One-Step Reforming of CO2 and CH4 into High-Value Liquid Chemicals and Fuels at Room Temperature by Plasma-Driven Catalysis

Article abstract of DOI:10.1002/anie.201707131

The conversion of CO₂ with CH₄ into liquid fuels and chemicals in a single-step catalytic process that bypasses the production of syngas remains a challenge. In this study, liquid fuels and chemicals (e.g., acetic acid, methanol, ethanol, and formaldehyde) were synthesized in a one-step process from CO₂ and CH₄ at room temperature (30 °C) and atmospheric pressure for the first time by using a novel plasma reactor with a water electrode. The total selectivity to oxygenates was approximately 50–60 %, with acetic acid being the major component at 40.2 % selectivity, the highest value reported for acetic acid thus far. Interestingly, the direct plasma synthesis of acetic acid from CH₄ and CO₂ is an ideal reaction with 100 % atom economy, but it is almost impossible by thermal catalysis owing to the significant thermodynamic barrier. The combination of plasma and catalyst in this process shows great potential for manipulating the distribution of liquid chemical products in a given process.

Full text of DOI:10.1002/anie.201707131

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Accepted Article
Title: One-step reforming of CO2 and CH4 to high-value liquid
chemicals and fuels at room temperature via plasma-driven
catalysis
Authors: Li Wang, Yanhui Yi, Chunfei Wu, Hongcheng Guo, and Xin Tu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201707131
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10.1002/anie.201707131
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One-step reforming of CO2 and CH4 to high-value liquid chemicals
and fuels at room temperature via plasma-driven catalysis
L. Wang,[a] Y. H. Yi,[b] C. F. Wu,[c] H. C. Guo,[b] and X. Tu*[a]
Abstract: Conversion of CO2 with CH4 into liquid fuels and
chemicals in single-step catalytic process bypassing the
attractive route as direct converting of CO2 and CH4 to acetic
acid is a reaction with 100% atom economy (R1). However, this
reaction is thermodynamically unfavorable under practical
conditions. The conventional indirect catalytic process often
proceeds through two steps (Scheme 1): (1) DRM to produce
syngas (CO and H2) at high temperatures (> 700 oC); (2)
conversion of syngas to liquid fuels and chemicals at high
pressures. Such an indirect route for CO2 valorisation and CH4
activation is inefficient as the DRM process for syngas
production is highly endothermic and requires high temperatures
and energy input (R2). Catalyst deactivation due to carbon
deposition is another challenge limiting the use of this reaction
on a commercial scale. It is almost impossible to directly convert
two stable and inert molecules (CO2 and CH4) into liquid fuels or
a
production of syngas remains a challenge. In this study, one-step
synthesis of liquid fuels and chemicals (e.g. acetic acid, methanol,
ethanol and formaldehyde) from CO2 and CH4 has been achieved at
room temperature (30 oC) and atmospheric pressure for the first time
using a novel plasma reactor with a water electrode. The total
selectivity to oxygenates was ca. 50-60%, with acetic acid the major
component at 40.2% selectivity, the highest value reported for acetic
acid so far. Interestingly, direct plasma synthesis of acetic acid from
CH4 and CO2 is an ideal reaction with a 100% atom economy, but it
is almost impossible via thermal catalysis due to the significant
thermodynamic barrier. The combination of plasma and catalyst in
this process shows great potential for manipulating the distribution of
different liquid chemicals.
chemicals in
a one-step catalytic process bypassing the
production of syngas. A step-wise method was proposed to
convert CO2 and CH4 into acetic acid over Cu/Co-based
Chemical transformation of CO2 into value-added chemicals
and fuels has been regarded as a key element of creating a
sustainable low-carbon economy in the chemical and energy
[4]
catalysts [2], Pd/C, Pt/Al2O3 [3], Pd/SiO2 and Rh/SiO2
via
heterogeneous catalysis. The catalyst was first exposed to CH4,
forming CHx species on the catalyst surface. Subsequently, the
feed gas was changed from CH4 to CO2, forming acetic acid
through the reaction of CO2 with CHx over the catalyst. This
indirect process was complicated as a periodic change of
industry.
A
particularly significant route currently being
developed for CO2 utilization is catalytic CO2 hydrogenation.
This can produce a range of fuels and chemicals including CO,
formic acid, methanol, hydrocarbons and alcohols; however,
high H2 consumption (CO2 + 3H2 → CH3OH + H2O) and high
operating pressure (~30-300 bar) are major challenges facing
this process.
reactant and collection of products was required [5]
.
CO2 + CH4 → CH3COOH, ΔG298 K = 71.17 kJ/mol
(R1)
(R2)
Instead of using H2, direct conversion of CO2 with CH4 (dry
reforming of methane, DRM) to liquid fuels and chemicals (e.g.
acetic acid) represents another promising route for both CO2
valorisation and CH4 activation. CH4 is an ideal H-supplier to
replace H2 in CO2 hydrogenation as CH4 has a high H density
and is available from a range of sources (e.g. natural gas, shale
gas, biogas and flared gas). Moreover, it is a cheap carbon
source which can increase the atom utilization of CO2
hydrogenation due to the stoichiometric ratio of C and O atoms,
as well as reducing the formation of water.
CH4 + CO2 → 2CO + 2H2, ΔH298 K = 247 kJ/mol
Non-thermal plasma (NTP) offers a unique way to enable
thermodynamically unfavorable chemical reactions to occur at
low temperatures due to its non-equilibrium character: the
overall gas temperature in a NTP remains low, while the
generated electrons are highly energetic with a typical electron
temperature of 1-10 e; sufficient to activate inert molecules (e.g.
CO2 and CH4) into reactive species, including radicals, excited
atoms, molecules and ions. These energetic species are
capable of initiating a variety of chemical reactions. Although
much effort has been expended on the use of NTP for the
destruction of gas pollutants, far less has been done in regard to
their use in the synthesis of fuels and chemicals [6]. Previous
Recently, Ge et al. investigated the direct C-C coupling of
CO2 and CH4 to form acetic acid on a Zn-doped ceria catalyst
using density functional theory (DFT) modeling [1]; this is an
works on DRM using NTP mainly focused on syngas production
[7]
,
while very limited efforts have been devoted to this
[a]
[b]
[c]
Dr. L. Wang, Dr. X. Tu
Department of Electrical Engineering and Electronics
University of Liverpool
Liverpool, L69 3 GJ, UK.
E-mail: xin.tu@liv.ac.uk
Dr. Y. H. Yi, Prof. H. C. Guo
State Key Laboratory of Fine Chemicals
School of Chemical Engineering
Dalian University of Technology
Dalian, 116024, P. R. China
Dr. C. F. Wu
challenging reaction – one-step conversion of CH4 and CO2 to
liquid fuels and chemicals [8]-[9]. A few groups reported the
formation of trace oxygenates (e.g., alcohols and acids) as by-
products in plasma DRM for syngas production [10]. So far, the
use of NTP for the direct conversion of CO2 and CH4 into
oxygenates has shown poor selectivity and yield.
School of Engineering,
University of Hull,
Hull, HU6 7RX, UK
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201707131
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COMMUNICATION
catalyst coupling mode. (Figure S2). These findings demonstrate
the feasibility of using NTP for the direct conversion of CH4 and
CO2 into higher value liquid fuels and chemicals in a single step
process at ambient conditions, bypassing the formation of
syngas.
Scheme 1. Direct and in-direct processes for the conversion of CO2 and CH4
to liquid fuels and chemicals.
In this work, a novel dielectric barrier discharge (DBD)
reactor with a ground water electrode (Schemes S1 and S2) has
been developed for one-step conversion of CO2 and CH4 to
oxygenates at room temperature (30 oC) and atmospheric
pressure. This setup is unique and has not before been reported.
Figure 1 shows that no reaction occurred in the ‘catalyst-alone’
mode at 30 oC without plasma. However, the use of a NTP
enables this thermodynamically unfavorable reaction to occur at
room temperature and produces liquid chemicals including
acetic acid, methanol, ethanol and acetone, with acetic acid
being the major product. Trace amounts of formic acid, propanol
and butanol were also detected in the condensed liquid. In the
plasma process without a catalyst (‘plasma-alone’), a total liquid
selectivity of 59.1% was achieved with 33.7%, 11.9%, 11.9%
and 1.6% for acetic acid, ethanol, methanol and acetone,
respectively (Figure 1a). The CO selectivity was limited at ca.
20.0% (Figure 1b), together with CH4 and CO2 conversions of
18.3 % and 15.4 %, respectively (Figure 1c).
Coupling the plasma process with a catalyst shows great
potential to manipulate the production of different oxygenates at
ambient conditions. Clearly, packing the Cu/γ-Al2O3 catalyst in
the DBD enhanced the selectivity of acetic acid to 40.2%,
compared to the ‘plasma-alone’ mode and the plasma reaction
using γ-Al2O3 only (20.2%). Acetic acid was the major product
regardless of the catalyst used, followed by methanol and
ethanol (Figure 1a). Note HCHO was formed only when using
the supported noble metal catalysts in the plasma reaction and
the Pt/γ-Al2O3 catalyst showed the highest selectivity to HCHO.
Compared to the ‘plasma-alone’ mode, placing the catalysts in
the DBD showed similar gaseous products, with H2, CO and
C2H6 being the major gas products (Figure 1b). However,
coupling the NTP with the catalysts enhanced the H2 selectivity
by 10-20% (except for Cu/γ-Al2O3), and slightly increased C2H6
production, but had a weak effect on CO selectivity (except
Cu/γ-Al2O3 which decreased CO selectivity to 13.5%) and other
CxHy (i.e., C2H2, C2H4, C2H6, C3H8 and n-C4H10). In addition,
compared to the ‘plasma-alone’ mode, the conversion of CO2
and CH4 slightly decreased with packing catalysts. This
phenomenon can be attributed to the change in discharge
behavior induced by the catalyst, which had a negative effect on
the reaction (Figure S1). Interestingly, acetic acid, hydroxyl-,
ethyl ester was found on the reactor inner wall in the plasma-
Figure 1. Effect of operating modes and catalysts on the reaction: (a)
selectivity of oxygenates, (b) selectivity of gas products, (c) the conversion of
CH4 and CO2 (total flow rate 40 ml/min, discharge power 10 W, catalyst ca. 2
g).
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To understand the formation pathways of acetic acid,
ethanol and methanol, optical emission spectroscopy (OES)
diagnostics was used to investigate the species produced in the
CH4/CO2 DBD (Figure 2). Reactive species, including CH, Hα, O
Acetic acid formation: Two possible reaction pathways could
contribute to the formation of acetic acid. CO can react with a
CH3 radical to form an acetyl radical (CH3CO) via reaction S14 in
table S3 with a low energy barrier of 28.77 kJ/mol [16], followed
by the recombination with OH to produce acetic acid via reaction
S15 with no energy barrier [10g], which was further confirmed by
Figures 3 and S4. Clearly, the selectivity of acetic acid increased
initially, then decreased with the CH4/CO2 ratio, with the optimal
acetic acid formation at a CH4/CO2 ratio of 1:1. Correspondingly,
the relative intensity of the CO band and O atomic line increased
with decreasing CH4/CO2 ratio from 3:1 to 1:2, while that of CH
band had a reverse evolution character (Figure S4). This
suggests that decreasing the CH4/CO2 mole ratio decreased the
generation of CH3 radicals, but increased OH formation. A
+
radical, C2, CO2 , CO2, and CO Angstrom band, were identified,
with CO, CH and H being the major species (Table S2).
CO is mainly derived from reaction S1-S3 (table S3) in the
DBD. Our simulation showed electron impact CO2 reactions
produced ~95% vibrational excited CO2 (CO2(V)) compared to
electronically excited CO2 (CO2(E)), as shown in Figure S3 and
table S4. O radicals generated from CO2 dissociation can attack
CO2(V) molecules to produce CO (S1-S2) [11]. Different from CH,
CH3-derived from CH4 dissociation cannot be detected using
OES, but recent simulation revealed that electron impact
dissociation of CH4 leads to 79% CH3 formation, whereas only
15% and 5% CH2 and CH formation, respectively [12]. Therefore,
CH3 is the dominant specie in the CH4/CO2 DBD. In addition to
electrons (S4 in table S3), reactive species such as OH, O and
H can also react with CH4 to produce CH3 radicals (S5-S7) in the
CH4/CO2 DBD. Additionally, OH is an important specie,
especially for alcohol formation. In the CH4/CO2 DBD, OH could
similar mechanism of acetic acid formation was proposed using
[10g]
DFT modeling
and by Eliasson et al. [10i]. In addition, direct
coupling of CH3 and carboxyl radicals (COOH) could also form
acetic acid via reaction S16, while COOH radicals may be
formed from reaction S17 and S18 in table S3 [10g]
.
be produced indirectly via reaction S8-S13, with S8 and S9 the
[13]
major channels based on the reaction rate coefficient and Ea
.
Special attention was given to S10, although a very low reaction
rate coefficient of 1.4E-29 and a high Ea of 111 kJ/mol were
observed for ground state CO2 reacting with H radical to produce
OH radical, this reaction (S10) can be accelerated by CO2(V)
[14]
instead of ground state CO2
and the vibrational energy of the
reagents is the most effective in overcoming the activation
barrier of the endothermic reaction [14-15]. Thus, the reaction
CO2(V) + H → CO + OH could be one of the major routes for OH
formation in this study, as CO2 mainly existed in vibrationally
exited states (Figure S3).
Scheme 2. Possible reaction pathways for the formation of CH3COOH,
CH3OH and C2H5OH in direct reforming of CH4 and CO2 using DBD.
Figure 2. Optical emission spectra of CH4, CO2 and CH4/CO2 plasmas (total
flow rate 40 ml/min, CH4/CO2 ratio 1:1, discharge power 10 W, 2 s exposure
time).
Figure 3. Effect of CH4/CO2 mole ratio on the selectivity of oxygenates without
a catalyst (total flow rate 40 ml/min, discharge power 10 W).
Based on the analysis of gas and condensed liquid products
combined with the OES, CO, CH3 and OH radicals were the key
species in the CH4/CO2 plasma reaction. Therefore, the possible
reaction pathways for the formation of acetic acid, methanol and
ethanol in this study are proposed in Scheme 2.
Alcohol formation: Decreasing the CH4/CO2 ratio decreased
the generation of CH3 radicals, but increased OH formation
(Figure S4). Simultaneously, the formation of CH3OH increased
initially with decreasing CH4/CO2 ratio and reached a peak at a
CH4/CO2 ratio of 1:1. By contrast, the formation of C2H5OH
decreased continuously as the CH4/CO2 ratio decreased (Figure
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10.1002/anie.201707131
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3). These findings suggest that the production of CH3OH mainly
depends on the generation of both CH3 and OH radicals, while
the formation of C2H5OH was more sensitive to the presence of
CH3 radicals in the plasma reaction as C2H5OH formation
requires twice the amount of CH3 radicals in comparison to the
formation of CH3OH. As shown in Scheme 2, CH3OH can be
directly formed from the coupling of CH3 and OH radicals with a
high rate coefficient (S19 in table S3) [17], while C2H5OH
Acknowledgements
The support of this work by the EPSRC SUPERGEN Hydrogen
& Fuel Cell (H2FC) Programme (EP/J016454/1) ECR Project
(Ref. EACPR_PS5768) is gratefully acknowledged.
Keywords: CO2 conversion • CH4 activation • non-thermal
plasma • dry reforming • liquid fuels and chemicals
formation required several elementary reactions (S20-S24). The
recombination of CH3 radical with itself forms C2H6 (S20)
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Clearly, placing the catalysts in the plasma reaction can tune
the distribution of oxygenates, especially for the formation of
HCHO after packing the Pt and Au catalysts, revealing the
occurrence of surface reactions in addition to the plasma gas
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CH3OH oxidation and methylene (CH2) oxidation could form
HCHO over noble-metal catalysts [22]. In this plasma process,
packing noble-metal catalysts in the plasma had almost no
influence on the CO selectivity, but decreased the selectivity of
CH3OH, C2H5OH and CH3COOH and increased the selectivity of
HCHO and C2H6 (Figure 1a). Considering the major species that
existed in the CH4/CO2 DBD, CHx (x = 4, 3, and 2) could be the
primary source for HCHO formation via oxidation reactions.
Namely, CHx in the gas phase could be adsorbed onto the
surface of the catalyst to form HCHO via the oxidation of CH2, ad
(CHx, ad + O, H, OH → CH2, ad), and to produce C2H6 via self-
recombination of CH3 radical instead of converting CH3 to
CH3OH, C2H5OH and CH3COOH. This could explain why the
presence of the Au and Pt catalysts in the plasma decreased the
formation of CH3OH, C2H5OH and CH3COOH, but enhanced the
production of C2H6 and HCHO (Figures 1a and 1b). The possible
pathways for the formation of major oxygenates on the catalyst
surface were proposed in Scheme S3. In addition, a range of
catalyst characterization (Figures S5-S8) suggest that metal
particle size and interaction of metal and support are not the
determining factors for the different reaction performances
(Figure 1), whereas the bonding strength of adsorbed
intermediates to the catalyst surface, i.e. oxygen adsorption
energy (ΔEO), could be a good activity descriptor towards the
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Entry for the Table of Contents
Layout 1:
COMMUNICATION
Single-step synthesis of
liquid fuels and chemicals from
CO2 and CH4 at ambient
conditions was achieved using
plasma-driven catalysis.
L. Wang,[a] Y. H. Yi,[b], C. F. Wu,[c]
H. C. Guo,[b] and X. Tu*[a]
One-step reforming of CO2 and
CH4
to
high-value
liquid
chemicals and fuels at room
temperature via plasma-driven
catalysis
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