Letter

Cite This: ACS Energy Lett. 2019, 4, 1663−1671 http://pubs.acs.org/journal/aelccp

Unraveling Mechanistic Reaction Pathways of

the Electrochemical CO2 Reduction on Fe−N−
C Single-Site Catalysts
Wen Ju,†,# Alexander Bagger,‡,# Xingli Wang,† Yulin Tsai,† Fang Luo,† Tim Möller,† Huan Wang,†
Jan Rossmeisl,‡ Ana Sofia Varela,*,§ and Peter Strasser*,†
†
The Electrochemical Energy, Catalysis, and Materials Science Laboratory, Department of Chemistry, Chemical Engineering
Division, Technical University Berlin, 10623 Berlin, Germany
‡
Department of Chemistry, University Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark
§
Institute of Chemistry, National Autonomous University of Mexico, 04510 Mexico City, Mexico
*
S Supporting Information
Downloaded by TU BERLIN at 01:30:28:879 on July 02, 2019
from https://pubs.acs.org/doi/10.1021/acsenergylett.9b01049.

ABSTRACT: We report a joint experimental−computational mech-

anistic study of electrochemical reduction of CO2 to CH4, catalyzed
by solid-state Fe−N−C catalysts, which feature atomically dispersed,
catalytically active Fe−Nx sites and represent one of the very rare
examples of solid, non-Cu-based electrocatalysts that yield hydro-
carbon products. Work reported here focuses on the identification of
plausible mechanistic pathways from CO2 to various C1 products
including methane. It is found that Fe−Nx sites convert only CO2,
CO, and CH2O into methane, whereas CH3OH appears to be an end
product. Distinctly different pH dependence of the catalytic CH4
evolution from CH2O in comparison with that of CO2 and CO
reduction indicates differences in the proton participation of rate-
determining steps. By comparing the experimental observations with
density functional theory derived free energy diagrams of reactive
intermediates along the CO2 reduction reaction coordinates, we unravel the dominant mechanistic pathways and roles of
CO and CH2O during the catalytic CO2-to-CH4 cascades and their rate-determining steps. We close with a comprehensive
reaction network of CO2RR on single-site Fe−N−C catalysts, which may prove useful in developing efficient, non-Cu-
based catalysts for hydrocarbon production.

coordinated macrocyclics,27 cyclams,28 bipyridines,29,30 as

T he direct electrochemical CO2 reduction reaction

(CO2RR) is a potentially attractive technology to
close the energetic carbon cycle by converting CO2
into useful carbon-based chemicals.1 Renewable electricity,
generated from solar or wind, could provide the energy needed
for this conversion in a sustainable manner.
Since the 1980s, when Hori and his co-workers pioneered
the field and extensively tested the process on metallic
electrodes,2 the CO2RR has been continuously studied. It is
well-known that the product distribution of the CO2RR
strongly depends on the nature of the catalytic metals.2−9
Copper has always been unique in its capability of producing
higher-value hydrocarbons and oxygenates.2,10 This is why
whenever “beyond CO” reaction products were concerned,
that is, molecules resulting from the protonation of CO, it was
Cu and its derivatives that were at the center of attention in
mechanistic studies or optimization developments.2,10−26
Non-Cu-based families of (molecular) catalysts with the
capability to electrochemically reduce CO2 are metal-
well as various metalated porphyrins.31−34 Density functional
theory (DFT) analyses have suggested that a metal (M)-
porphyrin-inspired M−N4 motif acts likely as the catalytically
active site.35 More importantly, our recent studies have shown
that the coordinative-isolated metal (ion) sites hold the key
structural advantage to kinetically suppress the competitive
hydrogen evolution reaction (HER), further benefiting the
selectivity to CO2RR.36 However, these molecular catalysts,
when immobilized on a solid substrate, have notoriously
suffered from poor electron transfer and low active-site
densities, restricting their practical technological usefulness.37
Pyrolyzed, solid-state M−N−C catalysts with their M−N4
motifs structurally embedded in a solid-state graphene matrix
could overcome the shortcomings of the molecular cata-
Received: May 15, 2019
Accepted: June 17, 2019
Published: June 17, 2019

© XXXX American Chemical Society 1663 DOI: 10.1021/acsenergylett.9b01049

ACS Energy Lett. 2019, 4, 1663−1671
ACS Energy Letters
Figure 1. Experimental electrochemical current densities on Fe−N−C catalysts in the neutral 0.05 M K3PO4 + 0.05 M H3PO4 buffer solution
in the presence of CO2 (saturated, 30 mM, pH: 6.4), CO (saturated, 1 mM, pH: 6.9), CH2O (1 mM, pH: 6.9), CH3OH (1 mM, pH: 6.9), and
formic acid (1 mM, pH: 6.7). (a) LSV (−5 mV s−1) and (b) chronoamperometric bulk electrolysis at constant iR-corrected electrode
potentials. Data points are averages over the 75 min electrolysis at each electrode potential. Lines are to guide the eye. Catalyst loading: 0.75
mg cm−2.
lysts.14,38−40 The carbon support not only hosts sufficient M−
Nx sites but also offers excellent electron conductivity. This
was demonstrated using a polyaniline-derived Fe−N−C
catalyst with favorable CO2RR activity of up to 6 mA cm−2
CO partial current density at −0.55 VRHE at 80% efficiency, as
well the generation of methane around −1.0 V.41 Subsequent
studies tuned the synthesis protocols, varied the central metal
ion, and deployed them in more efficient flow cell electrolyzer
reactors. Today, the M−N−C catalysts have demonstrated
great potential for becoming efficient, stable, and cost-effective
catalysts for electrochemical CO2 conversion into CO,41−47 the
vital intermediate for the “beyond CO” hydrocarbon
products.11,13 The details of these mechanistic catalytic
pathways, however, have remained elusive yet are critical for
a thorough understanding of the processes. This contribution
will change that.
In a previous study, we reported how the chemisorption of
*CO and *H on metals controls the experimental product and
its selectivity.13 Balanced *CO binding at moderate *H
binding, present for only Cu surfaces, favored the protonation
of adsorbed *CO associated with beyond CO products.11
However, Fe−Nx moieties of Fe−N−C catalysts were
predicted to generate beyond CO products, as well.13,36
Indeed, Fe−N−C catalysts showed measurable, though
moderate, selectivity for methane.44 To increase the faradaic
hydrocarbon production, the mechanistic obstacles causing
finite but low CH4 selectivity must be addressed.
We carried out a combined computational−experimental
study of the CO2RR to CH4 on single-site Fe−N−C catalysts.
To learn more about the molecular mechanism, we considered
the electrochemical reduction of a range of possible reactive
intermediates, such as CO (CORR), CH2O (CH2ORR),
CH3OH, and formate. We monitored the selectivity of each
reactant for CH4, and focusing on the CH2ORR, we studied
the influence of the reactant concentrations and pH and
arrived at new conclusions as to the involvement of protons in
the rate-determining step (RDS). Linking our experimental
results and computational reaction pathway predictions and
building on some previous works,32,48 we established the first
detailed reaction network of the CO2RR toward CH4 over a
member of the family of M−N−C single-site electrocatalysts.
Fe−N−C Catalyst Preparation and Characterization. The
polyaniline-derived single-site Fe−N−C catalysts with atomi-
cally dispersed Fe−Nx moieties employed here are identical to
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Letter
those described and characterized in our previous work.14,43
To ensure the role of the atomically dispersed Fe−Nx motifs,
an iron-free yet otherwise identical N−C catalyst was prepared
as used as a control. Conventional ex situ characterization of
physiochemical properties of the Fe−N−C material is shown
in the Supporting Information (Table S1, Figures S1−S3). X-
ray diffraction patterns (XRD, Figure S1) and transmission
electron microscopy (TEM, Figure S2) indicated that the Fe−
N−C catalyst had a similar amorphous carbon structure as the
metal-free N−C one. N2-specific adsorption and double-layer
capacity measurements were carried out, which suggested
comparable surface areas (Figure S3) of Fe−N−C and N−C.
Elemental analysis revealed the same or similar nitrogen
content in the two catalysts and absence of Fe in the control
(ICP). CO adsorption confirmed the absence of CO adsorbing
centers in the control (Table S1). Moreover, the dispersed
single-site Fe−Nx motifs were identified and confirmed using
N 1s X-ray photoelectron emission spectroscopy,41,43,49
Mossbauer spectroscopy,14 and also X-ray absorption spec-
troscopy43 in our previous approaches. All of these confirm the
dominant character of the coordinative Fe−Nx motifs in our
Fe−N−C model catalyst, whereas the inorganic iron species
remain in trace portion, catalytically not responsible for
methane evolution.2
Catalytic Products and Their Ef f iciencies during CO2RR on
Fe−N−C Catalysts. Upon electrochemical reduction of CO2
using CO2-saturated electrolytes in an H cell, CO, H2, and
CH4 were identified as the main CO2RR products over the
Fe−N−C catalyst.41,43,44 The overall faradaic efficiency
reached 95% during bulk electrolysis tests at constant electrode
potentials. Liquid products such as alcohols, aldehydes, and
formate were below the detection limit for the typical present
electrolysis time of 75 min. However, we also performed a few
longer-term, 1000 min CO2RR experiments (see Table S2).
Similarly, prolonged CO reduction reaction (CORR) was
carried out in buffered potassium phosphate solution for 480
min at the same pH. Now, very small yet clearly detectable
amounts of both methanol and formaldehyde were found
during these longer-term electrolysis tests (see Figures S4 and
S5), demonstrating that these two compounds are apparently
involved in the mechanistic network of the CO2RR as well as
of the CORR over the Fe−N−C catalyst.
Electrochemical Reduction of a Set of Dif ferent COxHy
Molecules. To get insight into the electrochemical CO2-to-
DOI: 10.1021/acsenergylett.9b01049
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Figure 2. (a) Catalytic methane production rate and (b) methane faradaic efficiency as a function of the applied iR-free electrode potential
during the electrochemical reduction of CO2 (saturated, 30 mM), CO (saturated, 1 mM), and CH2O (1 mM) on Fe−N−C (filled symbols)
and metal-free N−C (open symbol) control catalysts. Data are averages over 75 min of electrolysis. Lines are to guide the eye. Conditions:
0.05 M K3PO4 + 0.05 M H3PO4 buffer solution. Catalyst loading: 0.75 mg cm−2.

Figure 3. Production rate of CH4 at various pHs as a function of iR-corrected applied electrode potentials. (a) CO reduction and (b) CH2O
reduction plotted on the RHE scale. (c) CO reduction and (d) CH2O reduction plotted on the NHE scale. (e) Logarithm of the CH4
formation rate from CH2O at different pHs versus applied potential. Electrolytes are 0.05 M K2HPO4 + 0.05 M K3PO4 (pH = 11.9), 0.05 M
K3PO4 + 0.05 M H3PO4 (pH = 6.9), and 0.05 M KH2PO4 + 0.05 M H3PO4 (pH = 2.25) for pH variation. Data are averages over 75 min of
electrolysis. Lines are to guide the eye. Catalyst loading: 0.75 mg cm−2.

CH4 reaction pathways, CO2, CO, CH2O, CH3OH, and reaction cascade. Table S2 lists the reaction parameters used
formate were used separately as feed reactants in order to
in the experiments.
investigate their relative reaction rates and resulting product
spectra. The choice of these feeds was based on the fact that all The formal chemical transformations and their standard
of them may constitute reactive intermediates of the CO2RR potentials read
process. In particular, we were interested in whether and to
what degree these potential reactive intermediates can be CO2 + 8(H+ + e−) → CH4 + 2H 2O
electrochemically reduced to CH4 on the Fe−N−C catalysts,
which carries useful insight in the catalytic CO2-to-CH4 E0 = 0.17 VRHE (1)

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ACS Energy Lett. 2019, 4, 1663−1671
ACS Energy Letters
HCOOH + 6(H+ + e−) → CH4 + 2H 2O
E0 = 0.28 VRHE (2)
CO + 6(H+ + e−) → CH4 + H 2O
E0 = 0.26 VRHE (3)
CH 2O + 4(H+ + e−) → CH4 + H 2O
E0 = 0.45 VRHE (4)
CH3OH + 2(H+ + e−) → CH4 + H 2O
E0 = 0.63 VRHE (5)
The overall electrocatalytic polarization behavior comprising
all cathodic processes was studied for each individual feed
molecule using transient linear sweep voltammetry (LSV)
(Figure 1a) and stationary bulk electrolysis (Figure 1b).
Reactivity trends of transient and stationary measurements
matched well. CO2 outperformed the HER control activity (N2
as feed in Figure 1a), largely thanks to significant CO evolution
(Figure S6) below −0.4 VRHE. CO2 was followed by formic
acid, while the other reactants exhibited faradaic currents
comparable to the HER background. CO feeds, likely due to its
site blocking nature, displayed lower currents than the
background (Figure 1a). Liquid products remained below
the detection limit. Methane formation, however, was observed
for CO2, CO, and CH2O feeds (Figure 2) and became the
primary focus of subsequent kinetic studies.
First, we analyzed how the CH4 formation rate changed with
applied potential. Figure 2 shows the potential-dependent
electrocatalytic methane production rate and the faradaic
methane efficiency for each feed on Fe−N−C catalysts (solid
symbols) and Fe-free “N−C” control (open symbols) catalysts.
The Fe-free catalysts displayed little to no CH4 yield,
evidencing the catalytic role of the Fe−Nx single sites in the
CO protonation process. Closer inspection of Figure 2 reveals
more anodic CH4 onset potentials under CH2O feeds
compared to CO or CO2 feeds. This suggests that CH2O
activation and subsequent protonation to methane is fast, while
activation barriers in the catalytic cascade from CO2 or CO to
CH2O appeared to delay their reduction kinetics. Indeed, the
fact that the CH4 yields under CO2 and CO feeds track each
other so closely is an indication that they are kinetically limited
by a shared elementary process, more specifically the
protonation of adsorbed CO, *CO. Note that we will
abbreviate surface-adsorbed species with an asterisk on the
left to symbolize a surface site that binds to the element
adjacent to it. All three feeds showed steadily increasing
catalytic CH4 formation rates with increasing applied over-
potential up to −0.65 VRHE. Beyond −0.65 VRHE, catalytic CH4
rate hikes with potential slowed down for CO2 yet increased
sharply for CH2O. For CO feeds, the CH4 formation rates
actually peaked and subsequently dropped slightly at more
cathodic potentials. We attribute this distinct kinetic behavior
to the poisoning effect of adsorbed *CO on the Fe−N4 sites
due to their strong binding, which will be supported later by
computational analysis.11,13,15 For CO2, even though its
saturated bulk concentration is about 30 times that of CO,
local depletion in COx concentration at the double layer will
limit sustained CH4 formation rates at sufficiently cathodic
potentials. With the cathode at −0.65 VRHE, the CH4 formation
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Letter
Figure 4. Free energy diagrams toward CH4 starting from CO2, CO
and CH2O on Fe−N−C catalysts at 0 VRHE and with reference to
CH4(g). The three limiting potential steps are shown by V1, V2,
and V3, with the reduction of CH2O having the smallest limiting
potential step in line with the experiments.
rate from CH2O displayed a sudden growth, suggesting a shift
in the rate-determining reaction step. We want to point out
that previous kinetic studies invariably showed that the
electroreduction of aldehydes on metallic electrocatalysts
exclusively generated the respective primary alcohols.13,50,51
Here, however, the solid nonmetallic, single-site Fe−N−C
catalysts with graphene-embedded molecular sites generated
selectively the respective hydrocarbon (CH4). This is
consistent with results on molecular catalysts and suggests
mechanistic analogies between molecular and solid-state
catalysts.32
Next, we investigated the CH4 formation rate and its faradaic
efficiency as a function of the initial CH2O concentration in
the electrolyte; see Figure S7. The CH4 yield and its faradaic
efficiency scaled nearly linearly with the CH2O concentration
at a given applied potential, with the slope varying with the
applied potential. This suggests that the CH4 rate law is
approximately first order with respect to CH2O, which was
confirmed in kinetic log−log analysis (see Figure S8).
Proton-Coupled and -Decoupled Catalytic Reaction Steps. The
generation of CH4 during the electrochemical reduction of
CO2 on Fe−N−C (and similarly on molecular cobalt
protoporphyrin) is known to show a Nernstian dependence
on pH,32,43 suggesting that the rate-determining protonation of
adsorbed *CO does involve a concerted proton-coupled
electron transfer (PCET). To verify this, we studied the pH
dependence of the CORR on the single-site catalysts. Results
in Figure 3a,c confirmed the Nernstian behavior of the CH4
onset potentials and CH4 formation rates, evidenced by the 59
mV shift per pH unit on the NHE scale. Thus, on the present
Fe−N−C single-site catalysts, experiments suggest the
protonation of *CO at the carbon atom to *CHO to be the
slowest and thus RDS in the CORR pathway to methane. This
will be compared to computational predictions further below.
Similar pH tests were then conducted using CH2O as the
reactant feed (see Figure 3b,d,e). Now, the CH4 onset
potentials exhibited close to no pH dependence on the NHE
scale (Figure 3b) yet did so on the RHE scale (Figure 3b). We
conclude that the catalytic pathway from CH2O to CH4 is
limited by a proton-decoupled electron transfer (PDET) step
resulting in an experimental rate law following
RateCH4 ≈ k e−αη[CH 2O]1 [H+]∼ 0
(6)
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ACS Energy Letters Letter

Figure 5. Detailed protonation steps of *CO toward *CHO via the coadsorption of *CO + *H on (a) the Cu(111) facet and on (b) Fe−N−
C, respectively. Insets are schematic illustations of coadsorption of CO and *H (namely, *CO + *H).

Mechanistic DFT calculations are now needed to rationalize

Figure 6. Hypothesized paths of methanol and methane formation
on a single-site Fe−N−C catalyst.
where k is a heterogeneous rate constant, the exponential term
describes the rate dependence on the applied cathodic
overpotential η[V], and α[V−1] denotes a parameter related
to the inverse Tafel slope.
To summarize our experimental findings on Fe−N−C
catalysts, the CO2RR as well as the CORR generally exhibit a
wider range of products, primarily CO, methane, as well as
some formaldehyde and methanol. The CH2ORR exclusively
yields CH4. Both the CO2-to-CO and CH2O-to-CH4 reactions
appear to be rate-limited by a slow PDET, while the CO-to-
CH4 reaction features a concerted PCET as its slowest step.
the experimental findings and to establish a full mechanistic
network.
Density Function Theory Calculations of Reaction Pathways to
CH4. DFT predictions of possible mechanistic pathways from
CO2 to CH4 were carried out by calculating the free energy of
possible intermediates on single-site Fe−N4−C motifs at 0
VRHE. This particular metal coordination was chosen because
iron sites generally prefer four coordinative nitrogens.43
Calculation details are presented in the Supporting Informa-
tion (Experimental Section, Tables S3−S5, and Figure S9).
Figure 4 presents the free energy network diagram of the
individual reaction pathways from the different reactants to
methane. The calculations are assuming concerted proton
electron transfer and are evaluated at 0 VRHE and with
reference made to CH4(g) as this reference is common for the
reactions investigated. It shows that Fe−N4−C binds *CO
relatively strongly and the most difficult step from CO2/CO to
CH4 is the protonating *CO to *CHO (V2: ΔG*CO to

Figure 7. Comprehensive reaction network for the CO2 reduction toward CH4 via CO and CH2O over the Fe−N−C catalyst. PCET: proton-
coupled electron transfer; PDET: proton-decoupled electron transfer.

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ΔG*CHO). Indeed, the *COH has also been proposed as the
first reduced intermediate following *CO on metallic Cu
facets.52,53 However, considering that the M−N−C type
catalysts contribute isolated active sites, the free energy of
the *COH intermediate is about 1.5 eV higher than that of
*CHO, possibly accommodating an unfavorable triple bond
between Fe−Nx and the *COH intermediate.
In comparison, the reduction of CO2 to CO (V1: ΔGCO2 to
ΔG*COOH) and that of CH2O to CH4 (V3: ΔGCH2O to
ΔG*CH2OH/*OCH3) exhibit lower energetic pathways, leading to
less potential requirement to drive these two conversions,
which is in line with the experiment observations (see Figures
2 and S6).
We first focus on a discussion of the selectivity of the
reduction of CH2O. Notably, no methanol was observed over
Fe−N−C catalysts, which is distinctly different from metals
(Cu, Ag, and Au), which majorly produces methanol.
Previously, for metal catalyst, we tried to classify the two
types of products from aldehyde reductions to be a matter of
choice: oxygen bonding (*OCH3) gives alcohols, while the
carbon bonding (*CH2OH) leads to fully reduced hydro-
carbons.13 Nevertheless, we do observe that the calculated
*CH2OH and *OCH3 for the Fe−N−C on the free energy
scale are similar (see Figure 4). Given the fact that CH2O
reduction on Fe−N−C produces only CH4, we thus propose
that uniquely this catalyst offers a special reaction path or has
very different water stabilization as compared to the metal
catalyst. Water indeed highly influences the stabilization of
CO2RR intermediates for Cu facets,26 and for ORR/OER
intermediates, static water solvation has been shown on M−
N−C systems.54 Investigating water dynamics on the M−N−C
for this analysis was found to be challenging due to the spin-
polarized nature of the calculations. This issue could be
addressed with ab initio molecular dynamics (AIMD) of water
on the M−N−C system, which is out of scope of the present
study.
Second, we turn to the pH dependence of these reactions,
where the CO2RR into CO (performed in our early work;55
data is presented in Figure S10) and CH2ORR into CH4
showed a non-Nernstian behavior while the CO-to-CH4
process followed a Nernstian one. We hypothesize that a
PDET is the key to rationalize this pH dependence. A PDET
was reported to be more likely if the interaction of the
intermediates with the catalyst is weak.48 On the basis of this,
for weakly bound species, the adsorption becomes a slow RDS,
and the reaction is limited by a PDET, as shown in the
equations below
CO2 + ∗ + e− → *CO−2 (7)
CH 2O + ∗ + e− → *CH 2O− (8)
accounting for the experimentally observed pH-independent
catalytic rates on the NHE scale. Our DFT calculations using
the computational hydrogen electrode (CHE) assume a
concerted proton−electron transfer (equivalent to PCET)
and thus could not capture the feature of the PDET. Previous
investigations have indeed shown the simulation of stable [M−
N−C−CO2]− transition states,32,56 however, without clearly
pointing to the reference potential for such PDET. This
implies that both models have their limitations to clearly
describe the electrocatalytic process. The experiments,
however, provide important information about the reaction
mechanism.
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Letter
We now turn to the discussion of the relatively low (yet
finite compared to methanol) methane selectivity on the Fe−
N−C catalyst. The Fe−N4 motifs show similar “binding”
properties as copper (the well-known excellent hydrocarbon
producer), holding the ability to bind *CO without having *H
under the potential deposited. Upon this, to better understand
the performance difference in CH4 selectivity of these two
types of candidates, we compared the proton transfer details of
the *CO-to-*CHO steps on the single-site Fe−Nx motif and
the extended metal Cu(111) facet.57 Illustrated in Figure 5,
comparable PCET barriers (marked as V2 in Figure 5a,b,
ΔG*CO to ΔG*CHO, ∼1 eV) could be observed on these two
candidates. For the Cu(111) facet, a pre-*H/*CO coad-
sorption (the schematic is displayed in Figure 5a) is
energetically favored, leaving V2 (∼1 eV) as the major limiting
step. This is in agreement with a recent work focusing on CH4
evolution via CORR on a Cu-based catalyst,58 suggesting that
the protonation of adsorbed *CO into *CHO (RDS of CH4
formation) is preferentially via the Langmuir−Hinshelwood
reaction channel (*CO + *H → *CHO). On the contrary, on
the Fe−N−C motif, the coadsorption of *CO/*H step (V
marked in Figure 5b) sets the main dynamic barrier, emerging
as the limiting step, resulting in low hydrocarbon activity, and
forcing an Eley−Rideal-type protonation step (*CO + H+sol +
e− → *CHO).
In principle, the single-site Fe−N−C catalyst constitutes an
excellent catalytic CO producer and thus could contribute
sufficient reactive *CO intermediates for higher hydrocarbon
yields. Unfortunately, indicated by our simulations, the isolated
active site structure on the other hand causes difficulty in *CO
and *H coadsorption, precluding dominant formation of
hydrocarbons. This finding suggests that the highly active
CH4(g) product formation may require an extended surface or
a nearby proton source to lower the barrier of protonation.
Strategies to circumvent this would be to increase the number
of active sites and thus reduce their mutual distance, or else,
the introduction of suitable hydrogen adsorption/COx reactive
twin sites may be a way toward enhanced hydrocarbon yields.
As a summary, the present combined experimental and
theoretical mechanistic study has addressed the kinetics of the
electroreduction of various small molecules that may constitute
reactive intermediates on the way to methane, in particular,
CO2, CO, and CH2O. The study aimed at (i) identifying the
role of these reducible reactants during the overall CO2-
toward-CH4 pathway; (ii) understanding the rate-limiting
factor of these key reactions; and (iii) reasoning the obstructed
hydrocarbon selectivity of the Fe−N−C catalyst. This
knowledge will be crucial in the design of novel catalysts to
reduce CO2 into hydrocarbons.
To achieve the first two goals, unfortunately, neither our
experiments nor computation delivers direct evidence to
address the CH2O reduction details. By tracking the methanol
trace (see Figure 6), which is produced in terms of CO2/
CORR electrolysis (Figure S5) while denied in CH2O
reduction (Figures S7 and S8), we could speculate that
methanol more likely originated via a non-CH2O channel, and
the *CH2OH is the key intermediate (*CO → *CHO →
*CHOH → *CH2OH → CH3OH). Upon this hypothesis, the
*CH2OHrelevant for methanol formationcould be
filtered out from the pure CH2ORR, making methane as the
only end-product (CH2O → *OCH3 → *O + CH4, shown in
Figure 6). This shows that the Fe−N−C catalyst provides
different CH2ORR paths than the metals,13 and better
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understanding requires more systematical investigation upon a
broader catalyst benchmark.
On the basis of the preceding discussions, we establish an
overall reaction network of electrochemical CO2 reduction into
CH4, clearly addressing the contribution of CO2, CO, and
CH2O. Here, CO plays as the key intermediate toward
methane, formaldehyde, and methanol. Moreover, the
produced CH2O in this reaction network could be further
reduced and open up an extra reaction channel toward
methane. On the contrary, methanol is more likely yielded
from the non-CH2O reaction channel and poses as a
byproduct aside the methane. More interestingly, our
experimental studies have shown that some of the reduction
steps involve PCET (namely, CO-to-CH4) steps, whereas
others, in particular, such that involved rather weakly bounded
species, featured PDET (namely, CO2-to-CO and CH2O-to-
CH4) steps. This provided a broader and deeper understanding
of the reaction mechanism and reaction network of the CO2
reduction into a wide range of single-carbon chemicals on the
Fe−N−C single-site catalysts (see Figure 7).
As for the third goal, our simulations revealed that the low
hydrocarbon selectivity is primarily due to the isolated nature
of the active site of the Fe−Nx motifs, which limits the rate
with which further reduction and protonation of adsorbed
*CO can occur. To overcome this drawback, synthesis
approaches to achieve catalysts with novel site densities and
site structure are needed. We speculate that introducing dual
twin metal sites, where two metal centers are located in atomic
proximity, would mechanistically allow more rapid protonation
of CO, boosting the hydrocarbon formation on Fe−N−C
catalysts. Alternatively, “hybrid tandem catalyst” schemes are
conceivable to maximize the effective yield of hydrocarbons or
liquid oxygenates. One such scheme would consist of i) high
surface area Fe−N−C catalysts with atomically dispersed Fe−
Nx moieties acting as local CO producers and ii) dispersed Cu
nanoparticles, where the protonation of readsorbed CO occurs
generating hydrocarbons or oxygenates. In a next step, more
sophisticated “Tridem catalyst” schemes (also referred to as
“double tandem” or “hybrid cascade catalyst”) are conceivable,
consisting of Fe−N−C catalysts with supported and diffusively
coupled Cu and Ni nanoparticles, where the Ni particles take
care of reducing aldehydes into their respective alcohols,
thereby maximizing the effective alcohol yields.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsenergy-
lett.9b01049.
Description of the material, electrochemical character-
ization, and theoretical calculation (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: asvarela@iquimica.unam.mx.
*E-mail: pstrasser@tu-berlin.de.
ORCID
Wen Ju: 0000-0002-6485-1133
Alexander Bagger: 0000-0002-6394-029X
Xingli Wang: 0000-0003-2785-9707
Jan Rossmeisl: 0000-0001-7749-6567
1669
Letter
Peter Strasser: 0000-0002-3884-436X
Author Contributions
#
W.J. and A.B. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge Climate-KIC under the EnCO2re
project. P.S., W.J., and X.L.W are grateful for partial support by
the German Federal Ministry of Education and Research
(Bundesministerium für Bildung und Forschung, BMBF)
under Grant #03SF0523A,C−“CO2EKAT” and FCH Joint
Undertaking 2 (CRESCENDO Project, Grant Agreement No.
779366). A.B. and J.R. thank the Carlsberg Foundation (Grant
CF15-0165) and the Innovation Fund Denmark (Grand
Solution ProActivE 5124-00003A). A.S.V. acknowledges
funding from CONACyT (Project No. 282552). P.S. and
W.J. acknowledge financial support by the Cluster of
Excellence (“UniSysCat”) funded by the Deutsche For-
schungsgemeinschaft and managed by the TU Berlin.
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1671 DOI: 10.1021/acsenergylett.9b01049

ACS Energy Lett. 2019, 4, 1663−1671