pubs.acs.

org/acscatalysis Research Article

Direct Conversion of CO2 to Ethanol Boosted by Intimacy-Sensitive

Multifunctional Catalysts
Yang Wang, Kangzhou Wang, Baizhang Zhang, Xiaobo Peng, Xinhua Gao, Guohui Yang,* Han Hu,
Mingbo Wu,* and Noritatsu Tsubaki*
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ABSTRACT: It is still a challenge to realize highly efficient conversion of

CO2 to a single target chemical. Herein, substantial progress has been
made, both in catalyst design and reaction route exploration, for the direct
conversion of CO2 to ethanol. An alkene synthesis Na-Fe@C catalyst was
integrated with another potassium-doped methanol synthesis CuZnAl
catalyst to realize the direct conversion of CO2 (39.2%) to ethanol
(35.0%) selectively, accompanied by some useful alkene formation
(33.0%). More in-depth in situ characterizations and density functional
theory (DFT) calculations suggested that the unique catalytic interfaces,
intimacy modes of the multifunctional catalysts, as well as the
intermediate of aldehyde species played vital roles in the higher
conversion rate of CO2 to ethanol. Moreover, the multifunctional catalyst
is easy to fabricate, regenerate, and recycle, being very close to the real
industry application. Therefore, this work is promising to enrich the horizon of the economical utilization of CO2 for renewable
chemical synthesis.
KEYWORDS: CO2 hydrogenation, multifunctional catalyst, tandem catalysis, aldehyde intermediates, reaction network

1. INTRODUCTION noble-metal-based catalysts has turned our attention from

Excessive CO2 emission has aroused enormous environmental traditional methods to the exploration of abundant transition-
concerns, such as global warming, ocean acidification, climate metal-based ethanol synthesis catalysts in CO2 hydrogenation,
such as CoMo sulfide, CoAlOx, and Fe-based catalysts.16−20
change, etc.1 Hydrogenation of CO2 into value-added
Even though a series of advancements have been made in the
chemicals with H2 supplied by water photo/electrolysis is a
field of CO2 hydrogenation to ethanol, the current serious
promising way to alleviate the pressure from carbon
problems like the low yield and unsatisfied selectivity of
emissions.2,3 Recently, the oriented hydrogenation of CO2
ethanol obtained from both abundant transition-metal- and
into target products, for example, liquid fuels,4,5 light olefins,6,7
noble-metal-based catalysts (Table S1) encourage us to explore
and aromatics,8,9 has been extensively studied via a multifunc-
a novel strategy for ethanol synthesis by CO2 hydrogenation.
tional catalyst containing different types of zeolites (mainly,
Recently, higher alcohol synthesis from syngas has been
SAPO-34 and H-ZSM-5) as product regulators. However, the
boosted by rational introduction of a catalytic component for
catalyst efficiency and the selectivity of the desired value-added
oxygen-containing species synthesis into the catalytic sys-
product are still big challenges.
tem.21,22 For the CO2 hydrogenation process, what will happen
Ethanol, as a useful chemical closely related to our daily life,
if we introduce a catalytic component that catalyzes CO2
is mainly produced by the fermentation of cellulosic feedstock
conversion to oxygen-containing species into the traditional
or the hydration of fossil fuel-derived ethylene.10 With the high
CO2 transformation active constituent Fe-based catalyst?
demand of cellulosic feedstock for food and the diminishing of
Herein, we designed a novel multifunctional catalyst by
the nonrenewable resources (coal and crude oil), the integrating a Na-doped Fe-based catalyst (Na-Fe@C) and a
exploration of an alternative strategy in ethanol synthesis is
extremely urgent. The hydrogenation of CO2 into ethanol has
attracted considerable attention because this strategy can Received: April 1, 2021
eliminate greenhouse gas CO2 and produce value-added Published: September 7, 2021
chemicals simultaneously. Noble-metal-based catalysts (Pd,
Pt, and Rh) were usually employed to overcome the initial
barriers of C−O activation and the following C−C coupling
obstacles for ethanol synthesis.11−15 The high price of the

© 2021 American Chemical Society https://doi.org/10.1021/acscatal.1c01504

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Figure 1. CO2 hydrogenation performances. (a) Catalytic performances of Na-Fe@C with different amounts of Na doping. (b) Catalytic
performances of CuZnAl and multifunctional catalysts Na-Fe@C/K-CuZnAl with different amounts of Na and K doping on K-CuZnAl and Na-
Fe@C catalysts, respectively. Reaction conditions: 320 °C, 5 MPa (25.6% CO2, 71.36% H2, and 3.04% Ar), 15 mL min−1, and time on stream
(TOS) = 8 h. Catalyst weight: 0.1 g of Na-Fe@C or 0.1 g of K-CuZnAl, Na-Fe@C/K-CuZnAl (total weight: 0.2 g, weight ratios of 1:1) was
prepared by mixing two catalytic granules (20−40 mesh) in a vessel, and 1 g of quartz sand.

K-doped CuZnAl (K-CuZnAl) catalyst and by precisely
designing the intimacy degree, such as the moderate distance,
of two components in this catalyst to boost the direct synthesis
of ethanol and alkenes from CO2 hydrogenation. It should be
noted that alkenes are also highly demanded chemicals with
the rapid development of the polymer industry. As we know, a
Fe-based catalyst with alkali-metal modification is an effective
alkene synthesis catalyst in CO2 hydrogenation via the reverse
water gas shift reaction (RWGS, CO2 + H2 → CO + H2O) and
the following Fischer−Tropsch synthesis (FTS) process. In
CO2 hydrogenation, high alkene selectivity (45.7−54.9%) was
achieved using a Na-Fe@C catalyst with different amounts of
Na doping under 320 °C and 5 MPa, while only a small
amount of ethanol (10.9−14.0%) was obtained. After
combining with K-CuZnAl, the selectivity of ethanol was
increased to 35.0%, accompanied by the alkene selectivity still
being maintained at 33.0%. The ingeniously designed catalytic
interfaces with appropriate intermediate adsorption energy
guaranteed unprecedented ethanol and alkene selectivity
during this cascade process. In-depth mechanism insights
suggested that aldehyde served as a key intermediate for the
following ethanol synthesis by aldehyde hydrogenation.
2. RESULTS AND DISCUSSION
2.1. Fe@C Catalyst Characterization and Alkene
Synthesis Performance. Fe@C was obtained by pyrolyzing
the Fe-based metal−organic frameworks (Fe-MOFs) under a
N2 atmosphere. The typical diffraction peak of Fe@C overlaps
with that of the references FeO (PDF #069-0615) and Fe3O4
(PDF #19-0629), indicating that Fe species in Fe@C exist in
the form of FeO or Fe3O4 (Figure S1a). X-ray absorption
spectroscopy (XAS) studies were performed to clarify the
chemical state of Fe species in the Fe@C catalyst. The
chemical valence of Fe in Fe@C calculated based on the fitting
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data of X-ray absorption fine structure (EXAFS) results is 2.5
(Table S2). In the normalized Fe K-edge X-ray absorption
near-edge structure (XANES) spectra (Figure S1b), the
absorption edge of Fe@C is located between those of two
references FeO and Fe3O4 but closer to Fe3O4. Fe@C
exhibited a hierarchical structure with sharply increased N2
uptake at a low relative pressure (p/p0) and an obvious
hysteresis loop in the N2 adsorption−desorption isotherm
(Figure S2a and Table S3), which can also be clarified by the
pore size distribution (Figure S2b,c). As shown in the
transmission electron microscopy (TEM) image (Figure
S3a), Fe@C derived from Fe-MOFs exhibited a unique
morphology with Fe-based nanoparticles anchored on the
carbon carriers. The obvious lattice fringes of 0.25 nm, as
shown in the high-resolution TEM (HRTEM) image,
corresponded to the 111 plane of the wüstite FeO (Figure
S3b).
It has been proven that alkali-metal doping on a Fe-based
catalyst is beneficial for alkene synthesis from CO2 hydro-
genation due to the precisely controlled catalytic interfaces.
Therefore, different amounts of Na were doped onto the Fe@
C catalyst (xNa-Fe@C, where x represents the weight
percentage of Na) by the wetness impregnation method.
With Na content increasing, the selectivity of light olefins
(C2−C4) was increased at the expense of alkane selectivity
decreasing from 28.6 to 18.4% (Figure 1a and Table S4). This
phenomenon can be attributed to the suppression of H2
adsorption on the catalyst surface due to the similar
electron-donating property of H2 and Na. However, acidic
CO2 adsorption can be boosted by Na doping due to the
formation of a Fe−C bond by electron transfer from Na-Fe@C
to CO2 molecules.23 The H2-deficient catalytic interface is
beneficial for the unsaturated alkene synthesis. As shown in the
CO2/H2 temperature-programmed desorption (CO2/H2-
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Figure 2. Catalyst characterization. (a) XRD patterns of the spent Na-Fe@C catalysts after the cascade reaction. (b) 57Fe Mössbauer spectra of the
spent 2% Na-Fe@C catalyst after the cascade reaction. (c) Normalized Fe K-edge XANES spectra of the fresh Fe@C and the spent 2% Na-Fe@C
catalyst after the cascade reaction in reference to the Fe foil, FeO, Fe3O4, and Fe2O3. (d) EXAFS spectra of the fresh Fe@C and the spent 2% Na-
Fe@C catalysts after the cascade reaction in reference to the Fe foil.

TPD) profiles of the spent Na-Fe@C catalysts (Figures S4 and
S5), with the Na content increasing, the CO2 desorption peaks
shifted to higher temperatures due to the strong adsorption of
CO2 molecules on the catalytic interfaces. Conversely, the H2
adsorption ability of Na-Fe@C was decreased while the H2
adsorption peaks shifted to lower temperatures with increasing
Na doping amount. On the other hand, the readsorption of
alkenes on the catalyst is the primary cause of the decrease in
alkene selectivity due to the undesirable overhydrogenation
reaction. Alkenes, as typical Lewis bases, are difficult to
readsorb on the surface of Na-Fe@C with rich electronic
interfaces. Unfortunately, the selectivity of ethanol exhibited
no apparent change (in the range of 10.9−14.0%) with the
variation in the Na amount in the mono Na-Fe@C catalysts.
Among all of the Na-Fe@C catalysts, 2% Na-Fe@C exhibited
the highest ethanol selectivity of 14.0%. At the same time,
small amounts of higher alcohols (propanol of 1.5% and
butanol of 0.8%) were also produced on the 2% Na-Fe@C
catalyst from the CO2 hydrogenation reaction (Figure S6).
The ethanol selectivity was still low to meet the demand of the
practical application.
2.2. Ethanol Synthesis by Multifunctional Na-Fe@C/
K-CuZnAl Catalyst. Inspired by the CO2 activation and C−C
coupling with CH2* species as growth units for alkene
synthesis on the Na-Fe@C catalyst, what will happen if a lot
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of oxygen-containing intermediates are involved in the CO2
hydrogenation process at the same time? During the RWGS or
methanol synthesis process of CO2 hydrogenation, a lot of
oxygen-containing intermediates are formed.24 Therefore, a
methanol synthesis catalyst CuZnAl (Figure S7 and Table S3)
was combined with the alkene synthesis catalyst Na-Fe@C to
try to boost the ethanol synthesis from CO2 hydrogenation.
Surprisingly, high ethanol selectivity (28.6%) was achieved via
the multifunctional catalyst 2% Na-Fe@C/CuZnAl with two
kinds of granules mixed uniformly (Figure 1b and Table S5).
However, alkenes were hard to detect on 2% Na-Fe@C/
CuZnAl due to the strong hydrogenation capacity of the
CuZnAl catalyst. K doping on the CuZnAl catalyst was
employed to suppress the undesirable hydrogenation of
alkenes because alkali-metal doping can depress the read-
sorption behaviors of alkenes on the catalyst surface. CuZnAl
with K doping of 1 wt % (1% K-CuZnAl) still exhibited low
selectivity of alkenes (4.8%) after coupling with the 2% Na-
Fe@C catalyst (Figure 1b and Table S5). High alkene
selectivity (33%) was obtained from the multifunctional
catalyst 2% Na-Fe@C/5% K-CuZnAl due to the suppression
of hydrogenation capacity of the Cu-based catalyst by K
doping (Figure 1b and Table S5). As characterized by H2-TPD
(Figure S8), the H2 desorption peak at higher temperature
even disappeared on the 5% K-CuZnAl catalyst, which
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Figure 3. Morphology of the spent Na-Fe@C catalyst. TEM (a) and HRTEM (b) images of the spent 2% Na-Fe@C catalyst after the cascade
reaction; the inset is the fast Fourier transfer (FFT) image of the corresponding HRTEM image. (c) HAADF-STEM image of the spent 2% Na-
Fe@C catalyst after the cascade reaction and the corresponding elemental mapping images of Na, Fe, and C elements.

confirmed the extremely weak hydrogenation capacity of 5%
K-CuZnAl. Furthermore, 35.0% ethanol was produced on the
2% Na-Fe@C/5% K-CuZnAl multifunctional catalyst accom-
panied with small amounts of higher alcohols (Figure S6, 4.0%
propanol, 1.2% butanol, and 0.7% C5 alcohol).
2.3. Characterization of the Spent Na-Fe@C Catalyst
after the Cascade Reaction. Multiple characterization
techniques were resorted to clarify the nature of the active
sites in this cascade reaction. The XRD patterns (Figure 2a)
confirmed that Fe3O4 (PDF #19-0629) and χ-Fe5C2 (PDF
#51-0997) are the main phases in the spent Na-Fe@C catalysts
after the cascade reaction. Four kinds of Fe-based species (χ-
Fe5C2, Fe3O4, Fe3+, and θ-Fe3C) were detected in the 57Fe
Mössbauer spectra of the spent Na-Fe@C catalyst with χ-
Fe5C2 (spectra contribution, 51.8%) and Fe3O4 (34.3%) as the
major phases (Figure 2b and Table S6). X-ray photoelectron
spectroscopy (XPS) was carried out to analyze the chemical
property of Fe in the spent 2% Na-Fe@C catalyst (Figure S9).
In addition to the typical peaks of divalent Fe (Fe2+, Fe 2p3/2 at
712.1 eV and Fe 2p1/2 at 725.6 eV) and trivalent Fe (Fe3+, Fe
2p3/2 at 714.5 eV and Fe 2p1/2 at 732.9 eV), a weak typical
peak at 703.5 eV corresponding to the Fe−C bond
appeared.25,26 The experimental observations were further
supported by XAS studies. The XANES spectra (Figure 2c)
suggested that the Fe species in the catalyst were partially
reduced after the reaction with the absorption edge shifting to
lower energy compared with that of the fresh Na-Fe@C
catalyst. In the EXAFS spectra (Figure 2d), the intensity of the
Fe−Fe bond at 2.2Å was increased after the cascade reaction,
suggesting the reduction of the catalyst during the hydro-
genation reaction. The evolution trend of the Fe−C bond
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cannot be distinguished from the EXAFS spectra due to the
overlapping of the Fe−C and Fe−O scatterings at 1.39Å.
Therefore, we extracted the information of the bond distance
and the coordination number (CN) from the fitting Fe K-edge
EXAFS results. The CN of the Fe−C bond was increased from
3.7 of fresh Fe@C to 5.2 of the spent 2% Na-Fe@C, which
confirmed the formation of Fe-based carbide phases during the
reaction (Table S2). The increased CN of the Fe−Fe bond
and the decreased CN of the Fe−O bond further proved the
reduction of the catalyst, which were consistent with the
variation of XANES results.
The morphology of the spent Na-Fe@C was well
maintained after the reaction where active nanoparticles
individually anchored on the carbon carriers, as shown in the
TEM image (Figure 3a). The lattice fringes with a 0.20 nm
interspace shown in the HRTEM image (Figure 3b)
corresponded to the (510) plane of Fe5C2.27 The Fe3O4
phase in the spent Na-Fe@C catalyst can also be identified
in the HRTEM image with an obvious lattice fringe of 0.29 nm
(Figure S10), which was assigned to the (220) plane of Fe3O4.
In the high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) and the corresponding
elemental mapping images of the spent Na-Fe@C (Figure 3c),
Fe-based active components were mainly concentrated on the
nanoparticles, different from Na and C elements, which were
homogeneously dispersed on the whole substrate. The carbon
carriers in the catalyst acted as support grids to prevent the
aggregation of active nanoparticles during the reaction.
2.4. In-Depth Mechanism Insights into the Cascade
Reaction. In situ XRD was performed to monitor the crystal
structure evolutions of the catalysts under real reaction
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Figure 4. In situ XRD patterns of the 2% Na-Fe@C catalyst (a and b) and the 2% Na-Fe@C/5% K-CuZnAl multifunctional catalyst (c and d)
under a H2 reduction (a and c) or reactant gas (b and d) atmosphere.
conditions (Figure 4). During a H2 reduction process of the
sole Na-Fe@C catalyst, the crystal structure of MOF-derived
iron oxide (mainly FeO) had no obvious change. The typical
XRD peaks corresponding to the (031) and (112) planes of
Fe3C at 44.9 and 45.8°, respectively, appeared when the
reduction temperature reached 400 °C and was held for 2 h.
This phenomenon can be attributed to the carburization of
FeO with the help of a H2 atmosphere and carbon species in a
Na-Fe@C catalyst that is derived from the pyrolysis of Fe-
based MOFs. Different from the traditional Fe-based catalyst
preparation method (impregnation or coprecipitation), the
MOF pyrolysis method not only ensures the homogeneous
dispersion of the Fe active sites due to the periodic
arrangement of the organic linkers and metallic centers but
also endows a variety of possibilities to regulate the
physicochemical properties of the MOF-derived heterogeneous
catalysts as required.28 Furthermore, the rational fabrication of
a unique catalytic interface that possesses RWGS (iron oxide)
and FTS (iron carbide) active sites simultaneously is essential
to realize the direct conversion of CO2 into desired products
via the modified FTS process. By means of Fe-based MOF
pyrolysis, FeO formed in situ can be employed as an RWGS
active site and the rapid formation of the Fe3C phase in the
Na-Fe@C catalyst after H2 reduction could shorten the
carburization period of the formation of iron carbide for
carbon chain growth and facilitate the catalytic efficiency.26
After switching the reduction gas H2 to reactant gas CO2/H2,
as well as increasing the reaction temperature from 50 to 320
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°C, the Fe3O4 crystal phase with high RWGS activity appeared
due to the partial oxidation of FeO by oxidative CO2 (Figure
4b). The reduction intensity of the diffraction peak at 44.9°
corresponding to (031) planes of Fe3C accompanied with the
appearance of the diffraction peak at 44.1° for the (510) plane
of Fe5C2 confirmed the further carburization effect (Fe3C →
Fe5C2) of the Fe-based catalyst during the CO* activation and
following C−C coupling processes.
After introduction of a 5% K-CuZnAl component, the crystal
phase of a Fe-based catalyst underwent tremendous changes
under a H2 reduction and reactant gas atmosphere. The FeO
phase produced in situ by MOF pyrolysis gradually disappeared
with the reduction temperature increasing (Figure 4c). At the
same time, Fe3C became the only phase that was associated
with the Fe component. This different evolution trend
compared with that of the sole 2% Na-Fe@C catalyst can be
attributed to the strong H2 activation capacities of Cu active
sites for H* species formation. The H* spillover from 5% K-
CuZnAl to 2% Na-Fe@C enhanced the reduction degree of
the Fe-based catalyst, hence facilitating the carburization
process to a greater extent. The H2 temperature-programmed
desorption (H2-TPD) curves also confirmed the change in the
Na-Fe@C reduction process originated from 5% K-CuZnAl.
As shown in Figure S11, a novel reduction peak at ∼330 °C,
lower than the reduction temperature of the Na-Fe@C
catalyst, appeared in the H2-TPD curve of the 2% Na-Fe@
C/5% K-CuZnAl multifunctional catalyst, which can be
attributed to the consumption of H2 during the carburization
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Figure 5. In situ DRIFT spectra of CO2 hydrogenation reactions via 2% Na-Fe@C (a) and multifunctional catalyst 2% Na-Fe@C/5% K-CuZnAl
(b). Characterization conditions: 320 °C and 3 MPa; 2% Na-Fe@C/5% K-CuZnAl was prepared by physically mixing two catalytic components.
of FeO. Under the reactant gas atmosphere, no Fe3O4 phase
was formed with increasing reaction temperature (Figure 4d).
The stronger CO2 adsorption capability of 5% K-CuZnAl than
that of 2% Na-Fe@C, as confirmed by the CO2-TPD curves
(Figure S12), could decrease the coverage of CO2 on the
surface of 2% Na-Fe@C when 5% K-CuZnAl was present,
therefore inhibiting the oxidation of iron carbide to Fe3O4. A
Fe5C2 phase was also formed at the expense of decreasing the
diffraction peak intensity of Fe3C with the increase in reaction
temperature and time. The CuO phase in the fresh 5% K-
CuZnAl catalyst was evolved into metallic Cu either under a
reduction or under reaction atmosphere. It should be noted
that the appearance of the Fe3O4 phase in the spent Na-Fe@C
catalyst after the cascade reaction, as shown in Figure 2a, can
be attributed to the partial oxidation of Fe5C2 when exposing
the spent catalyst to an air atmosphere.
In situ time-resolved diffuse reflectance infrared Fourier
transform spectroscopy (DRIFTS) was performed to monitor
the surface intermediates evolved in the reaction. HCOO* and
CHxO* species were identified on the surface of methanol
synthesis catalyst K-CuZnAl (Figure S13). The infrared (IR)
peaks at 1540 and 1379 cm−1 were assigned to the asymmetric
and symmetric OCO stretching vibrations of the adsorbed
HCOO* species, respectively, and the IR peak at 2821 cm−1
was of the C−H stretching vibration.29,30 Kattel et al. revealed
that formate was an intermediate species for methanol
synthesis on the Cu/ZnO catalyst by combining the
experimental and theoretical evidence. Furthermore, a
formate-mediated pathway for CO2 hydrogenation to meth-
anol was also proposed, in which CO2 was first hydrogenated
to a formate intermediate followed by its hydrogenation and
dissociation to CHxO* species, and then CHxO* could be
hydrogenated to methanol.31 The appearance of typical IR
peaks at 1048 and 2961 cm−1 for CO and C−H stretching
vibrations, respectively, confirmed the existence of CHxO*
species on the K-CuZnAl catalyst.32,33 For the Na-Fe@C
catalyst (Figure 5a), the IR peaks corresponding to the
stretching vibrations of CC (1645 cm−1) and C−H (3010
and 3100 cm−1) in the unsaturated alkenes (−CC−H) were
detected. The typical IR peak at 2880 cm−1 can be assigned to
the stretching vibration of C−H in CHm* species.34 Intuitively,
unsaturated alkenes with different carbon chain lengths were
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evolved as confirmed by the DRIFT spectra, which is
consistent with the catalytic performance of Na-Fe@C due
to the tailor-made active sites and basic catalytic interfaces for
alkenes synthesis. After combining these two catalysis
components, the IR peaks corresponding to the C−H (2852
cm−1) and CO (1705 cm−1) stretching vibrations in
aliphatic aldehyde species appeared in addition to the typical
IR peaks derived from unsaturated alkenes and HCOO*
species, implying that aldehyde species was an important
intermediate during the tandem reaction (Figure 5b).35,36 The
aldehyde species could originate from the direct C−C coupling
of CHm* and CHxO* species (CHm* + CHxO* → * +
CHmCHxO*) or the indirect process involved C−C coupling
between CHm* and CO* species (CHm* + CO* → * +
CHmCO*) and the following hydrogenation step (CHmCO* +
H*→ * + CHmCHO*). Notably, the typical IR peaks of CHm*
(2880, 3010, and 3100 cm−1) and CC (1645 cm−1) species
in DRIFT spectra of the Fe/Cu-based multifunctional catalyst
are negligible compared with that of the sole Na-Fe@C
catalyst. This phenomenon can be attributed to the altered
reaction network induced by the introduction of the K-CuZnAl
component. For the sole Na-Fe@C catalyst, CO from the
RWGS could dissociate and hydrogenate to CHx* species, and
the coupling of CHx*−CHx* for hydrocarbon synthesis is the
main reaction in the reaction network (alkenes of 49.5%,
alkanes of 22.8%). However, after introducing the K-CuZnAl
catalyst, the high coverage of CHxO*/CO* species on the
active sites guaranteed that the C−C coupling of CHm* and
CHxO*/CO* dominates the reaction network for oxygenate
synthesis (39.4%), especially for ethanol (32.2%). This
variation trend of DRIFT spectra is similar with the result
recently reported by Sun et al., who employed sulfate on the
Fe-based catalyst with an electron-withdrawing effect to
weaken the dissociation of CO* species, therefore boosting
the formation of ethanol via C−C coupling of CHm* and
CO*.37 It should be noted that even though no ketone species
(acetyl CHCO* or ketene CH2CO*) were detected in the in
situ DRIFT spectra, as well as the fact that the coupling barrier
for CHm* with CO* (CHm* + CO* → * + CHmCO*) is
higher than that of CHm* with CHxO*,38,39 the important role
of ketone species for ethanol synthesis should not be neglected
because CHm* species are ready to couple with CO* on the
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Figure 6. Reaction network for ethanol synthesis from CO2 hydrogenation via the Na-Fe@C/K-CuZnAl multifunctional catalyst.
catalyst surface with such a high CO* coverage.40 The ketones
can be hydrogenated to aliphatic aldehyde species identified in
the DRIFT spectra.
Combining the variations in catalytic performances and the
information obtained from the in situ characterization results,
the plausible reaction pathways for ethanol synthesis during
the cascade reaction were proposed. For the CO2 hydro-
genation reaction on the sole Fe-based catalyst, CO2 was
initially reduced to CO by H2 via an RWGS reaction on Fe3O4
active sites (Figure S14). Subsequently, the dissociation of CO
and the following hydrogenation step guaranteed the
formation of CHm* species on the iron carbide (mainly
Fe5C2) active sites, which has been recognized as the
intermediate for carbon chain growth via the Fischer−Tropsch
synthesis (FTS) process. The alkene synthesis ability of the Fe-
based catalyst could be boosted by alkali-metal doping due to
the weakened readsorption of alkenes on the catalyst surface,
thereby suppressing the excessive alkene hydrogenation
reactions.41 Interestingly, in addition to plenty of alkenes,
ethanol with a selectivity of ∼10% could also be produced on
the sole Na-Fe@C catalyst. As shown in Figure S14, two
possible pathways ensure the formation of ethanol on the sole
Na-Fe@C catalyst: (a) the CO produced from the RWGS
reaction could be nondissociatively adsorbed by Fe5C2 catalytic
sites, and then the C−C coupling of CHm* and CO* and the
following hydrogenation step complete the ethanol syn-
thesis;42,43 (b) the nondissociatively adsorbed CO is first
hydrogenated into CHO* species, and then ethanol could be
obtained from the C−C coupling of CHm* and CHO* and the
following hydrogenation process.39
The introduction of the K-CuZnAl catalyst into the catalytic
system had great effects on both the crystal structure of the Fe-
based catalytic component and the catalytic network. As
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confirmed by the in situ XRD results (Figure 4d), Fe3O4 active
sites for the RWGS reaction were not detected on the Fe/Cu-
based multifunctional catalyst during the CO2 hydrogenation
reaction due to the deep reduction and carburization process
of the MOF-derived Fe/carbon composite catalyst in the
presence of the Cu-based component with hydrogen spillover
capability, and the CuZnAl catalyst played a more important
role in the RWGS reaction to supply CO* species for the
following FTS process and ethanol synthesis. Figure 6 shows
the plausible reaction routes (I, II, III, and IV) for ethanol
synthesis via Fe- and Cu-based multifunctional catalysts. In the
I and II reaction routes, CO* species produced from the Cu-
based catalyst diffused onto the surface of the iron carbide
(mainly Fe5C2) active site, where the dissociation and
hydrogenation of CO* species for CHm* formation and the
different C−C coupling processes happened. It is obvious that
the reaction routes of I and II on Fe and the Cu-based
multifunctional catalyst are consistent with the routes that
occurred on the sole Fe-based catalyst (Figure S14 routes a
and b) in addition to the different CO* species suppliers.
Furthermore, CuZnAl is also a highly efficient catalyst for
methanol synthesis with formate and CHxO* species as the
reaction intermediates. During the multifunctional composite-
catalyzed tandem process, the reaction intermediates produced
from one catalytic site could diffuse onto the interface of
another catalytic component to realize the selective synthesis
of target products. For example, Bao et al. developed the so-
called OX-ZEO concept for the direct conversion of syngas
into light olefins or aromatics, during which the ketene species
(CH2CO*) produced from the metallic oxide will diffuse into
the channels of zeolites for the following reactions.40
Therefore, we hypothesized that the reaction intermediates
formate and CHxO* could desorb from K-CuZnAl and diffuse
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onto the interface of the Fe-based component for the following
C−C coupling steps under the reaction flow (Figure 6): (III)
the coupling of CHm* (from Fe-based catalyst) and CHxO*
(from Cu-based catalyst) on the basic surface of the alkali-
promoted Fe catalyst resulted in the formation of aldehyde
species, and then the hydrogenation of aldehyde species
guaranteed the formation of ethanol;44 (IV) CHm* species
directly coupled with formate to form CHmCOO* species on
the interface of the Fe-based catalyst, which could be
hydrogenated into ethanol with aldehyde as the intermediate
(2H* + CHmCOO* → CHmCHO* + OH*). The above-
mentioned hypotheses (III and IV) can be partially supported
by the typical spectra of formate and aldehyde species, as
monitored by the in situ DRIFTS of the 2% Na-Fe@C/5% K-
CuZnAl multifunctional catalyst. Ding et al. developed a Cu@
Na-β catalyst for highly selective conversion of CO2 into
ethanol and built a reaction network with the coupling of
CHm* and CO2* (CHm* + CO2* → * + CHmCOO*) as the
key step for ethanol synthesis.45 This work confirmed that the
coupling of CHm* and CO2* and the following hydrogenation
step are also probably the reaction pathways for ethanol
synthesis from CO2 hydrogenation. At last, even though the
yield of ethanol obtained from 2% Na-Fe@C/5% K-CuZnAl is
markedly higher than the reported values of the previous
literature (Figure 7 and Table S1), and the aldehyde species
Figure 7. Comparison of the yield of ethanol obtained in this work
with other literature studies.
produced from different pathways (routes I, II, III, and IV,
Figure 6), as confirmed by the in situ DRIFTS (Figure 5b),
seems to be the most important intermediate for ethanol
synthesis during the tandem process, the ethanol synthesis
from CO2 hydrogenation via the multifunctional catalyst is an
extremely complex process and more in-depth theoretical
analysis and in situ characterization are needed to elucidate the
exact and the dominant reaction pathways and intermediates
for ethanol synthesis from CO2 hydrogenation in the near
future.
On the other hand, Na content in Na-Fe@C/5% K-CuZnAl
was also sensitive for ethanol synthesis (Figure 1b and Table
S7). Na-Fe@C/5% K-CuZnAl with a low Na content (0.5 and
1 wt %) exhibited lower ethanol selectivity (23.5 and 23.1%,
respectively). Na-Fe@C with 2 wt % of Na doping was
appropriate to boost the ethanol synthesis (35.0%) after
combining with the 5% K-CuZnAl catalyst. However, further
increasing the Na content had no obvious effect on the ethanol
selectivity (33.8%). Therefore, too much Na doping on the
catalyst surface with low alkene readsorption capacity was
favorable for alkene synthesis but inhibits the formation of
ethanol. We concluded that the ingeniously tailored catalytic
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interface with appropriate intermediate adsorption capacity
was essential for the highly selective transformation of CO2 to
ethanol and alkenes.
As monitored by the in situ DRIFTS, aldehyde species
derived from the C−C coupling of CHm* with CHxO* or
CO* was the reaction intermediate for ethanol synthesis from
the cascade reaction; the effect of the Na amount on the
ethanol selectivity was clarified by estimating the C−C
coupling barriers with the help of density functional theory
(DFT) calculations. Based on the experimental results, two
surface models of Fe5C2(510) and Na2O/Fe5C2(510) were
established to represent the Fe-based catalyst with and without
Na doping. The C−C coupling step was first simulated by the
elementary reaction of CH2* + CHO* → * + CH2CHO*. The
C−C coupling barrier on Fe5C2(510) (0.73 eV) is much
higher than that on Na2O/Fe5C2(510) (0.14 eV), indicating
that Na doping is beneficial for ethanol synthesis by weakening
the C−C coupling of CHx* and CHO* species (Figure 8a).
The calculation results are in line with the variation of ethanol
selectivity obtained from the multifunctional catalyst with
different amounts of Na doping. Furthermore, to understand
how Na doping affects the electronic structure of Fe5C2(510),
the projected density-of-state (PDOS) was calculated (Figure
8b). The PDOS near the Fermi level (Ef) disclosed that the d-
band center of Fe on Na2O/Fe5C2(510) (−2.42 eV) was
farther away from Ef than that on Fe5C2(510) (−2.27 eV),
indicating the weaker adsorption energy of the intermediate
species on the Na doping Fe5C2(510) surface due to the more
occupancy of the antibonding states. This weakened
adsorption energy could facilitate the migration of CH2* and
CHO* on the Na2O/Fe5C2(510) surface, resulting in the
decreased coupling barrier between CH2* and CHO*. The
C−C coupling barriers between CH2* and CO* species on
Fe5C2(510) and Na2O/Fe5C2(510) were also evaluated by
DFT calculation (Figure 8c). As expected, Na doping
decreased the coupling barrier from 1.2 eV of Fe5C2(510) to
0.69 eV of Na2O/Fe5C2(510), which further confirmed that
Na doping played a vital role in the formation of reaction
intermediates for ethanol synthesis. It should be noted that
even though the coupling barrier (0.69 eV) between CH2* and
CO* on Na2O/Fe5C2(510) was higher than that between
CH2* and CHO* (0.14 eV), ketone (CHmCO*) derived from
the coupling of CHm* and CO* (pathway II in Figure 6) was
also inevitably an important ethanol synthesis intermediate due
to the high coverage of CO* species on the surface of Fe5C2
active sites.
2.5. Optimal Reaction Conditions of the Cascade
Reaction for Ethanol Synthesis. The intimacy modes of the
multifunctional catalyst had a tremendous impact on the
catalytic performance of the cascade reaction.46,47 The
multifunctional catalyst 2% Na-Fe@C/5% K-CuZnAl with
the closest proximity exhibited lower ethanol selectivity
(32.2%) and CO2 conversion (38.1%) compared with those
of the granule-mixed 2% Na-Fe@C/5% K-CuZnAl catalyst
(quartz sand of 1.0 g) that achieved an ethanol selectivity of
35.0% at a CO2 conversion of 39.2% (Figure 9a and Table S8).
This phenomenon should be attributed to the coverage of the
active sites in the physical-mixing mode multifunctional
catalyst. The spatial distance between the different catalytic
components could be increased by loading the multifunctional
catalyst with the granule-mixing mode (Figure 9b and Table
S9), and the effect of the quartz sand amount (0, 1, 2 g) on the
catalytic performance was also investigated. Ethanol selectivity
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Figure 8. DFT calculation results. (a) Energy profiles of the C−C coupling between CH2* and CHO* species (CH2* + CHO* → * +
CH2CHO*) on Fe5C2(510) and Na2O/Fe5C2(510). (b) Calculated d-band states of the Fe atom in Fe5C2(510) and Na2O/Fe5C2(510). (c)
Energy profiles of the C−C coupling between CH2* and CO* species (CH2* + CO* → * + CH2CO*) on Fe5C2(510) and Na2O/Fe5C2(510).
Na, Fe, C, O, and H are shown in purple, blue, gray, red, and white, respectively.

of 30.6% at a CO2 conversion of 40.1% was achieved from the
granule-mixing multifunctional catalyst without quartz sand,
which is even similar to that of the physical-mixing
multifunctional catalyst mode. However, further increasing
the spatial distance of the different catalytic components
(quartz sand of 2 g) led to a decrease in ethanol selectivity
(24.4%). The decrease in ethanol selectivity can be attributed
to the difficult CO insertion process (C−C coupling) for
ethanol synthesis, as confirmed by the increased CO selectivity
(13.3%). For the dual-bed mode with 2% Na-Fe@C loaded on
the upper of 5% K-CuZnAl (denoted as 2% Na-Fe@C||5% K-
CuZnAl, Figure 9c and Table S8), the intermediates produced
from the two catalysts bed were difficult to combine directly
due to the enlarged distance of the reaction active sites, which
led to the low ethanol selectivity (22.0%). The higher ethanol
selectivity obtained from 2% Na-Fe@C||5% K-CuZnAl
compared with that of the sole 2% Na-Fe@C catalyst can be
attributed to the increase in the CO partial pressure in the
catalytic system, which can be partially diffused onto the
surface of 2% Na-Fe@C for C−C coupling of ethanol
synthesis. The dual-bed mode also lowered the driving force
in the tandem reaction process with the CO2 conversion
decreasing to 34.0%. The ethanol selectivity was further
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decreased to 7.2% by reversing the catalyst arrangement (5%
K-CuZnAl||2% Na-Fe@C, Figure 9d), which was even lower
than that of the sole 2% Na-Fe@C catalyst (14.0% ethanol
selectivity). Even though this configuration mode also
increased the partial pressure of CO in the catalytic system,
the methanol produced from the upper CuZnAl catalyst bed
could diffuse and cover the catalytic interface of the 2% Na-
Fe@C catalyst, hence lowering the ethanol selectivity.
The effect of weight ratios of two catalysis components on
the catalytic performance was also investigated. The less K-
CuZnAl catalyst provided insufficient CHxO* species for the
following coupling reaction with the CHm* species, therefore
leading to the decrease in the ethanol selectivity to 22.4%
(Table S10). On the other hand, even though too much K-
CuZnAl increased the CO2 conversion, CO selectivity was
increased due to the enlarged RWGS reaction. At the same
time, the undesirable alkane selectivity was increased since the
overhydrogenation reaction of alkenes happened on the
excessive Cu active sites. When the K-CuZnAl catalyst was
replaced by the traditional high-temperature methanol syn-
thesis catalyst ZnCrOx, a low ethanol selectivity of 11.5%
(Table S11) was obtained. The reaction pressure is also an
important factor affecting the selectivity of ethanol. As
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ACS Catalysis pubs.acs.org/acscatalysis
Figure 9. Effect of intimacy modes on the catalytic performance. (a)
Physical-mixing of the catalyst powder, 2% Na-Fe@C/5%-K-CuZnAl.
(b) Granule-mixing, 2% Na-Fe@C/5% K-CuZnAl with different
amounts of quartz sand (0, 1, and 2 g). (c) Dual-bed with 2% Na-
Fe@C loaded above 5% K-CuZnAl and 2% Na-Fe@C||5% K-CuZnAl.
(d) Dual-bed with 2% Na-Fe@C loaded below 5% K-CuZnAl and 5%
K-CuZnAl||2% Na-Fe@C. Reaction conditions: 320 °C, 5 MPa
(25.6% CO2, 71.36% H2, and 3.04% Ar), 15 mL min−1, and time on
stream (TOS) = 8 h. Catalyst weight: 0.1 g of Na-Fe@C, 0.1 g of 5%
K-CuZnAl, and 1 g of quartz sand.
confirmed by the higher CO selectivity (Table S12), a low
reaction pressure (3 MPa) is unfavorable for the CO*/CHxO*
insertion process, which is the vital step for reaction
intermediate aldehyde formation, hence lowering the ethanol
selectivity both on 2% Na-Fe@C and 2% Na-Fe@C/5% K-
CuZnAl catalysts. The long-term stability of 2% Na-Fe@C and
2% Na-Fe@C/5% K-CuZnAl has been tested under 320 °C
and 5 MPa (Figure S15); no obvious degradation was detected
for the CO2 conversion and product selectivity. Especially, for
the 2% Na-Fe@C/5% K-CuZnAl multifunctional catalyst, an
ethanol selectivity of 33.8% was maintained after a stability test
of 100 h. However, the ethanol selectivity of the multifunc-
tional catalyst 2% Na-Fe@C/5% K-CuZnAl with the closest
proximity mode was gradually decreased to 25.9% after long-
term operation of 100 h, which can be attributed to the easy
migration of metallic elements between different components
with a close distance and the catalytic active site sintering
during the CO2 hydrogenation reaction.48
3. CONCLUSIONS
A novel multifunctional catalyst and a new reaction path were
both successfully designed to realize highly efficient conversion
of CO2 to ethanol, at the same time, accompanied by the
formation of some value-added alkenes. It was demonstrated
that tuning the moderate intimacy of active components of
bifunctional catalysts was very rewarding. The rationally
designed catalytic interfaces and a moderate intimacy mode
endowed the multifunctional catalyst 2% Na-Fe@C/5% K-
CuZnAl with excellent ethanol (35%) and alkene (33%)
selectivity at a CO2 conversion of 39.2%. Aldehyde species
trapped by the in situ DRIFTS was recognized as the
intermediate for ethanol synthesis in the new reaction path.
This study will not only pave a new way for the highly efficient
utilization of greenhouse gas CO2 to produce ethanol but also
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be very promising to really industrialize multifunctional
catalysts because of their facile separation, easy recycling,
and a low-cost assembly model.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.1c01504.
Experimental section, catalyst preparation, catalyst
characterization, computational details, catalytic activity
test, Tables S1−S10, and Figures S1−S10 (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Guohui Yang − Department of Applied Chemistry, Graduate
School of Engineering, University of Toyama, Toyama 930-
8555, Japan; State Key Laboratory of Coal Conversion,
Institute of Coal Chemistry, Chinese Academy of Sciences,
Taiyuan 030001, China; Email: thomas@eng.u-
toyama.ac.jp
Mingbo Wu − Institute of New Energy, College of New Energy,
State Key Laboratory of Heavy Oil Processing, China
University of Petroleum (East China), Qingdao 266580,
China; orcid.org/0000-0003-0048-778X;
Email: wumb@upc.edu.cn
Noritatsu Tsubaki − Department of Applied Chemistry,
Graduate School of Engineering, University of Toyama,
Toyama 930-8555, Japan; orcid.org/0000-0001-6786-
5058; Email: tsubaki@eng.u-toyama.ac.jp
Authors
Yang Wang − Institute of New Energy, College of New Energy,
State Key Laboratory of Heavy Oil Processing, China
University of Petroleum (East China), Qingdao 266580,
China; Department of Applied Chemistry, Graduate School
of Engineering, University of Toyama, Toyama 930-8555,
Japan
Kangzhou Wang − Department of Applied Chemistry,
Graduate School of Engineering, University of Toyama,
Toyama 930-8555, Japan
Baizhang Zhang − Department of Applied Chemistry,
Graduate School of Engineering, University of Toyama,
Toyama 930-8555, Japan
Xiaobo Peng − Department of Applied Chemistry, Graduate
School of Engineering, University of Toyama, Toyama 930-
8555, Japan
Xinhua Gao − State Key Laboratory of High-Efficiency
Utilization of Coal and Green Chemical Engineering, College
of Chemistry & Chemical Engineering, Ningxia University,
Yinchuan 750021, China
Han Hu − Institute of New Energy, College of New Energy,
State Key Laboratory of Heavy Oil Processing, China
University of Petroleum (East China), Qingdao 266580,
China; orcid.org/0000-0002-3755-7342
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.1c01504
Author Contributions
This manuscript was written through the contributions of all
authors. All authors have given approval to the final version of
the manuscript.
https://doi.org/10.1021/acscatal.1c01504
ACS Catal. 2021, 11, 11742−11753
ACS Catalysis pubs.acs.org/acscatalysis
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the JST-MIRAI project
(JPMJMI17E2) of the Japan Science and Technology Agency,
the Science and Technology Innovation Project of the
Shandong Energy Group Co., Ltd (SNKJ2021BJ04), the
China Postdoctoral Science Foundation (No. 2020M672169),
the CNPC Innovation Foundation (2020D-5007-0407), and
the Foundation of State Key Laboratory of High-efficiency
Utilization of Coal and Green Chemical Engineering (2020-
KF-34). The authors thank the staff at the State Key
Laboratory of High-efficiency Utilization of Coal and Green
Chemical Engineering (Ningxia University) for assistance with
the in situ XRD measurements.
■
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11753 https://doi.org/10.1021/acscatal.1c01504
ACS Catal. 2021, 11, 11742−11753