenges of reversible catalysis using a
single metal catalyst to perform CO/HCO2− conversions.2
Instead of exploring reversible catalysis, we sought to realize
bidirectional conversions between CO2 and HCO2− by
effectively exploiting the versatile coordination chemistry and
the rich redox properties of a well-defined base metal catalyst
such that the two transformations neither follow the same route
nor share the same metal hydride intermediate.7 The two
transformations are thus detangled and can be easily tuned by
the substrate coordination. In this case, the catalysis could
proceed via stepwise electron transfer (E) to achieve chemical
substrate binding and proton transfer steps (C),26 rather than
undergoing successive two-electron transfers prior to any
chemical steps, as observed for the most noble metal
26916
catalysts.20,24 The implementation of this strategy presents a
remarkable opportunity to utilize base metals for multielectron
and multistep catalysis.13,27,28 The hypothesis is that the
oxidized catalyst is capable of binding formate in a bimolecular
way that facilitates electron and proton transfer to improve rates
of the electrochemical HCO2−-to-CO2 oxidation (Figure 1b),
while upon 1e− reduction, the catalyst undergoes protonation
with weak acid and can efficiently convert to metal hydride
species, which can be further reduced at a mild reduction
potential to perform selective CO2-to-HCO2− reduction.
Herein, we report the first iron−sulfur system, Cp*Fe(1,2-
Ph2PC6H4S),29,30 which displays intriguing bidirectional elec-
trocatalytic activity toward CO2/HCO2− interconversions
(Figure 1c). Upon oxidation, the iron complex readily interacts
with formate to generate a diferric bridging formate species,
which can be further oxidized for C−H bond cleavage. This
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Figure 3. Electrochemical analysis of formate oxidation and characterizations of bridging formate diiron complexes. (a) CVs of [1-HCO2][BAr4F] (1
mM in THF) with varying [nBu4NHCO2·HCO2H] (0−350 mM) at a scan rate of 0.1 V/s and plot of the catalytic current versus [nBu4NHCO2·
HCO2H] (inset). (b) Plot of the turnover frequency versus [nBu4NHCO2·HCO2H]. (c) CVs of [1-HCO2][BAr4F] (1 mM) with [nBu4NHCO2·
HCO2H] (350 mM) in the THF solution with a varying scan rate and the plot of the catalytic current versus the scan rate (0.1−1 V/s). Conditions for
CVs: a glassy carbon electrode was used as the working electrode, a Pt wire as the counter electrode, and a Ag wire as the reference electrode; nBu4NPF6
(0.3 M) was used as the supporting electrolyte. (d) X-ray structures of [1-HCO2]+ and [1-HCO2]2+ cations with 50% probability thermal ellipsoids.
For clarity, the BAr4F counterions, H atoms at the Cp*, and phenyl rings were omitted; Cp* and the two phenyl rings at the phosphorus site were drawn
in lines. (e) Summary of the X-ray structural and 57Fe Mössbauer parameters of [1-HCO2]+ and [1-HCO2]2+. (f) Zero-field 57Fe Mössbauer spectra of
[1-HCO2][BAr4F] and [1-HCO2][BAr4F]2 recorded at 120 K. The solid lines represent the best fit obtained with the parameters listed in Table (e).

bimetallic reaction mode represents the fastest record for
HCO2−-to-CO2 electrocatalysis. At a relatively low voltage, this
iron−sulfur system is capable of catalyzing highly selective CO2-
to-HCO2− conversion, and the key intervening intermediate of
an [Fe(II)-H]− monomer was independently synthesized and
structurally characterized. Comprehensive experimental and
theoretical investigations offer valuable insights into such a
bidirectional 2e−/H+ transformation on the multifunctional
iron-thiolate platform.
■ RESULTS AND DISCUSSION
Bidirectional CO2/Formate Electrocatalysis with 1-N2.
We initiated a study by assessing the catalytic performance of 1-
N2 in formate oxidation and CO2 reduction through cyclic
voltammetry (CV) measurements, respectively. Under a N2
atmosphere, the CV of 1-N2 (1 mM) in a THF-nBu4NPF6
solution (0.3 M) displayed two reversible events at −1.85 V (ipc/
ipa = 0.98) and −0.33 V (ipa/ipc = 0.95) vs Fc+/0, which are
tentatively assigned to FeII/I and FeII/III redox couples (Figure 2).
Upon addition of nBu4NHCO2·HCO2H as the formate source,
the couple at −0.33 V was eliminated, and a new redox event
emerged with a significant increase in the anodic current at an
onset potential of 0.30 V. These electrochemical observations
suggest the occurrence of a catalytic process for formate
oxidation.31 In contrast, the oxidation of formate with a glassy
26917
carbon electrode was observed at an onset potential of 0.50 V
versus Fc+/0 in the absence of the iron complex.
Complex 1-N2 was also identified as an active electrocatalyst
for CO2 reduction, with CF3CH2OH (TFE, pKa = 24.0 in
DMF)32,33 acting as the proton source. When a THF solution of
1-N2 was saturated with CO2, the reduction wave at −1.85 V
became irreversible and slightly shifted to a less positive
potential (Figure 2b). Notably, adding TFE into a CO2-
saturated solution resulted in a significant increase in the
cathodic current at the onset potential of −1.65 V vs Fc+/0, and
the reduction current rises to ca. 3-fold of that generated by [1-
N2]−/0 under CO2. In the absence of CO2, the CV of 1-N2 with
TFE showed an enhanced reduction wave shifted to a more
negative onset potential of −1.80 V. These CV observations
indicate that the iron catalyst achieves selective electrochemical
CO2 reduction over proton reduction when TFE is employed as
the proton source. The preliminary results from cyclic
voltammetry experiments demonstrate the bidirectional electro-
catalytic activity of the iron-thiolate complex in CO2/HCO2−
interconversion. These findings motivated us to investigate the
electrochemical kinetics and delve into the underlying reaction
mechanism, which are discussed below.
Formate Oxidation. To achieve electrocatalytic CO2/
HCO2− interconversion, the critical task lies in effectively
realizing the C−H bond formation and breakage through
consecutive 2e−/H+ transfer steps with a single metal
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complex.34,35 Regarding the electrochemical formate oxidation,
Appel and Kubiak et al. reported the first nickel electrocatalysts
[Ni(P2RN2R′)2(CH3CN)]2 for HCO2−-to-CO2 oxidation (with
a maximum TOF ∼ 16 s−1), and the C−H cleavage was
proposed through binding formate to the nickel center, followed
by a rate-limiting proton and two-electron transfer step to
liberate CO2.31,36 Based on the preliminary analysis, we
hypothesized that the electrocatalytic formate oxidation is
triggered by the oxidation of 1-N2, which is followed by a
chemical transformation with the substrate. Typically, the
binding of formate to metal catalysts represents a crucial step
in electrocatalytic formate oxidation.
To verify the proposition, we therefore attempted to
synthesize the corresponding iron formate complex, [1-
HCO2]+. Oxidation of 1-N2 by [Cp2Fe][BAr4F] (where Cp =
C5H5−, BAr4F = (3,5-(CF3)2C6H3)4B) in MeCN generated the
corresponding ferric nitrile complex, [Cp*Fe(1,2-Ph2PC6H4S)-
(NCMe)]+ ([2-NCMe]+), in a high yield. Treating [2-NCMe]+
with HCO2Na in THF caused a gradual color change from deep
blue to purple and finally afforded the target formate complex,
[1-HCO2][BAr4F]. X-ray structural analysis revealed that [1-
HCO2][BAr4F] is a cationic diiron complex wherein the two
Cp*Fe(1,2-Ph2PC6H4S) fragments are bridged by a formate
ligand (Figures 3d and S60) with C−O distances of 1.255(4)
and 1.250(4) Å, and ∠O−C−O = 121.7(3)°. In the Fourier-
transform infrared (FT-IR) spectrum, a weak νC−O band was
displayed at 1560 cm−1,37 which shifts to 1522 cm−1 for the 13C-
labeled formate isotopologue, i.e., [1-H13CO2][BAr4F] (Figure
S47).
Complex [1-HCO2][BAr4F] in THF-nBu4NPF6 at a scan rate
of 100 mV/s showed an irreversible redox event at 0.30 V vs
Fc+/0, tentatively attributed to a FeIII,III/III,IV redox couple, which
becomes increasingly reversible at higher scan rates (Figure S8).
More important is that the anodic current rises upon adding
n
Bu4NHCO2·HCO2H. Increasing [nBu4NHCO2·HCO2H]
leads to a gradual shift of the anodic wave to more positive
potentials accompanied by the current ascending (Figure 3a).
When [nBu4NHCO2·HCO2H] reached 300 mM, the catalytic
current was independent of its concentration. Alternatively, at a
constant concentration (100 mM) of nBu4NHCO2·HCO2H, the
anodic current also increases linearly with the concentration of
[1-HCO2][BAr4F] over the range of 0.5−2.5 mM (Figures S15
and S16). All of these results indicate the occurrence of
electrochemical catalysis in formate oxidation.31 To analyze the
kinetics of the electrochemical formate oxidation, the catalytic
current enhancement, icat/ip (where icat and ip represent the
current in the presence and absence of the substrate,
respectively), was converted into an observed rate constant
(kobs). This conversion was done using eq 2, which incorporates
Faraday’s constant (F), the universal gas constant (R), the
temperature (T), the diffusion coefficient (D), the area of the
working electrode (A), the number of electrons transferred in
the catalytic process (ncat), the number of electrons transferred
in the redox event (np), and the scan rate (v).31,38,39
Additionally, a catalytic turnover frequency (TOF) was
calculated using eq 3 (the Supporting Information, page
S8).31,38−40
icat ncat ij RT yz
jj z S61). Except for the counteranions, the framework of [1-
= jj 3 zzzkobs
ip 0.4463 j np Fv z
k { (2)
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ij i yz
2 2
ij 0.4463 yz n p3Fv
TOF = kobs = jjjj cat zzzz jj
jj n
zz
zz
j ip z k cat { RT
k { (3)
In Figure 3b, the TOF of the catalyst is plotted against
[nBu4NHCO2·HCO2H]. Initially, The TOF increases linearly
with increasing [nBu4NHCO2·HCO2H] and reaches a plateau at
300 mM, indicating that the TOF becomes independent of the
formate concentration. The linear region of this plot indicates a
first-order dependence of the TOF on [nBu4NHCO2·HCO2H]
when it is below 300 mM. The dependence of the catalytic
current on the scan rate was also investigated with the
[nBu4NHCO2·HCO2H] of 350 mM. As shown in Figure 3c,
the catalytic current becomes scan rate-independent when the
scan rate is increased to 0.6 V/s, indicating that the catalysis is
operating in the pure kinetic regime, where the substrate
consumption is negligible.41,42 The icat/ip value, determined
from the CV, was found to be 50, and a TOFmax value of 2.91 ×
103 s−1 was calculated. Furthermore, the turnover frequency was
also determined from the preparative-scale electrolysis of
formate oxidation.43−45 This analysis yielded a TOFCPE value
of 1.05 × 103 s−1, which aligns with the value obtained from the
icat/ip method. Remarkably, the present iron-based catalysis
exhibits the highest reaction rate for formate oxidation
compared to related homogeneous catalysts ever re-
ported.17,19,31,36
Controlled potential electrolysis (CPE) was conducted on a
THF solution containing 100 mM [nBu4NHCO2·HCO2H] and
1 mM [1-HCO2][BAr4F]. At a potential of 0.35 V vs Fc+/0, a total
charge of 12.4 C was passed through the system over the course
of the 6 h bulk electrolysis. Notably, the current remained almost
constant at 0.6 mA throughout the electrolysis process (Figure
S17). Analyses of the headspace gas with GC indicated that the
reaction produced 59.0 μmol of CO 2 (TON ∼ 12),
corresponding to a Faraday efficiency of 91.8(±4)%. X-ray
photoelectron spectroscopy (XPS) and rinse testing on the
glassy carbon working electrode confirmed the absence of active
iron species attached to the electrode surface (Figures S49 and
S50).46 These findings collectively demonstrated that [1-
HCO2][BAr4F] is a highly selective and robust catalyst for
electrochemical formate oxidation.
According to the electrochemical analysis, the iron-catalyzed
formation oxidation is based on the oxidation of [1-HCO2]-
[BAr4F]. To ensure the uncommon one-electron oxidation of
this cationic diferric complex, bulk chemical oxidation was
subsequently carried out (eq 4). Treating a fluorobenzene
solution of [1-HCO 2 ][BAr 4 F ] with one equiv of
[(C6F5Cp)2Fe][BAr4F] (E1/2 = 0.345 V vs Fc+/0) at −30 °C
resulted in a rapid color change from violet to black. After being
warmed to room temperature, the reaction mixture was dried
under vacuum. The crude product, [1-HCO2][BAr4F]2, was
washed with hexane and purified through crystallization from a
fluorobenzene/hexane solution at −30 °C.
[1 HCO2 ]+ e [1 HCO2 ]2 + (4)
[1 HCO2 ]2 + + collidine CO2 (5)
X-ray crystallographic analysis revealed the solid-state
structure of [1-HCO2][BAr4F]2, presumably a formate bridged
dicationic [Fe(III)(μ-HCO2)Fe(IV)]2+ species (Figures 3d and
HCO2]2+ is identical to that of [1-HCO2]+, but the one-electron
oxidation causes slightly asymmetric binding of the formate
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Figure 4. Schematic molecular orbital diagrams and spin density plots of (a) [1-HCO2]+ and (b) [1-HCO2]2+.
ligand to the two iron centers as evidenced by the different Fe1−
O1 (1.989(3) Å) and Fe2−O2 distances (1.905(2) Å).
Analogously, the two C−O bond lengths (1.255(4) and
1.250(4) Å) of the formate ligand in [1-HCO2]+ are almost
identical, whereas those (1.272(4) and 1.250(4) Å) in [1-
HCO2]2+ differ by ca. 0.02 Å, although the O−C−O bond angle
of 121.7(3)° in the former complex is comparable with that of
121.5(3)° in the latter (Figure 3e). Notably, this new iron
species readily furnishes CO2 in the presence of a base (eq 5).
Treatment of [1-HCO2]2+ with one equiv of 2,4,6-trimethylpyr-
idine (pKa = 8.1 in THF) produced CO2 in 83(±5)% yield as
determined by GC analyses. This finding revealed that [1-
HCO2]2+ is indeed an intervening intermediate in the catalytic
cycle of formate oxidation.
Electronic Structure Analyses for [1-HCO2]2+ and [1-
HCO2]+. To elucidate the electronic structures of [1-HCO2]+
and [1-HCO2]2+, we undertook comprehensive spectroscopic
characterizations. Variable temperature magnetic susceptibility
(χ) measurements using a superconducting quantum interfer-
ence devices (SQUID) unequivocally established that [1-
HCO2]+ possesses an S = 1 ground state with an energetically
closely spaced S = 0 excited state. Complex [1-HCO2]2+ features
an S = 1/2 ground state. Furthermore, the electron paramagnetic
resonance (EPR) spectrum of [1-HCO2]2+ registered a highly
anisotropic rhombic signal with g = 2.00, 2.03, and 2.31 (Figure
S56). Interestingly, [2-NCMe]+ elicited a similar EPR spectrum
with g = 2.00, 2.03, and 2.35 (Figure S55), typical of
mononuclear S = 1/2 ferric complexes.47 Zero-field 57Fe
Mössbauer spectra of [1-HCO2]+ and [1-HCO2]2+ showed
only one well-resolved quadrupole doublet (Figure 3f);
therefore, their respective two Fe centers are more or less
equivalent. More importantly, both species have nearly identical
isomer shifts (δ = 0.43, 0.43 mm/s) and quadrupole splittings
(ΔEQ = 1.38, 1.29 mm/s), which are comparable to those
measured for [Cp*FeIII(1,2-Ph2PC6H4NH)(NH3)]+ (δ = 0.40
mm/s and ΔEQ = 1.35 mm/s), a related mononuclear S = 1/2
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FeIII complex.26 These findings evidenced that [1-HCO2]+ and
[1-HCO2]2+ contain two low-spin ferric centers each, and their
interconversion is a ligand-centered redox process.
The electronic structure analyses mentioned above were
confirmed by density functional theory (DFT) calculations,
which successfully replicated the experimentally observed
Mössbauer parameters. Specifically, the triplet ground state of
[1-HCO2]+ was found to consist of two ferromagnetically
coupled low-spin ferric centers and the broken-symmetry singlet
state that represents the corresponding antiferromagnetic
coupling is nearly isoenergetic with the triplet state (Figure
4a). Consequently, the computed key geometric parameters of
both states are almost identical, as are their estimated Mössbauer
parameters.
For the doublet state of [1-HCO2]2+, DFT computations
predicted two different electronic structures; namely, one is best
described as two ferromagnetically coupled low-spin ferric
centers that are antiferromagnetic coupled to a thiyl radical
delocalized onto the two supporting ligands denoted by
BS(2,1)-A, and the other as two antiferromagnetically coupled
low-spin ferric centers that interact with the same delocalized
thiyl radical, denoted by BS(2,1)-B (Figure S63). The
corresponding quartet state of [1-HCO2]2+ is distinguished by
the three unpaired spins aligning up. These three states were
estimated to be essentially isoenergetic within the uncertainty
range of DFT calculations.48 In line with their energy near-
degeneracy, the computed geometries of the three states are all
in reasonable agreement with those of the experiment. However,
because EPR measurements disclosed that the sole unpaired
electron of [1-HCO2]2+ is primarily localized on a low-spin ferric
center, the BS(2,1)-A solution should represent its real
electronic structure (Figure 4b). As depicted in Figure 4b,
upon oxidation, the spin populations of the two Fe centers are
exactly the same, but those of the two S atoms substantially
decrease from 0.14 to −0.49, along with appreciable negative
spin densities being delocalized on the two phenyl rings
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Figure 5. Electrocatalytic CO2 reduction with 1-N2. (a) CVs of 1-N2 recorded in the CO2-saturated THF solution in the presence of varying [TFE]
(0−125 mM), (b) plots of the turnover frequency versus [TFE], and (c) plots of icat/ip versus [TFE]1/2 to determine kH/kD.
attached. The oxidation is, therefore, best interpreted as being
primarily ligand-centered and does not engender highly covalent
Fe(IV)-S bonding interactions.
CO2 Reduction. As mentioned above, 1-N2 also serves as an
active catalyst for electrochemical CO2 reduction; the following
electrochemical analyses were conducted to investigate the
kinetics of CO2 reduction.13,41 As shown in Figure 5a, a addition
of TFE to the CO2-saturated solution of 1-N2 (1 mM in THF)
resulted in a continuous increase in the catalytic current,
accompanied by an anodic shift in the wave potentials. The
catalytic current reached a limiting value at [TFE] of 125 mM.
At this stage, the catalytic cyclic voltammogram exhibited a
characteristic S-shape response, and the catalytic current was
also found to be independent of the scan rate (Figure S24).
These observations suggest that the catalysis is operating in the
pure kinetic regime.41,42 To quantify the catalytic current
enhancement (icat/ip) and the TOF, eqs 2 and 3 were employed,
respectively. Plotting the TOF against [TFE] revealed a linear
increase of the TOF with [TFE], which leveled off at [TFE] =
125 mM (Figure 5b). Under these conditions, TOFmax was
determined to be 1.05 × 102 s−1, which is consistent with the
TOF value of 1.22 × 102 s−1 obtained from the preparative-scale
electrolysis experiments (the Supporting Information, page S9
and Figure S27).43−45
Additionally, when the concentration of TFE is below 125
mM, the catalytic current enhancement (icat/ip) varies linearly
with the square root of the CF3CH2OH concentration
([TFE]1/2), which indicates that the electrocatalytic process is
first-order with respect to [TFE] (Figure 5c).49,50 At a constant
[TFE] of 28 mM, we also found that the catalytic current (icat)
increases linearly as a function of [Fe] in the range of 0.5−2.5
mM (Figures S25 and S26). When CF3CH2OD was used as the
proton source instead of CF3CH2OH, the catalysis progressed at
much slower rates (Figure S21). A primary H/D kinetic isotope
effect (KIE) value of 4.8 ± 0.5 was obtained (Figure 5c). A KIE
value of such a magnitude is close to the reported KIE values
observed in electrochemical CO2-to-HCOOH reduction
catalyzed by [CpCo(P2BuN2Cy)I]+ (5.0 ± 0.4)42 and Fe-
(tbudhbpy)Cl (4.8 ± 0.9),51 both of which involve a metal
hydride (M-H) intermediate.20,23,52,53
To determine the product of the electrocatalytic CO2
reduction, a CPE experiment was carried out at −1.85 V (vs
Fc+/0) in a CO2-saturated THF-nBu4NPF6 (0.3 M) solution
containing 1 mM 1-N2 and 50 mM TFE. Over the course of 4 h
electrolysis, a total charge of 10.2 C was passed through the
system. After the reaction, the product was analyzed by 1H NMR
spectroscopy, which confirmed the production of formate
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(Figure S34). The total catalytic turnover number (TON) for
formate production was calculated to be 4.9, corresponding to a
Faraday efficiency of 93(±3)%. A minor amount of H2 was also
detected by GC-TCD, accounting for approximately 4.5(±1)%;
no CO was detected (Figure S35). By contrast, when the CPE
was conducted in the absence of 1-N2, neither formate nor H2
was generated.
Prior research has highlighted difficulties in achieving
selective production of formate over CO and H2 from
electrocatalytic CO2 reduction21,22,54,55 because the reaction
paths heavily depend on the redox property of the catalyst and
the acidity of the proton source.23,32,43,56 For formate
production, the majority of reactions involve crucial metal-
hydride (M-H) species generated by protonation of the reduced
catalyst.7,12,22 However, subsequent CO2 reduction by M-H to
furnish HCO2− encounters competition with proton reduction
to produce H2.57 Consequently, only a limited number of
homogeneous catalysts have been reported to exhibit high
(>90%) FE for selective CO2-to-HCO2− reduction.42,58,59
Notably, the incorporation of a basic site into the catalysts′
coordination sphere enables the utilization of abundant metals
such as Fe,35,49,51,53,57,60 Co,42,52 and Ni61 for the selective
formate production at mild potentials.22,43 Remarkably, recent
research on iron−porphyrin systems yielded valuable mecha-
nistic and synthetic insights and established the structure−
property relationships that govern selectivity for CO2-to-
HCO2− reduction.12,53,60,62
According to the CV analyses, the present iron-based catalysis
is initiated by the reduction of 1-N2. We propose an anionic
iron(II)-hydride intermediate [Cp*FeH(1,2-Ph2PC6H4S)]−
(abbreviated to [2-H]−) responsible for selective CO2 reduction
(for detailed information, refer to Figure 7). Particularly, the
hypothesized anionic hydride can be accessed by employing an
alternative method to incorporate a hydride ligand onto the
Cp*FeL platform (eq 6). The addition of LiBHEt3 (1 M in
THF) to a THF solution of 1-N2 at −30 °C resulted in a rapid
transformation of the brown solution to deep green. Following
the workup, the desired hydride product, [2-H]−, was obtained
by crystallization from the ether solution in 70 (±5)% yield. The
1
H NMR spectrum of [2-H]− displays a characteristic hydride
doublet at δ − 18.19 with JH,P = 64.2 Hz, while the phosphorus
resonance is observed at δ 106 in 31P NMR. The solid-state
structure of [2-H]Li, determined by X-ray crystallographic
analysis, reveals an anion−cation framework composed of
[Cp*FeH(1,2-Ph2PC6H4S)]Li(THF)(Et2O) (Figure 6). The
position of the hydride ligand was located by inspection of the
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Journal of the American Chemical Society pubs.acs.org/JACS Article

difference density map, and the Fe−H bond length was refined
to be 1.46(3) Å.
1 N2 + LiBHEt 3 [2 H]Li (6)

[2 H]Li + CO2 2 + HCO2 Li (7)

As anticipated, [2-H]Li reacts with CO2 to produce formate

(eq 7). When a THF solution of [2-H]Li was exposed to CO2, its
color immediately changed from dark green to brown. The
reaction yielded formate salt in 72% yield, as determined by 1H
NMR analyses (Figure S36). The organoiron byproduct,
presumably Cp*Fe(1,2-Ph2PC6H4S) (2), was further trapped
by CO to furnish a stable adduct, Cp*Fe(1,2-Ph2PC6H4S)(CO)
Figure 6. X-ray structure of [2-H]Li with 50% probability of thermal (Figure S37).28 These results confirm that [Cp*FeH(1,2-
ellipsoids. Ph2PC6H4S)]− is highly hydridic and capable of triggering the
conversion CO2 to formate (ΔGH− = 44 kcal/mol in MeCN).55

Figure 7. Proposed mechanisms and the transition states (TS1 and TS2) for electrocatalytic formate oxidation and CO2 reduction with the iron-
thiolate complex. All reaction and activation energies are given in units of kcal/mol, and the experimental redox potentials are referenced to the Fc+/0
couple.

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J. Am. Chem. Soc. 2023, 145, 26915−26924
Journal of the American Chemical Society
Mechanism. Based on the experimental observations,
computational studies were conducted to gain further
mechanistic insights into the iron-based bidirectional CO2/
formate electrocatalysis (Figure 7). Regarding the formate
oxidation, starting from [1-HCO2]2+, the second HCO2−
molecule functions as a Brønsted base and deprotonates the
bridging HCO2− ligand, which is coupled with a single electron
transfer (SET) from the formate substrate to the supporting
ligand radical cation. This process has to overcome a barrier
(TS1) of +6.8 kcal/mol in the doublet relative to [1-HCO2]2+
plus HCO2 − and results in the formation of doublet
intermediate Int1. For 2TS1 (Figure S64), the spin populations
on Fe1, Fe2, and the (HCO2)2 moieties are 1.13, −1.09, and
0.85, respectively. Hence, the electronic structure of 2TS1 can be
described as the (HCO2−)2 radical anion ferromagnetic
coupling with two Fe(III) centers [FeIII-(HCO2−)2•-FeIII]+. As
shown in Figure 7, the distances of the C1−H1 and H1−O3
bonds are 1.26 and 1.33 Å in 2TS1. The formed CO2 links the
iron centers, and HCO2H interacts with the S atom of the
catalyst through the hydrogen bonding interaction. The spin
populations on Fe1, Fe2, and CO2 are 1.15, −1.15, and 0.91,
respectively (Figure S64). Based on the spin population analysis
of Int1, the CO2 moiety (total spin population of 0.91) is
suggested to be a radical anion. Finally, a SET from CO2•− to
Fe1 takes place and releases CO2 and HCO2H, accompanied by
the generation of ferrous and ferric monomer catalysts 2 and
[2]+. The process was calculated to be exergonic by 36.1 kcal/
mol. This formate oxidation pathway is reminiscent of the
orthogonal hydride (electron/proton) transfer mechanism for
Mo-dependent formate dehydrogenase, in which the formate
proton is delivered to a Brønsted base (anionic selenium
cysteine residue) and the two electrons to the metal center.2
The pathway for the iron-catalyzed electrochemical reduction
of CO2-to-formate was also elucidated by DFT calculations. Our
previous studies29,30 indicated that dissolution of 1-N2 in THF
causes N2 expulsion and forms monomeric complex Cp*Fe(1,2-
Ph2PC6H4S) (2). Reduction of 2 at −1.85 V vs Fc+/0 generates
catalytically active species [2]−, which allows for protonation by
(CF3CH2OH)2 through transition state TS2 (Figure 7). The
barrier of TS2 is calculated to be +8.2 kcal/mol (Figure S65).
The geometric features of TS2 (Figure S66), having Fe−H1 and
H1−O1 bond distances of 1.61 and 1.46 Å, respectively, affirm
that it is on the way of a proton transfer process. This reaction
generates a neutral ferric hydride compound, 2-H, after releasing
the (CF3CH2O)−HOCH2CF3. Further, one-electron reduction
of 2-H produces anionic hydride [2-H] − , which was
independently synthesized and characterized, as revealed
above. The facile insertion of CO2 into the Fe−H bond in [2-
H]− was achieved via a barrierless diffusion-control way (Figure
S67). The formation of the formate complex [2-OCHO]− lies at
−21.0 kcal/mol relative to [2-H]− (Figure 7). The final step of
HCO2− release from [2-OCHO]− to regenerate 2 is a slightly
endergonic process with a Gibbs free energy change (ΔG0) of
+1.5 kcal/mol. The possibility that CO2 direct attacks 2-H to
generate HCO2− (via TS4, Figures S65−S66) can be ruled out
due to the high barrier of +28.6 kcal/mol.
■ CONCLUSIONS
We have demonstrated the first iron system that achieves
electrocatalytic CO2 and formate interconversion by exploiting
the coordination chemistry and redox chemistry of a Cp*Fe(1,2-
Ph2PC6H4S) platform. Upon oxidation, the iron-thiolate
complex readily binds formate to form a diferric bridging
26922
pubs.acs.org/JACS Article
formate complex that exhibits efficient electrochemical catalytic
activity with a maximum turnover frequency of ∼103 s−1.
Remarkably, the resulting diiron system undergoes further one-
electron oxidation, leading to an uncommon [(L2)−•Fe(III)(μ-
HCO2)Fe(III)]2+ dicationic radical species, which allows for
facile deprotonation of the HCO2− ligand under mild conditions
to liberate CO2. Upon reduction, the iron-thiolate monomer
exhibits ∼93(±3)% FE in electrocatalytic CO2 reduction to
formate. The reaction likely passes through an anionic [Fe(II)-
H]− intermediate, with the ensuing hydride transfer represent-
ing the rate-limiting step, as evidenced by a primary H/D KIE
value of 4.8(±0.5). Combining electrochemical kinetic studies
and stoichiometric reaction sequences with DFT studies, the
mechanistic intricacies for the 2e−/H+ bidirectional CO2-
formate catalysis were meticulously elucidated. In terms of
carbon efficiency, however, the current electrocatalytic HCO2-
to-CO2 oxidation system necessitates the addition of an extra 1
equiv of formate as a Lewis base. This, to some extent, reduces
the reaction efficiency, highlighting a potential area for
improvement in future systems.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.3c09824.
Discussions of experimental details, synthesis and
characterization information, electrochemical studies,
spectroscopic data, crystal data, structure refinement
parameters, and DFT calculations (PDF)
Accession Codes
CCDC 2278772−2278773, 2278777, and 2278818 contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, or by emailing data_request@ccdc.cam.ac.
uk, or by contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033.
■ AUTHOR INFORMATION
Corresponding Authors
Rong-Zhen Liao − School of Chemistry and Chemical
Engineering, Huazhong University of Science and Technology,
Wuhan 430074, China; orcid.org/0000-0002-8989-
6928; Email: rongzhen@hust.edu.cn.
Shengfa Ye − State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China; orcid.org/0000-0001-9747-1412;
Email: shengfa.ye@dicp.ac.cn.
Wenguang Wang − College of Chemistry, Beijing Normal
University, Beijing 100875, China; orcid.org/0000-0002-
4108-7865; Email: wwg@bnu.edu.cn.
Authors
Yongxian Li − College of Chemistry, Beijing Normal University,
Beijing 100875, China
Jia-Yi Chen − School of Chemistry and Chemical Engineering,
Huazhong University of Science and Technology, Wuhan
430074, China
Xinchao Zhang − State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China; University of Chinese Academy of
Sciences, Beijing 100049, China
https://doi.org/10.1021/jacs.3c09824
J. Am. Chem. Soc. 2023, 145, 26915−26924
Journal of the American Chemical Society
Zhiqiang Peng − College of Chemistry, Beijing Normal
University, Beijing 100875, China
Qiyi Miao − State Key Laboratory of Catalysis, Dalian Institute
of Chemical Physics, Chinese Academy of Sciences, Dalian
116023, China; University of Chinese Academy of Sciences,
Beijing 100049, China
Wang Chen − State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China; University of Chinese Academy of
Sciences, Beijing 100049, China
Fei Xie − State Key Laboratory of Catalysis, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian
116023, China
Chen-Ho Tung − School of Chemistry and Chemical
Engineering, Shandong University, Jinan 250100, China;
orcid.org/0000-0001-9999-9755
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.3c09824
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
W.W. thanks the financial support from the National Natural
Science Foundation of China (22022102 and 22071010) and
the Natural Science Foundation of Shandong Province
(ZR2019ZD45). S.Y. gratefully acknowledges the financial
support from the National Natural Science Foundation of
China (92161204). R.-Z.L. acknowledges the financial support
from the National Natural Science Foundation of China
(21873031).
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