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Core–shell-structured CNT@hydrous RuO2 as a H2/

Cite this: J. Mater. Chem. A, 2021, 9,
CO2 fuel cell cathode catalyst to promote CO2
7617 methanation and generate electricity†
Jixiang Hu, Ting Qu, Yan Liu, Xin Dai, Qiang Tan, Yuanzhen Chen,
Shengwu Guo and Yongning Liu*

Received 17th November 2020
Accepted 3rd February 2021
DOI: 10.1039/d0ta11232a
rsc.li/materials-a
H2/CO2 fuel cells are important devices that convert CO2 into CH4 while generating electricity at mild
temperatures. Anhydrous ruthenium oxide (RuO2) on carbon nanotubes (CNT) as a cathode catalyst
causes CO2 methanation, but the methane production rate needs to be improved. In this paper, a core–
shell structure of CNT@hydrous RuO2 was fabricated by a simple sol–gel method. Unlike anhydrous
RuO2, which is a single electronic conductor, CNT@hydrous RuO2 is a proton–electron mixed
conductive material. Therefore, protons transfer not only in thepolybenzimidazole (PBI) film but also in
the catalyst layer with the assistance of crystalline water in hydrous RuO2. CO2 methanation involving
a reaction of multiple protons and electrons can be accelerated. The methane generation rate of
CNT@hydrous RuO2 reached 331.2 mmol gcat
1 h
1 at 190  C which is 3 times higher than that of
anhydrous RuO2. This research result provides an effective strategy for the catalytic reaction of multiple
proton–electron transfers.

research direction of CO2 reduction.10,21,23,24 The large amount of

1. Introduction
Since the industrial revolution, the content of atmospheric
carbon dioxide (CO2) has continuously increased from 280 ppm
in the early 1800s to 417 ppm in the present day (https://
www.CO2.earth/), which makes global warming an urgent
issue.1–4 To reduce the CO2 content in the atmosphere, the rst
step is the capture of CO2. The cryogenic air separation method
was successfully industrialized in the 1950s.2,5,6 The remaining
challenge is how to deal with the captured CO2. Traditional
underground landlls and deep ocean dissolution have poten-
tial leakage risks and are not sustainable.2,7 In recent years, the
conversion of carbon dioxide into high value chemicals or fuels
under mild conditions has attracted researchers' attention.1,2,8
However, CO2 has high thermodynamic stability, and the
dissociation energy of the C]O bond is as high as
750 kJ mol
1.9,10 A large amount of energy is needed to activate
the chemical bond of CO2 and convert it into products such as
methanol (CH3OH),11,12 methane (CH4),13,14 carbon monoxide
(CO),15–18 formate,19,20 and ethylene (C2H4).21,22
The electrocatalytic reduction of CO2 reduces CO2 to higher-
value chemicals through the input of electrical energy. Due to
its mild reaction conditions, easy operation, and high Faraday
efficiency, electrocatalysis has become the most popular
State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University,
Xi'an, 710049, P. R. China. E-mail: ynliu@xjtu.edu.cn
† Electronic supplementary information (ESI) available.
10.1039/d0ta11232a
electrical energy required for electrocatalysis is a problem. At
present, the solution to this problem is to use green energy such
as wind energy and solar energy to generate electricity.2,25 Due to
the limitations of natural factors and geographical conditions,
green energy power generation is discontinuous and unstable
so it is difficult to connect to the grid.26,27
Is there a device that can achieve CO2 reduction without
relying on an external power input? The prerequisite for the
excellent catalytic effect of common cathode catalysts for the
electrochemical reduction of CO2 is to an input of a large
amount of electrical energy to overcome a large reduction
overpotential, such as some Cu overpotentials that exceed
1 V.28,29 However, the Pt electrode achieves the electrical
reduction of CO2 to CO at a low overpotential (close to the
standard electrode potential).30,31 Minoru Umeda et al.
combined the fact that CO2 reduction has a reduction potential
higher than hydrogen oxidation with the operating principles of
fuel cells. They used Pt/C as the cathode and anode catalyst for
H2/CO2 fuel cells to achieve simultaneous CO2 reduction and
power generation for the rst time.32 Pt/C is poisoned by CO2
reduction products (CO), making the reduction process
discontinuous. To solve this problem, Ru, which does not
strongly adsorb CO, was added. Compared with Pt/C, Pt0.8Ru0.2
as a cell cathode catalyst has a discharge power density that
exceeds 1 mW cm
2 at 60  C, which is 5 times greater than the
discharge power density of Pt/C.33 These studies have proven the
See DOI:
feasibility of H2/CO2 fuel cell power generation but neglected to
explore the CO2 reduction products of the cathode. Instead, the

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Journal of Materials Chemistry A
catalyst that generates electricity is used for electrocatalytic CO2
reduction.
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Ru-Based catalysts are well-known in the eld of CO2
methanation for their high conductivity, excellent catalytic
activity and thermodynamic stability.34–37 The catalytic activity
of Ru catalysts for CO2 hydrogenation to methane is second to
none.35 Ru-Containing catalysts are used commonly as precious
metal catalysts with relatively low overpotentials,38 so we aimed
to introduce them into H2/CO2 fuel cells as cathode catalysts. In
a previous work,39 we assembled a H2/CO2 fuel cell to reduce
CO2 while generating electricity at mild temperatures in the
range of 130–170  C. This temperature range was maintained
using industrial waste heat. It has been shown that nano-RuO2
supported on CNT as a cathode catalyst and Pt/C (40%) as an
anode catalyst can stably and effectively achieve CO2 methana-
tion. The methane generation rate of a single cell reaches 66.25
mmol gcat
1 h
1, and the electrode reaction equation40,41 is as
follows:
Anode:
H2–2e
/ 2H+, E ¼ 0.000 V vs. SHE (1)
Cathode:
CO2 + 8H+ + 8e
/ CH4 + 2H2O, E ¼ 0.169 V vs. SHE (2)
Eqn (2) shows that CO2-to-CH4 is a complex eight-proton and
eight-electron transfer process. Hence, we prepared a catalyst
that conducts both protons and electrons to promote the reac-
tion. Finally, CNT@hydrous RuO2, which features a CNT core
with a diameter of approximately 14 nm and a hydrous RuO2
shell with a thickness of approximately 5 nm, was synthesized
by a simple sol–gel method.42 Hydrous RuO2 combines effective
electron transport (along dioxo bridges in RuO2) and convenient
proton transfer (through crystalline water) for CO2 reduction.43
Under the same test conditions, the methane production rate of
CNT@hydrous RuO2 as the cell cathode catalyst is 331.2 mmol
gcat
1 h
1, which is almost 3 times higher than that of anhy-
drous RuO2 on CNT.
2. Experimental section
2.1 Materials
Anhydrous RuO2 and RuCl3$3H2O were purchased from
Shaanxi Kaida Chemical Engineering Co., Ltd. Pt/C (HiSpec
4000, 40% Pt) was obtained from Johnson Matthey (UK). Mul-
tiwalled carbon nanotubes (CNT) were supplied by Chengdu
Organic Chemicals Co., Ltd (Chengdu, China). Naon solution
(Du Pont D520, 5 wt%) and carbon paper (0.21 mm in thickness)
were purchased from Shanghai Hesen Electric Co., Ltd. PBI
membranes (60 mm in thickness) were purchased from
Shanghai Shengjun Polymer Technologies Co., Ltd. Nitric acid
(HNO3, 65%), phosphoric acid (H3PO4, 85%) and sodium
bicarbonate (NaHCO3) were provided by Sinopharm Chemical
Reagent Co., Ltd. Polytetrauoroethylene (PTFE) gaskets were
supplied by Shenzhen Xinlongyuan Plastic Materials Co., Ltd
(Shenzhen, China). N2 (99.999%), Ar (99.999%), and air (O2 z
7618 | J. Mater. Chem. A, 2021, 9, 7617–7624
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21%, N2 z 79%) were supplied by Shaanxi Xinkang Medical
Oxygen Co., Ltd. CO2 (99.999%) was purchased from Praxair
(Shanghai) Industrial Gas Co., Ltd. H2 (99.999%) was obtained
using a QPH-300Ⅱ Hydrogen Generator.
2.2 Preparation of CNT@hydrous RuO2 and hydrous RuO2
CNT were treated with 2 M nitric acid reux at 80  C for 8 h. CNT
(200 mg) were dispersed in a 20 mL 0.1 M RuCl3 solution by
ultrasonication for 30 minutes. Then, 0.3 M NaHCO3 was slowly
added to the solution while stirring until the pH reached 7. Aer
stirring for 15 h, the solution was ltered and washed with
deionized water (Milli-Q, 18.25 MU) several times, and then
dried in an oven under vacuum at 50  C for 8 h. Finally, the
dried particles were ground and heat-treated at 150  C for 8 h.
The black powder was collected and shown to be CNT@hydrous
RuO2. The preparation of hydrous RuO2 was the same as that of
CNT@hydrous RuO2 except that CNT were not added.
2.3 Fuel cell assembly
The PBI membrane was soaked in H3PO4 at room temperature
for 48 hours for subsequent use. First, the cathode and anode
catalytic ink needed to be prepared. Twenty-ve milligrams
CNT@hydrous RuO2 was weighed for the cathode catalyst (the
comparison group included 15 mg anhydrous RuO2 and 10 mg
nitric acid-treated CNT), 1.5 mL alcohol and 15 mL Naon
solution were added in order, 10 mg Pt/C was weighed for the
anode, and 0.3 mL deionized water, 1.5 mL alcohol and 15 mL
Naon solution were added in order, and then the electrode
mixed solution was dispersed by ultrasonication for 0.5 h. Well-
dispersed catalytic ink was sprayed onto hydrophobic carbon
paper as a gas diffusion layer by using a gas-powered airbrush
(Ruiyi HD-130). Catalyst loading was calculated by weighing the
mass of carbon paper before and aer spraying. The membrane
electrode assembly (MEA) was hot-pressed by using a powder
tablet press at 130  C and 1.5 MPa force for 3 minutes. Finally,
PTFE gaskets with a thickness of 0.2 mm were embedded on
both sides of the MEA for heat transfer and sealing, and the fuel
cell structure is shown in Fig. 1.
Fig. 1 Schematic diagram of cell structure operated with high-purity
CO2 at the cathode and H2 at the anode. The membrane electrode
assembly (MEA) is composed of a PBI membrane soaked in phosphoric
acid and a catalytic layer supported on the gas diffusion layer (carbon
paper) on both sides.
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2.4 Fuel cell measurements
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Aer cell assembly was completed, residual air was passed out
of the cell device by introducing N2 until the open-circuit
voltage (OCV) of the cell system (Neware BTS-5V1A) was zero.
Then, CO2 was passed into the cathode, H2 was passed into the
anode, and the gas ow was controlled by a gas mass ow meter
(Sevenstar D07–19B). Aer 10 minutes, the thermal conductivity
detector (TCD) of the gas chromatograph (GC, Techcomp
GC7980) was used to detect whether H2 was in the cathode gas
to determine whether the MEA leaked. Under normal cell
operating conditions, the cell discharge data were measured at
each test temperature. When the cell was run and tested, the
CO2 ow rate at the cathode was 5 sccm (mL min
1), and the H2
ow rate at the cathode was 20 sccm. Aer the cell's limiting
current remained stable for 0.5 hours, the cathode outlet gas
was detected by the thermal conductivity detector and the
hydrogen ame ionization detector (FID).
2.5 Material characterization
Powder X-ray diffraction (XRD) patterns were collected on
a PANalytical X'Pert PRO diffractometer equipped with Cu Ka
radiation. The morphology of the material was observed by
scanning electron microscopy (SEM, JSM-6700F). The micro-
structure of the sample was obtained by transmission electron
microscope (TEM) and high-resolution TEM (HRTEM) on
a JEM-2100 instrument (JEOL, Japan). The specic surface area
was tested by using a Brunauer–Emmett–Teller (BET) method
for N2 adsorption–desorption (ASAP-2460, Micromeritics, USA).
The thermogravimetric (TG) curve of the CNT@hydrous RuO2
Fig. 2 XRD patterns: (a) CNT, (b) CNT@hydrous RuO2, and (c) anhydrous RuO2; XPS spectra of the O 1s for (d) anhydrous RuO2/CNT and (e)
CNT@hydrous RuO2.
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sample was obtained using a Setaram Labsys Evo (France). X-ray
photoelectron spectroscopy (XPS) was measured on a Thermo
Fisher ESCALAB Xi+ instrument (Al Ka radiation).
3. Results and discussion
Fig. 2a and b shows the X-ray diffraction (XRD) information
before and aer CNT were coated with hydrous RuO2. The two
diffraction peaks at 25.9 and 43.1 represent the (003) and (101)
planes of the CNT (PDF#26-1079), respectively; CNT@hydrous
RuO2 has three broadened humps at 28.0 , 35.0 , and 54.2 ,
which are assigned to the (110), (101), and (211) planes of RuO2
(PDF #43-1027), respectively; since the heat treatment temper-
ature was only 150  C, its crystallinity is lower than that of
anhydrous RuO2 (Fig. 2c). To gain a deep understanding of the
catalyst composition and element valence information, XPS
analysis was performed. For the XPS studies of the catalytic
material, the charge shis were corrected using the binding
energy (BE) of polluted carbon, centred at 284.6 eV as a refer-
ence.44 Deconvolution analysis of the full spectrum, Ru 3d, and
Ru 3p peaks for CNT@hydrous RuO2 is shown in Fig. S1.† In the
full spectrum (Fig. S1a†), C 1s and Ru 3d overlap signicantly at
a BE of approximately 285 eV. The C 1s spectrum can be
deconvolved into three peaks at 284.6 eV, 285.2 eV, and 286.8 eV
corresponding to C–C, C–O, and C]O in acid-treated CNT,
respectively;44,45 Ru 3d5/2 and Ru 3d3/2 are located at 281.3 eV
and 284.8 eV, and the two peaks at 283.4 eV and 287.9 eV belong
to satellites (Fig. S1b†).46 Due to the overlap of the spectral
peaks, to more clearly identify the valence state of Ru, Ru 3p
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Fig. 3 (a) TGA/DTG curves of CNT@hydrous RuO2 in the flowing nitrogen (N2); (b) TGA/DTG curves of CNT@hydrous RuO2 in the flowing air.
deconvolution (Fig. S1a†) was processed.47 Similarly, Ru 3p3/2
and Ru 3p1/2 are assigned at 462.9 eV and 485.1 eV, and the two
peaks at 465.6 eV and 487.4 eV are satellites.46 XPS analysis once
again proved that RuO2 was successfully prepared. In the O 1s
XPS spectra (Fig. 2d and e), the deconvolution of the electron
binding energy of Ru–O–Ru (529.6 eV), OH–C]O (532.4 eV),
and H2O (free water, ca.534 eV)48 was observed for anhydrous
RuO2/CNT and CNT@hydrous RuO2; the difference is that at an
electron binding energy of 530.9 eV, CNT@hydrous RuO2
corresponds to Ru–O–H and satellite peaks, however, anhy-
drous RuO2/CNT only corresponds to satellite peaks,46 and the
Ru–O–H peak represents hydrous ruthenium dioxide (RuO2-
$xH2O),43,49–51 Fig. 2e shows that crystalline water was success-
fully introduced into the catalyst prepared by the sol–gel
method.
The presence of crystal water was conrmed. To further
quantify the components of the catalyst, thermogravimetric
analysis/differential thermogravimetry (TGA/DTG) of different
gas environments was executed. In owing high-purity
nitrogen, the weight loss comes from moisture. The thermog-
ravimetric results of anhydrous RuO2/CNT show that the small
amount of free water adsorbed on the surface slowly contributes
to the weight loss from room temperature to 280  C (Fig. S2†).
XPS shows that the free water content of CNT@hydrous RuO2 is
lower than that of anhydrous RuO2/CNT (Fig. 2d and e), so the
water loss comes from crystalline water (approximately 99% or
more), except for a very small amount from the loss of free
water. This weight loss corresponds to the composition of
RuO2$2.76H2O. RuO2 will not decompose into Ru metal when
the temperature is lower than 1000  C in an air stream,43 so 52%
of the mass loss is contributed by CNT and moisture. In other
words, the mass percentages of RuO2 and CNT are divided into
48% and 24.8% in CNT@hydrous RuO2, respectively.
To gain more insight, the microscopic morphology of the
material was observed by scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). Compared to the
morphology of the acid-treated CNT, the surface of CNT@hy-
drous RuO2 has an obvious coating layer (Fig. S3†), which is
apparent in the scanning transmission electron microscope
(STEM) image shown in Fig. 4a. As shown in Fig. 4b and c,
7620 | J. Mater. Chem. A, 2021, 9, 7617–7624
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a single carbon tube before and aer being coated indicates that
the thickness of the hydrous RuO2 coating layer is approxi-
mately 5 nm. In other words, CNT@hydrous RuO2 features
a CNT core with a diameter of approximately 14 nm and
a hydrous RuO2 shell with a thickness of approximately 5 nm.
To characterize the pore size distribution of the catalyst, Bru-
nauer–Emmett–Teller (BET) analysis was performed
(Fig. S4†).52,53 CNT@hydrous RuO2 (91.2 m2 g
1) is a combina-
tion of hydrous RuO2 (12.7 m2 g
1) and CNT (160.8 m2 g
1) with
a large difference in specic surface area. CNT@hydrous RuO2
disperses hydrous RuO2 and retains more than half of the
mesopores in CNT. The result is consistent with the above TEM
image. The specic surface area of anhydrous RuO2/CNT is
larger than that of CNT@hydrous RuO2 due to its greater
number of micropores, so the surface adsorption free water
content is higher,54 which is consistent with the difference in
the free water content from XPS analysis. The high-resolution
transmission electron microscopy (HRTEM) image in Fig. 4d
shows that hydrous RuO2 (coexisting of crystalline water and
weakly crystalline RuO2 in a mixed solid-state) has no graininess
and low crystallinity. The interplanar spacings of 0.222 and
0.225 nm match the (200) and (111) planes of RuO2, respec-
tively. The energy-dispersive X-ray (EDX) elemental mapping of
the C element in Fig. 4f corresponds to the high-angle annular
dark-eld (HAADF)-STEM situation (Fig. 4e). Fig. 4g and h
shows that O and Ru are uniformly distributed around the
CNTs.
The performance of CNT@hydrous RuO2 as the cathode
catalyst of the cell at different temperatures in Fig. 5a shows
that the discharge current decreases with increasing tempera-
ture. In contrast, when anhydrous RuO2/CNT is the cathode
catalyst, no current decay occurs from 130 to 190  C (Fig. 5b). It
is further found that the open-circuit voltage (OCV) in Fig. 5a is
signicantly lower than the theoretical value (0.169 V) of CO2
methanation40 and the OCV decreases with increasing temper-
ature. The higher resistance of hydrous RuO2 than anhydrous
RuO2 has been conrmed by electrochemical impedance anal-
ysis.43 Therefore, the OCV of hydrated RuO2 is lower than the
theoretical potential. Based on these data and the TGA/DTG
curve (Fig. 3), it can be determined that there is a small loss
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Fig. 4 (a) STEM image of the CNT@hydrous RuO2. (b) acid-treated CNT and (c) CNT@hydrous RuO2 are TEM images of a single structure,
respectively. (d) HRTEM image of CNT@hydrous RuO2. (e) HAADF-STEM image and (f–h) EDX elemental mapping images of CNT@hydrous
RuO2: (f) C, (g) O, and (h) Ru elements.

Fig. 5 Cell performance curve at different temperatures. (a) Anhydrous RuO2/CNT as a cell cathode catalyst; (b) CNT@hydrous RuO2 as a cell
cathode catalyst.

of crystalline water from 130 to 210  C. Mesopores formed at the
site of crystalline water loss can be used as substance exchange
channels.55 However, the overall continuity of the proton–elec-
tron hybrid conduction network is slightly affected, as
described in detail in the discussion later. The effect is man-
ifested as a decrease in external voltage, followed by a decrease
in current. To determine the type and content of the product,
the gas from the cathode outlet of the cell is passed into the gas
chromatograph (GC) for testing. The test showed that the
contents of the products are mainly H2 (Fig. S5†) and CH4
(Fig. 6a and b). In previous reports,39 nano-RuO2 supported on
CNTs (RuO2/CNTs) was used as a CO2 reduction reaction
(CO2RR) catalyst to achieve CO2 methanation, and the possible
reaction paths for the formation of CH4 were determined by
density functional theory (DFT) calculations. Before each cell
test, the TCD test of the cathode outlet gas was performed under
the open-circuit voltage conditions, as shown in Fig. S6,† and
H2 was not found in the open circuit. The purpose of this test is
to show that the H2 of the cathode under operating conditions
comes from the competitive hydrogen evolution reaction
(HER)56 rather than diffusion or leakage from the anodic side of
the cell. Regardless of whether CNT@hydrous RuO2 or anhy-
drous RuO2/CNT is used as the cathode catalyst of the cell, the
amounts of CH4 (Fig. 6a and b) and H2 (Fig. S5†) in the cell
increase as the operating temperature range increase from 130
to 190  C increases with temperature. To explain the decay of
current and cathode products at higher temperatures, the cells
were disassembled and compared aer running at various
temperatures (Fig. S7†) because the phosphoric acid-soaked PBI
membrane is mechanically damaged.57,58 This is one of the
limitations in the long-term research of PBI membranes as
electrolyte. Therefore, before this limit is reached, it is more
appropriate to operate the cell at 190  C. Fig. 6a and b shows
that the catalytic ability of CNT@hydrous RuO2 to reduce CO2 is
higher than that for anhydrous RuO2/CNT, especially at 190  C,
which shows a signicant abrupt increase, and the

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Fig. 6 (a and b) Flame ionization detector spectra of gas chromatography at different temperatures, (a) is the reference group, that is, anhydrous
RuO2/CNT as the cell cathode catalyst, and (b) is CNT@hydrous RuO2 as the cell cathode catalyst; (c) CH4 yield under extreme discharge at
different temperatures; (d) Stability test of the cell at constant and extreme current at 190  C.

concentration of the reduction product CH4 reaches 147.8 ppm. RuO2 as a CO2RR catalyst is 1.3% at 190  C. The stability test was
The material conduction mechanism of the material, excluding carried out at the limit discharge current of the cell at 30 mA
the CNT contained in both anhydrous RuO2/CNT and and 190  C. Fig. 6d shows that the cell is quite stable within 470
CNT@hydrous RuO2, involves anhydrous rutile RuO2 acting as minutes. According to these data and the DTG curve in the N2
a single metal conductor (electron conduction along dioxo gas ow, only a small amount of crystalline water is lost
bridges),34,43 and its catalytic reaction site is found at the three- (Fig. 2a). To sum up, the CNT@hydrous RuO2 catalytic stability
phase reaction interface contact with the PBI lm. However, the was conrmed.
crystalline water in hydrous RuO2 can transport protons from
the anodic reaction,34,43,59,60 which occurs in the entire three-
dimensional space of the catalytic layer of the CO2 methana- 4. Conclusions
tion reaction. In other words, the introduction of crystalline
In summary, CNT@hydrous RuO2 as the cathode catalyst of
water greatly increases the number of active sites in the catalytic
CO2/H2 fuel cell was prepared by a simple sol–gel method, and
reaction, and the effectiveness of the catalyst is increased
the presence and content of crystalline water were identied by
accordingly. Next, calculations of the test results will be used to
XPS and TGA/DTG, respectively. Unlike anhydrous RuO2, which
support this nding.
relies on single electron conduction, CNT@hydrous RuO2
The calculated result of the CH4 generation rate based on the
embedded crystalline water that maintains a continuous
ESI† is shown in Fig. 6c. The trend of the CH4 generation rate is
conductive network so that the crystalline water conducts H+ in
similar to that of the change in the CH4 concentration, and the
the entire catalytic layer to increase the active sites of the cata-
maximum reduction generation rate of CNT@hydrous RuO2
lytic reaction. At 190  C, the methane generation rate of
reaches 331.2 mmol gcat
1 h
1 at 190  C, which is 3 times that of
CNT@hydrous RuO2 reaches 331.2 mmol gcat
1 h
1, which is
anhydrous RuO2/CNT under the same conditions. Compared
almost 3 times that of anhydrous RuO2/CNT under the same
with the previously reported39 highest single cell CH4 yield of
conditions, and the reaction can remain stable for 470 min.
66.25 mmol gcat
1 h
1, the current work successfully achieved
Although the TE of the catalytic reaction still needs to be further
a 5-fold increase. The transfer efficiency (TE) calculation for the
improved, we hope that the study of this catalyst will provide
CO2RR setup in detail is shown in the ESI,† and the relevant
a strategy for the future design of catalysts of multi-proton–
data are shown in Fig. S8.† The TE value for CNT@hydrous
electron catalytic reaction.

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Paper
Author contributions
Published on 10 February 2021. Downloaded by Indian Institute of Chemical Technology (IICT), Hyderabad on 5/10/2022 8:03:34 AM.
Jixiang Hu: Investigation, methodology, data curation, writing –
original dra. Ting Qu: Data curation, project administration.
Yan Liu: Investigation, formal analysis. Xin Dai: Visualization.
Qiang Tan: Formal analysis. Yuanzhen Chen: Formal analysis.
Shengwu Guo: Resources. Yongning Liu: Conceptualization,
supervision, writing – reviewing and editing.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The research acknowledges the instrument analysis center of
Xi'an Jiaotong University for material structure characteriza-
tion. The work was supported by the National Natural Science
Foundation of China (No. 51602246, 21603171 and 51801144)
and the China Postdoctoral Science Foundation (No.
2018M643629).
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