Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 14435−14442 pubs.acs.org/journal/ascecg

Dynamic Interplay between Copper Tetramers and Iron Oxide

Boosting CO2 Conversion to Methanol and Hydrocarbons under
Mild Conditions
Bing Yang,*,†,‡,■ Xin Yu,∥,⊥ Avik Halder,‡ Xiaoben Zhang,†,■ Xiong Zhou,∥,⊥ Gilbère J. A. Mannie,∥
Eric Tyo,‡ Michael J. Pellin,‡ Soenke Seifert,§ Dangsheng Su,†,■ and Stefan Vajda*,‡,#,●
†
Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457
Zhongshan Road, Dalian 116023, China
‡
Materials Science Division and §X-ray Science Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois
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60439, United States

∥
National Energy Center for Coal to Clean Fuels, Synfuels China Co., Ltd., Huairou District, Beijing 101400, China
⊥
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
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#
Institute for Molecular Engineering, The University of Chicago, 5640 S. Ellis Avenue, Chicago, Illinois 60637, United States
■
University of Chinese Academy of Sciences, No. 19(A) Yuquan Road, Beijing 100049, China
●
Department of Nanocatalysis, J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 18223
Prague, Czech Republic
*
S Supporting Information

ABSTRACT: Atomically precise subnanometer catalysts are of

significant interest because of their remarkable efficiency in a
variety of catalytic reactions. However, the dynamic changes of
active sites under reaction conditions, in particular, the transition
of cluster−oxide interface structure have not yet been well-
elucidated, lacking in situ measurements. By using multiple state-
of-the-art in situ characterizations, here we show a dynamic
interplay between copper tetramers and iron oxides in a single-size
Cu4/Fe2O3 catalyst, yielding an enrichment of surface Cu4−Fe2+
species under reaction conditions that boosts CO2 hydrogenation
at near-atmospheric pressures. During reaction, Cu4 clusters
facilitate the reduction of Fe2O3 producing surface-rich Fe2+
species in the proximate sites. The as-formed Fe2+ species in
return promotes CO2 activation and transformation over Cu4 cluster, resulting in strikingly high methanol synthesis at low
temperatures and C1/C3 hydrocarbon production in a high-temperature regime. The discovery of highly active Cu4−Fe2+ sites
thus provides new insights for the atomic-level design of copper catalyst toward high-efficiency CO2 conversion under mild
conditions.
KEYWORDS: CO2 conversion, Synergistic interaction, In situ characterization, Copper catalyst, Iron oxide

■ INTRODUCTION
Transformation of carbon dioxide to value-added chemicals is
an attractive solution to the growing environmental concerns
and increasing demand for carbon feedstocks.1,2 Chemical
inertness of CO2, however, makes it a great challenge,
particularly under mild conditions. Many efforts have been
devoted to developing high-efficiency and cost-effective
catalyst materials for catalytic CO2 conversion. Copper
catalyst, as one promising candidate, has been extensively
studied for CO2 hydrogenation/reduction.3−6 A variety of
oxide supports, for example, ZnO, ZrO2, and CeO2, was
utilized as promoters that can substantially improve the
dispersion and reactivity of copper catalyst.7,8 Recent studies
on copper-decorated iron oxides indicate that the iron oxides
can effectively reduce the size of copper clusters and
significantly increase CO2 conversion.9−11 To date, however,
the nature of active sites in copper catalyst is still under debate.
Therefore, the identification and precise control of the active
sites is highly demanded in the pursuit of effective CO2
conversion.
Atomically precise subnanometer catalysts including single
atoms,12,13 dimers,14,15 and ultrasmall clusters16−18 have
Received: March 18, 2019
Revised: June 21, 2019
Published: July 15, 2019

© 2019 American Chemical Society 14435 DOI: 10.1021/acssuschemeng.9b01561

ACS Sustainable Chem. Eng. 2019, 7, 14435−14442
ACS Sustainable Chemistry & Engineering
recently attracted tremendous interest because of their specific
activity and remarkable efficiency in a variety of catalytic
reactions, and they provide a new route for the design of high-
efficiency catalyst with atomic precision. Among a wide range
of synthetic methods,19−22 soft landing of mass-selected
clusters is a unique method that enables the fabrication of
atomically precise catalyst with high tunability.23,24 Utilizing
this technique, we have previously synthesized size-selected
metal clusters, for example, Ptn, Agn, and Cun, and described
their specific size effect in both thermo- and electrocatalytic
reactions.16,17,25−27 The ultrasmall copper clusters with a
certain number of atoms (Cu4−5) have shown remarkable
activity in catalytic CO2 conversion.25,26 Beyond cluster size,
support interaction is found particularly essential in single-
atom/subnanometer catalysts in terms of stabilizing the
ultrasmall clusters and modifying their catalytic properties.22,28
Numerous reports have evidenced that the strong coordina-
tion/charge transfer at the interface can greatly influence the
electronic properties of metal atoms/clusters.20,25,29,30 How-
ever, most of the previous studies have considered only a
stationary catalytic structure based on ex situ characterization,
that is, aberration corrected scanning transmission electron
microscopy (AC-STEM) and/or extended X-ray absorption
fine structure (EXAFS). A dynamic change of the active sites at
subnanometer level, in particular, the transition of cluster−
oxide interface under reaction conditions, has been less
concerned lacking in situ measurements.
Herein, we synthesized size-selected copper tetramers (Cu4)
on a support of iron oxide and carried out a variety of state-of-
the-art in situ characterizations for the study of CO2
hydrogenation at atmospheric pressure. The choice of Cu4
was based on our previous studies that it exhibits superior
reactivity compared to other Cun (n = 3 or 20) clusters on an
inert Al2O3 support.17,25 The evolution of active sites and the
correlated catalytic reactivity were investigated in situ using
grazing-incidence X-ray absorption spectroscopy (GIXAS)
along with online mass spectrometry. Semi in situ X-ray
photoelectron spectroscopy (XPS) further identified a dynamic
transition of Cu4/Fe2O3 interface, yielding surface-rich Cu4−
Fe2+ species under reaction conditions that account for highly
active methanol and hydrocarbon production. Near ambient
pressure XPS (NAP-XPS) studies on Fe1−xO/Cu(100) were
performed to unveil the synergistic role of Cu−Fe2+ interface
in favor of CO2 activation and transformation.
■
EXPERIMENTAL SECTION
Material Synthesis. Copper tetramers (Cu4) were mass-selected
and deposited onto a thin layer (∼2 nm) of iron oxide on silicon
wafer via soft landing, using a method previously described.17,31 In
brief, a variety of copper cluster ions were produced by magnetron
sputtering before being mass-selected within a quadrupole mass filter.
The positively charged Cu4+ clusters were selected and soft-landed
onto the supports. The cluster ions were immediately neutralized
upon landing and the deposition rate was counted by monitoring the
flux of charges using a picoammeter (Keithley Model 6489). The
surface coverage of Cu4 clusters was set at 10% atomic Cu monolayer
equivalent to avoid aggregation upon deposition (1 monolayer
equivalent = ∼1.4 × 1014 atoms/cm2). All samples were fully aged in
air and oxidized copper clusters were identified in the subsequent
experiments.
A thin layer (∼2 nm) of iron oxide (Fe2O3) film was prepared by
atomic layer deposition (ALD) using alternative exposures to
ferrocene and ozone on top of an n-type (phosphorus-doped) silicon
wafer.32 At this thickness, the Fe2O3 thin layer is pinhole-free, but a
well-defined crystallinity is not attained. Previous studies have also
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shown that such an ALD film can keep a variety of clusters from
sintering under mild reaction conditions.18,33
Catalytic Testing and in Situ X-ray Absorption Spectrosco-
py. Catalytic testing and in situ grazing-incidence X-ray absorption
spectroscopy (GIXAS) measurements of Fe 2O3-supported Cu4
clusters were performed at beamline 12-ID-C of the Advanced
Photon Source at the Argonne National Laboratory. The experimental
setup has previously been reported elsewhere.17,25,34 The Cu4/Fe2O3
samples were placed in a home-built cell reactor17,34 equipped with
Kapton windows that allow X-ray transmission. The reaction gases
were mixed in a manifold gas mixer to maintain a 20 sccm flow of 1%
CO2 and 3% H2 gas mixture carried in helium at a constant pressure
of 1.05 atm. After an initial 30 min purge of the reactor with the gas
mixture, the samples were heated stepwise from 25 °C up to 425 °C
(50 °C interval) with duration of 25 min at each temperature for data
acquisition.
The X-ray absorption near edge structure (XANES) spectra in
GIXAS measurements were collected at both Cu K edge (8.9 keV)
and Fe K edge (7.1 keV) by a fluorescence detector (Vortex)
mounted parallel to the sample surface, to minimize background from
elastic scattering. The X-ray beam was scattered off the sample surface
close to the critical grazing incident angle (αc = 0.18) to
enhance surface sensitivity. The spectra of both Cu (Cu metal foil,
Cu2O, and CuO powder compounds) and Fe (Fe metal foil, Fe3O4,
and Fe2O3 powder compounds) bulk standards were collected in
transmission mode as reference spectra for linear combination fit
(LCF) analysis. The XANES data were processed and analyzed using
Athena software.
The catalytic test was carried out in the cell reactor simultaneously
monitored by an online quadrupole mass spectrometer (Pfeiffer
Prisma QMS 200). An electronic gas regulating valve (EVR 116,
Pfeiffer) was placed on the outlet of gas flow for sampling, ensuring a
constant pressure of 5 × 10−6 mbar in the mass spectrometer. All gas
reactants and products were calibrated to 0.5−3% standard gas
mixtures balanced in helium. The mass spectrometer was precali-
brated to ensure a linear response to the gas concentration. To ensure
a measurement of steady state, we chose the MS data from the last 5
min at each temperature step and averaged for further reactivity
calculation, which has proved to be reliable in reactivity measure-
ments, according to our previous studies.17,25
Semi in Situ X-ray Photoelectron Spectroscopy. The semi in
situ XPS measurements were performed by a Thermofisher
ESCALAB 250Xi spectrometer in a ultra-high-vacuum (UHV)
chamber with base pressure of 5 × 10−9 mbar. The system was
equipped with an additional high-pressure cell that allows the sample
treatments in atmospheric gas environment (reducing/oxidizing) at
elevated temperatures. After the gases were pumped out, the sample
was transferred back under UHV conditions for XPS measurements.
All XPS spectra were recorded with an Al Kα X-ray source (hv =
1486.6 eV) and the binding energy (BE) was calibrated by setting the
Si 2p peak of nonoxidized silicon from substrate to 99.4 eV. The Cu4/
Fe2O3 sample was stepwise reduced in 1 bar of 3% H2 in helium at
175, 275, 325, and 425 °C before each XPS acquisition.
STM and NAP-XPS Studies on Fe1−xO/Cu(100). The scanning
tunneling microscopy (STM) study on Fe1−xO/Cu(100) was carried
out in an Omicron UHV chamber (base pressure of 1 × 10−10 mbar)
equipped with low-energy electron diffraction (LEED), Auger
electron spectroscopy (AES), infrared reflection-adsorption spectros-
copy (IRAS), scanning tunneling microscopy (STM), and a
quadrupole mass spectrometer for temperature-programmed desorp-
tion (TPD). The Cu(100) sample, which is 4 mm × 4 mm × 1 mm in
shape, was mounted to a Mo sample plate. The sample temperature
was calibrated by measuring the temperature of the Mo sample plate
using infrared thermometer. The clean Cu(100) surface was obtained
by cycles of Ar+ sputtering at 300 K and annealing in UHV to ∼850
K. Fe (99.99%) was deposited using an e-beam assisted evaporator
(EMT3, Omicron). The Fe1−xO on Cu(100) was prepared by
depositing a submonolayer amount of Fe onto the substrate at 300 K,
followed by subsequent oxidation to ∼800 K in 1 × 10−6 mbar oxygen
ambience. Surface coverage was estimated by STM images. All STM
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ACS Sustainable Chem. Eng. 2019, 7, 14435−14442
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Figure 1. (a, b) XANES spectra of Cu4/Fe2O3 with increasing temperatures under in situ reaction conditions (1% CO2/3% H2 balanced with
helium, 1 atm) collected at Cu K edge (a) and Fe K edge (b); (c, d) results of linear combination fit (LCF) for XANES data. Fraction of copper in
Cu4/Fe2O3 (c), fraction of iron in Cu4/Fe2O3 (d), and blank Fe2O3 support (e); (g) calculated Fe2+ concentration in Cu4/Fe2O3 and blank Fe2O3
support deduced from the LCF results.
measurements were performed at room temperature with bias voltage
applied on the sample.
Near ambient pressure X-ray photoelectron spectroscopy (NAP-
XPS) experiments were performed in a separate SPECS system with
base pressure of 5 × 10−10 mbar. NAP-XPS experiments were
conducted in situ in an environment of 0.53 mbar CO2 and 0.26 mbar
H2 at room temperature. All XPS spectra were acquired using a
monochromatic Al Kα X-ray source (hv = 1486.6 eV). The
spectrometer was calibrated using Au 4f7/2 peak of a clean Au(111)
sample before experiments.
■
RESULTS AND DISCUSSION
In Situ GIXAS Characterization. The as-prepared Cu4/
Fe2O3 was fully aged in the air before transferring to beamline
for in situ GIXAS measurements. The single-size selectivity
with atomic precision and the integrality of Cu4 tetramers
upon landing were previously verified.16,17,23,25 Both Cu4/
Fe2O3 and the blank Fe2O3 support was characterized under
identical reaction conditions in CO2/H2. The XANES spectra
of Cu4/Fe2O3 collected at Cu K edge (Figure 1a) demonstrate
a gradual reduction of copper clusters with increasing
temperature by comparing to reference spectra of standard
copper compound (Figure S1, Supporting Information). At 25
°C, an oxidized feature of Cu4Ox was identified with the
adsorption edge of ∼8.980 keV, suggesting the Cu4 clusters
were fully oxidized after exposure to the air.31 After heating up
to 125 °C in CO2/H2, a postedge feature at ∼9.0 keV (marked
by red arrow) along with the downshift of the adsorption edge
(∼1 eV) characteristic of Cu metal indicate the reduction of
Cu4Ox to metallic phase at 125 °C. In terms of Fe K edge, no
prominent changes were observed for either Cu4/Fe2O3
(Figure 1b) or the blank Fe2O3 support (Figure S1). Both
resemble Fe2O3 with adsorption edge at ∼7.125 keV,
indicating a stable phase of Fe3+ oxide during the entire
reaction. No carbide peaks (∼7.117 keV) were detected under
experimental conditions.
Linear combination fit (LCF) analysis was performed to
quantitatively describe the evolution of Cu and Fe oxidation
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state with increasing temperature. As shown in Figure 1c, the
copper tetramers in Cu4/Fe2O3 possess a nearly even
proportion of CuO and Cu2O at 25 °C, giving an approximate
chemical state of Cu4O3. At above 125 °C, nearly 60% of
copper is thus reduced, resulting in an average valence state of
∼0.5. This infers a reduced Cu4O phase which remains
constant up to 425 °C. In the case of Fe, the iron oxide thin
layers in Cu4/Fe2O3 (Figure 1d) are primarily composed of a
mixture of α-Fe2O3 (60−65%) and γ-Fe2O3 (35−40%). Only a
minor reduction can be observed in a high-temperature regime,
resulting in 1−6% of Fe3O4 at above 175 °C and a small
fraction (∼2%) of FeO at 325 °C. In comparison, the blank
Fe2O3 (Figure 1e) does not undergo any obvious reduction,
keeping a nearly constant composition of ∼60% α-Fe2O3 and
∼40% γ-Fe2O3. Though minor (<4%), the enhanced Fe2+
content in Cu4/Fe2O3 can still suggest the reduction of iron
oxides facilitated by the addition of copper tetramers under
reaction conditions (Figure 1f).
Catalytic Performance of Cu4/Fe2O3 for Atmospheric
CO2 Hydrogenation. The catalytic test of Cu4/Fe2O3 was
carried out along with in situ GIXAS experiments. The
products were monitored by an online quadrupole mass
spectrometer at their characteristic m/z ratio, for example, CH4
(m/z 15), CH3OH (m/z 31), and C3H6 (m/z 41). The
turnover rate (TOR) was defined as the rate of molecules
produced over the total number of Cu atoms as deposited (s−1·
atom−1). Note that although many C3+ hydrocarbons have a
common fragment ion at m/z 41, here, we consider only
propylene (C 3 H 6 ) in the calculation of TOR as a
representative for C3+ hydrocarbons. The selectivity was
calculated based on the TOR of three monitored products of
CH4, CH3OH, and C3H6 (see Supporting Information).
Figure 2a,b presents the TOR and selectivity of CH3OH,
CH4, and C3H6 (C3+ hydrocarbons) of both Cu4/Fe2O3 and
blank Fe2O3. As for Cu4/Fe2O3, the yield of methanol
dominates in the low-temperature regime (125−325 °C)
with a TOR(CH3OH) as high as ∼1.4 × 10−3 s−1·atom−1 at
325 °C and a selectivity of ∼63%. At higher temperatures
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Figure 2. (a) Reactivity of Cu4/Fe2O3 (fully filled symbol and solid
line) and blank Fe2O3 (half-filled symbol and dashed line) for CO2
hydrogenation monitored by online mass spectrometer. Turnover rate
(TOR) is calculated per copper atoms for CH3OH (m/z 31), CH4
(m/z 15), and C3H6 (m/z 41). (b) Selectivity of Cu4/Fe2O3 and
blank Fe2O3 support based on the production of CH3OH, CH4, and
C3H6. (c) Comparison of methanol activity on Cu4/Fe2O3 (red) with
respect to Cu4/Al2O3 (yellow), showing a promotive role of iron
oxide. The plot of methanol activity on Cu4/Al2O3 was reproduced
from the previous experiments.25
(>325 °C), the reaction path switches from methanol synthesis
to methanation (CO2 + 4H2→ CH4 + 2H2O) and Fischer−
Tropsch synthesis (FTS, nCO2 + 3nH2 → CnH2n + 2nH2O).
Methanol production declines because of its exothermic
nature35 and further hydrogenation becomes more favorable
with increasing activity of CH4 and C3+ hydrocarbons. The
TOR(CH4) increases significantly to 6.5 × 10−2 s−1·atom−1 at
425 °C and the production of CH4 dominates (selectivity of
∼98%). The blank Fe2O3, on the other hand, shows extremely
low activity of all products, with ∼60−70% C3+ selectivity
below 325 °C and ∼90% CH4 at temperatures above. By
comparing the two sets of results, we thus find out that the
copper tetramers can promote methanol synthesis at low
temperatures and significantly improve the yield of C1/C3
hydrocarbon in high-temperature range.
Carbon monoxide is another possible byproduct in CO2
hydrogenation via reverse water−gas shift (rWGS, CO2 + H2→
CO + H2O). In our experiments, no prominent CO signal (m/
z = 28) was observed during the entire reaction, despite a
higher noise level. This is likely caused by its overlap with
fragment ions of CO2 from the feedstock.17 Note that
althought the quantification of CO is less well-defined in the
mass spectrometry, we can still largely rule out the production
of CO, particularly in a low-temperature regime because of the
endothermic nature of rWGS reaction.36,37
Figure 2c presents the methanol production of copper
tetramers on two different supports of Fe2O3 and Al2O3,
respectively. The Cu4/Fe2O3 catalysts show an onset of
methanol activity at 125 °C and the TOR rapidly rises up to
∼1.4 × 10−3 s−1·atom−1 at 225−325 °C, which is among the
highest reported values in the literature.17,35,38 Cu4 clusters on
relatively inert Al2O3(Cu4/Al2O3), however, show only ∼30%
activity of Cu4/Fe2O3 because of a higher activation barrier
(Figure S2). This thus reflects the synergistic role of iron
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oxides on Cu4 tetramers in favor of methanol synthesis from
CO2.
Tracking the Interface Transition in Cu4/Fe2O3.
Considering the subtle change of iron oxides in the bulk
sensitive XAS measurements, we further performed semi in situ
XPS to track the changes of active sites in Cu4/Fe2O3 with
enhanced surface sensitivity.Figure 3a presents the XPS results
Figure 3. Cu 2p (a) and Fe 2p (b) XPS spectra of Cu4/Fe2O3 after
reduction in 1 bar of 3% H2 (in helium) at elevated temperatures. The
tilted background in Cu 2p region is caused by the overlap with Fe
LMM Auger peak. The characteristic shake-up features in Fe 2p
region are marked by black arrow for Fe3+ and red arrow for Fe2+; the
surface and bulk composition of Cu4/Fe2O3 are plotted with
increasing temperature for Cu (c) and Fe (d). The bar plots indicate
the average valence state of Cu (Fe) deduced from XANES analysis
(bulk sensitivity, scale bar to the left), and the line plots (red)
represent the surface concentration of Cu2+ (Fe2+) species reproduced
from XPS results (surface sensitivity, scale bar to the right).
of Cu 2p core level. The high background signal was caused by
its overlap with Fe LMM Auger band. The deconvolution of
Cu 2p3/2 (Figure S3) indicates the presence of oxidized Cu2+
species at 933.5 eV and Cu+/Cu0 species at 932.5 eV. The
difference of Cu+ and Cu0 species is less than 0.2 eV, which is
hardly distinguishable.39 A significant attenuation of Cu 2p
signal is observed at 425 °C, which likely infers the migration
of copper cluster into the iron oxide film, though a formation
of aggregates (sintering) at high temperatures cannot be fully
excluded either. This phenomenon can thus be rationalized
either by strong metal−support interaction (SMSI)7 or the
formation of mixed oxides, that is, CuFeO2.40 The Fe 2p XPS
spectra in Figure 3b show a remarkable reduction of iron oxide
in Cu4/Fe2O3, which is distinct from XANES measurements
due the surface sensitivity of XPS. By comparison of the BE of
Fe 2p3/2 peak and characteristic shake-up features (as marked
by black arrow for Fe3+ and red arrow for Fe2+), a surface
composition of Fe2O3 (25−175 °C), Fe3O4 (275 °C), and
FeO (325 °C) can thus be identified with increasing
temperature.
As shown in Figure 3c,d, both the bulk and surface
composition of Cu4/Fe2O3 are plotted accordingly as deduced
from XANES and XPS. The Cu valence (Figure 3c) deduced
from XANES declines in parallel with the concentration of
Cu2+ in XPS as all copper species are located near the surface
region. Nevertheless, the Fe valence (Figure 3d) remains
nearly constant at∼2.98, whereas the surface Fe2+ concen-
tration rises up with increasing temperature. In contrast, the
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Figure 4. Surface characterization of CO2 activation on Fe1−xO/Cu(100). (a) STM image of 0.5−0.7 ML of Fe1−xO on Cu(100) single-crystal
surface (400 × 400 nm2). Tunneling condition: Vs = 1.0 V, It = 0.1 nA. NAP-XPS spectra of C 1s (b) and O 1s (c) core level of Fe1−xO/Cu(100) in
exposure to 0.53 mbar CO2 and 0.26 mbar H2 at room temperature.
blank Fe2O3 itself however does not show any reduced feature
in Fe 2p spectra (Figure S4). The surface-rich Fe2+ species in
Cu4/Fe2O3 alone infers that only the topmost layers of iron
oxide with access to both Cu4 and H2 are able to be reduced,
which is likely attributed to the hydrogen dissociation and
spillover facilitated by the Cu tetramers.41
Accordingly, we can determine the composition of the active
sites in Cu4/Fe2O3 and further correlate with their reactivity.
(Table S1) Initially, the oxidized Cu4O3 clusters were
identified on a support of Fe2O3 (a mixture of α-Fe2O3 and
γ-Fe2O3) at 25 °C. Increasing to 125 °C, copper tetramers
were readily reduced to Cu4O while the iron oxides remain as
Fe2O3 phase. The coincidence with the onset of methanol
activity infers that the partially reduced copper (Cu4O) is
responsible for methanol synthesis. In the range of 275−325
°C, Cu4O and reduced Fe2+ (Fe3O4/FeO) are found on the
outer surface of Fe2O3 support as the active sites (Cu4−Fe2+/
Fe2O3), leading to highly active methanol production. Above
325 °C, CH4 production dominates, which is likely associated
with the migration of copper to deep surface. Furthermore,
when the unreduced blank Fe2O3 is compared under the same
condition, Cu4/Fe2O3 catalyst reveals a dynamic interplay
between Cu4 cluster and iron oxide. Under reaction conditions,
the hydrogen dissociation and spillover on reduced Cu4O
cluster facilitates the reduction of iron oxide, resulting in
surface-rich Fe2+ species at the proximate sites. The formation
of Cu4−Fe2+ in return promotes methanol and methane at
elevated temperatures (275−425 °C), as highly active sites for
the enhanced activity in hydrogenation of CO2.
NAP-XPS Study of Preferential CO2 Activation on
Fe1−xO/Cu(100) Interface. To reveal the synergistic role of
reduced iron oxide in CO2 activation, we prepared a
submonolayer (ML) of Fe1−xO on Cu(100) as an inverse
catalyst model analogue to the Cu−Fe2+ active sites in Cu4/
Fe2O3, using the recipe reported elsewhere.42,43 Figure 4a
presents the typical STM images of Fe1−xO on Cu(100) with a
surface coverage of 0.5−0.7 ML. The Fe1−xO layers are
characterized as parallel stripes forming rectangular patches on
Cu(100) with a typical height of ∼1.5 Å. The Fe 3p XPS
spectra of Fe1−xO islands (Figure S7) reveals a BE of 55.9 eV,
which indicates a mixed phase of Fe3O4 and FeO.44
NAP-XPS was employed to investigate in situ the reaction
pathway of CO2 activation/hydrogenation on Fe1−xO/Cu-
(100) by exposing 0.53 mbar CO2 plus 0.26 mbar H2 at room
temperature. On the Cu(100) surface only gas-phase CO2 (g-
CO2) at ∼293.3 eV and graphitic carbon (C−C) at ∼284.6 eV
are visible in C 1s region (Figure S5). The C−C species
probably originate from the dissociation of the background
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gases which can be hardly avoided in NAP-XPS studies.45−47
The absence of other higher oxidized carbon and chemisorbed
CO2 species indicates the Cu(100) surface itself interacts
weakly with CO2 at this condition.
On Fe1−xO/Cu(100) surface, additional bands are visible
between 286 and 292 eV in C 1s spectra (Figure 4b). The
deconvolution indicates the presence of carbonate (CO32−)
centered at 291.4 eV,48 formate species (HCOO−) at 289.5
eV,46 carbonyl (−CO) at 287.6 eV,48,49 and hydroxyls (C−
OH) at 286.2 eV.47,50 The O 1s region shows the most intense
peak at 530.0 eV corresponding to oxygen species in Fe1−xO.
The broad peak around 531.5 eV can be assigned to a sum of
CO32−, −CO, and C−OH species, whereas the small band
at 532.5 eV is thus ascribed to HCOO− species, based on
reported values in the literature.45−48 The NAP-XPS results
clearly evidence that the reduced Fe2+ (Fe1−xO) promotes the
CO2 adsorption by forming CO32− species, and further
facilitates CO2 hydrogenation, forming HCOO−, −CO,
and C−OH species as key intermediates,3,25 which can be
further transformed to methanol and hydrocarbon at elevated
reaction temperatures.
■ CONCLUSIONS
We have synthesized copper tetramers (Cu4) on Fe2O3 thin
film as highly active single-size copper catalyst toward catalytic
CO2 conversion at atmospheric pressures. Reactivity study
demonstrates extraordinary activity of Cu4/Fe2O3 for methanol
synthesis of 1.4 × 10−3 s−1·atom−1 at low temperatures (225−
325 °C) and high C1/C3 production rate of 6.5 × 10−2/3.0 ×
10−3 s−1·atom−1 in high-temperature regime (>375 °C),
respectively.
In situ X-ray absorption spectroscopy (XAS) and X-ray
photoelectron spectroscopy (XPS) studies reveal the enrich-
ment of surface Fe2+ species under reaction conditions,
forming Cu4−Fe2+ as highly active sites responsible for
enhanced activity in CO2 hydrogenation. NAP-XPS study on
Fe1−xO/Cu(100) reveals the synergistic role of reduced Fe2+
(Fe1−xO) in favor of CO2 adsorption (CO32−) and activation
(HCOO−, −CO, C−OH) on copper, reflecting the
plausible reaction pathways for CO2 transformation on Cu4−
Fe2+ sites toward methanol and hydrocarbon formation.
In conclusion, we discover a dynamic interplay between
copper tetramers and iron oxides (Figure 5) in single-size Cu4/
Fe2O3 catalyst that boosts CO2 conversion to produce
methanol and hydrocarbons. The Cu4 clusters facilitate the
H2 dissociation/spillover to reduce the iron oxides in the
proximate sites, yielding surface-rich Fe2+ species near copper
tetramers. The formation of Cu4−Fe2+ on Fe2O3 in return
DOI: 10.1021/acssuschemeng.9b01561
ACS Sustainable Chem. Eng. 2019, 7, 14435−14442
ACS Sustainable Chemistry & Engineering
Figure 5. Schematic road map of dynamic interplay between copper
tetramers and iron oxides toward highly active CO2 conversion.
promotes the CO2 activation, yielding CO32−, HCOO−, −C
O, and C−OH as reaction intermediates, which eventually
leads to enhanced activity for methanol and C1/C3 hydro-
carbon production. Our results provide new insights for the
atomic-level design of copper catalyst toward high-efficiency
CO2 conversion under mild conditions.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.9b01561.
XANES spectra of blank Fe2O3 support and references,
calculation of TOR and selectivity, and XANES and XPS
fittings (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: byang@dicp.ac.cn (B.Y.).
*E-mail: stefan.vajda@jh-inst.cas.cz (S.V.).
ORCID
Bing Yang: 0000-0003-3515-0642
Xin Yu: 0000-0002-8390-4034
Stefan Vajda: 0000-0002-1879-2099
Author Contributions
B.Y. and E.C.T. performed the mass-selected cluster
deposition. M.J.P. prepared the iron oxide thin film. B.Y.,
E.C.T., A.H., and S.S. performed the in situ GIXAS
experiments at Advanced Photon Source (APS). X.Y., X.Z.,
and G.M. performed the NAP-XPS measurements. X.B.Z.
assisted with semi in situ XPS measurements and the data
analysis. B.Y. analyzed the XANES and reactivity data and
wrote the manuscript. X.Y., A.H., D.S.S., and S.V. assisted with
the manuscript writing. S.V. and B.Y. conceived the project and
designed the experiments.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The work at the Argonne National Laboratory (B.Y., A.H.,
E.C.T., M.J.P., S.S., and S.V.) was supported by the U.S.
Department of Energy, Office of Science, BES-Materials
Sciences, under Contract DE-AC-02-06CH11357 with UChi-
cago Argonne, LLC, operator of Argonne National Laboratory.
The work at the Advance Photon Source (S.S., beamline 12-
ID-C) was supported by the U.S. Department of Energy,
Scientific User Facilities under Contract DE-AC-02-
06CH11357 with UChicago Argonne, LLC, operator of
14440
Research Article
Argonne The work at Dalian institute of Chemical Physics
(B.Y., X.B.Z., and D.S.S.) was supported by Talents Innovation
Project of Dalian (2016RD04) and the National Natural
Science Foundation of China (21872145). S.V. also acknowl-
edges support from the European Union’s Horizon 2020
Research and Innovation Programme under grant agreement
no. 810310, which corresponds to the J. Heyrovsky Chair
project (“ERA Chair at J. Heyrovský Institute of Physical
Chemistry AS CR − The institutional approach towards
ERA”) during the finalization of the paper. The funders had no
role in the preparation of the article.
■
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