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Liu 2017
Liu 2017
Accepted Article
Authors: Yanming Liu, Yujing Zhang, Kai Chen, Xie Quan, Xinfei Fan,
Yan Su, Shuo Chen, Huimin Zhao, Yaobin Zhang, Hongtao
Yu, and Michael R. Hoffmann
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content of this Accepted Article.
COMMUNICATION
Abstract: Electrochemical reduction of CO2 to ethanol, a clean and morphology,[5] exposed surface facet[6] or surface
[7]
renewable liquid fuel with high heating value, is an attractive strategy functionalization of metals. Although metals exhibit competent
for global warming mitigation and resource utilization. However, activity, they often undergo easy deactivation or poor selectivity
converting CO2 to ethanol remains great challenge due to the low for high energy density products. Transition metal oxides and
activity, poor product selectivity and stability of electrocatalysts. Here, chalcogenides (e.g. Co3O4) have also been explored for
B and N codoped nanodiamond (BND) was reported as an efficient electrocatalytic CO2 reduction.[8] Their primary products are
and stable electrode for selective reduction of CO2 to ethanol. Good limited to CO or HCOO- with maximum Faradic efficiency of 60.0-
ethanol selectivity was achieved on BND with high Faradaic efficiency 85.1%. Recently, carbon based nanomaterials[9] such as B doped
of 93.2% (-1.0 V vs RHE), which overcame the limitation of low diamond (BDD), N doped carbon nanotubes and graphene have
selectivity for multicarbon or high heating value fuels. Its superior been proposed as promising electrocatalysts for CO2 reduction
performance was mainly originated from the synergistic effect of B due to their earth abundant component, good activity and
and N codoping, high N content and overpotential for hydrogen durability, which reduce CO2 to CO, HCHO or HCOO- with
evolution. The possible pathway for CO2 reduction revealed by DFT maximum Faradic efficiency of 74.0-87.0%. Although notable
computation was CO2 → *COOH → *CO → *COCO → *COCH2OH progress has been achieved, there remains a major challenge to
→ *CH2OCH2OH → CH3CH2OH. develop durable electrocatalysts that can efficiently and
selectively convert CO2 to high heating value fuels, especially that
with multicarbon such as CH3CH2OH.
The world-wide utilization of fossil fuels deplete feasible fossil
B and N codoped diamond (BND) is a potential electrocatalyst
fuel sources and produce large amount of CO2. Electrocatalytic
with good stability. B and N doping regulate the electronic
reduction of CO2 to fuels or other chemicals can reduce CO2
structure of diamond,[10] which enable to form defect-induced
accumulation in atmosphere and alleviate energy crisis, which is
active sites for CO2 reduction. BND has a more negative H2
a promising method for carbon recycling if powered by renewable
evolution potential than the electrocatalysts mentioned above,
energy sources. Electrocatalytic CO2 reduction can yield a variety
which is more favorable for CO2 reduction with higher Faradic
of products, including CO, HCOO-, HCHO, CH3COO-, CH3OH,
efficiency. These properties make BND an attractive alternative
CH3CH2OH, CH4, etc. However, CH3CH2OH is preferred product
electrocatalyst for CO2 reduction. N doped diamond (NDD)
because it is a clean and renewable liquid fuel with high heating
preferentially reduces CO2 to C2 product CH3COO-,[11] while the
value (-1366.8 kJ/mol, higher than -283.0~-890.4 kJ/mol for
main product reported for BDD is HCHO.[9b] Given the observed
others listed above). It is also an important raw material for
synergistic effect of B and N codoping on electrocatalytic activity
organic chemicals and disinfectants. Industrial production of
of carbon nanomaterials,[10a,12] codoped BND may afford better
CH3CH2OH consumes large amount of agricultural feedstocks or
electrocatalytic performance than BDD and NDD, and convert
ethylene. Thus, there is a pressing need to find efficient
CO2 to highly reduced product. Moreover, CO2 reduction
electrocatalysts that can selectively convert CO2 to CH3CH2OH.
performance of BND can be tuned by altering its chemical
Homogeneous metal-ligand complex and heterogeneous
composition. However, electrocatalytic CO2 reduction on BND
electrocatalysts have been reported for CO2 reduction.[1] Metals[2]
and the impact of codoping with B and N on CO2 reduction have
and metal alloys[3] have been found to be active for
never been reported before. Herein, BND was explored for
electrocatalytic reduction of CO2, where product selectivity and
electrocatalytic reduction of CO2. The effect of codoped B and N
efficiency could be tailored by controlling particle size, [4]
on CO2 reduction performance was elucidated by experiments
combined with density function theory (DFT) calculation.
[*] Dr. Y. M. Liu, Y. J. Zhang, Prof. X. Quan, Dr. X. F. Fan, Dr. S. Chen, Prof. BND electrodes were prepared by depositing BND film on Si
H. M. Zhao, Prof. Y.B Zhang, Dr. H. T. Yu substrate using hot filament chemical vapor deposition method
Key Laboratory of Industrial Ecology and Environmental Engineering with a gas mixture of CH4/B2H6/N2/H2 that had 2.5% CH4. BNDs
(Ministry of Education), Faculty of Chemical, Environmental and
with the same B2H6 content (12.5%) but different N2 levels (2.5%,
Biological Science and Technology
Dalian University of Technology, Dalian 116024, China 5.0% and 10.0%) were prepared, which are denoted as BND1,
E-mail: quanxie@dlut.edu.cn BND2 and BND3, respectively. The surface morphology of
Dr. Y. Su, Prof. J. J. Zhao prepared BND electrodes was characterized by SEM images
School of Physics and Opto-Electronic Technology
(Figure 1a-c), which show BND films are composed of pyramidal
Dalian University of Technology, Dalian 116024, China
Prof. M. R. Hoffmann nanoparticles that cover the entire substrates. Well-faceted
Linde+Robinson Laboratories diamond crystals with clear edges and corners are observed on
California Institute of Technology, California 91125, United States BND1. When N content of BND is increased, twin crystals appear
[#] These authors contributed equally to this work.
on the grain boundaries of BND2 and BND3.
Supporting information for this article is given via a link at the end of the
document.
COMMUNICATION
a b c example, at -1.1 V, the measured production rate of CH3CH2OH
is 9.3 times, 17.5 times, 51.0 times as large as that of CH3OH,
and 11.4 times, 16.1 times, 12.9 times as large as that of HCOO -
for BND1, BND2 and BND3, respectively. Moreover, CH3CH2OH
production rate is significantly increased as potential negatively
500 nm 500 nm 500 nm
shifted from -0.8 V to -1.1 V (decrease at -1.1 V due to competition
d e from H2 evolution), while CH3OH and HCOO- production rates
-1 -1
1220 cm 1320 cm
BND3 (111)
(220)
(311) Intensity (a.u.) remain low in the range of potential applied. The CH 3CH2OH
BND3
Intensity (a.u.)
CH3OH CH3OH
lattice (Figure S1). The B contents of BND1, BND2 and BND3 are
-2
Rate (g h cm )
- -
-2
54 HCOO HCOO
54
-1
similar (2.4 at.%, 2.4 at.%, 2.5 at.%), while their N contents
-1
C2H5OH CH3OH
manifesting that the three BNDs are active for electrocatalytic 72
CH3OH
80
C2H5OH
Rate (g h cm )
-2
80 80
very negative potential for H2 evolution (-1.0~-1.1 V), on which
CO2 reduction can outcompete proton reduction even at potential 60
-
60 -
HCOO HCOO
as negative as -1.1 V. Its high overpotential for H2 evolution is CH3OH CH3OH
40 40 C2H5OH
C2H5OH
favorable for improving CO2 reduction efficiency.
To confirm the occurrence of CO2 reduction on BNDs and 20 20
COMMUNICATION
Achieving high Faradaic efficiency is still a great challenge for morphology and dopant content, identical crystal structure and
electrocatalytic reduction of CO2, especially for producing high dominated facet, the main factors contributing to the high activity
heating value fuels such as CH3CH2OH. Here, Faradaic efficiency and selectivity for CH3CH2OH on BND could be the synergetic
for CO2 reduction on BNDs was determined to further evaluate effect of B and N codoping. Both NDD and BND preferentially
their performance (Figure 3d-f). As expected, the Faradaic convert CO2 to C2 product, which suggests doping N into
efficiency for CH3CH2OH is much higher than those for CH3OH diamond may be key for effective C-C coupling reaction. CO2
and HCOO- on BNDs under any potential applied. It increases reduction on N doped graphitic carbon materials is reported to
gradually as potential is shifted from -0.8 V to -1.0 V, and then yield either HCOOH or CO.[9c,9d] Thus, the high CH3CH2OH
decreases at more negative potentials which may be due to selectivity of BND appears to be correlated to the intrinsic property
competition from H2 evolution reaction (Figure S1). The maximum of codoped diamond.
Faradaic efficiency for CH3CH2OH achieved on BND3 is 93.2% at Both CH3CH2OH production rate and current efficiency of BNDs
-1.0 V, which is 3107.7 times as great as that for CH3OH and 69.6 are in the order of BND3> BND2> BND1 before H2 evolution
times as great as that for HCOO-. It illustrates BND presents very occurred (Figure 3). As the three BNDs have the same crystal
high efficiency and selectivity for CH3CH2OH, which is the highest structure, similar morphology and B content, it can be deduced
among electrocatalysts reported to date.[5a,13] The Faradaic that the enhanced CH3CH2OH production performance of BND
efficiencies for CH3CH2OH follows the order BND1<BND2<BND3, may be originated from its increased N content and/or altered
elucidating that higher N content of BND is favorable for main facet (during BND preparation, its main facet changes from
converting CO2 to CH3CH2OH. (111) to (220) with increased N content). BND3 is more active
The durability of BND3 for electrocatalytic reduction of CO 2 was than BND2 for CH3CH2OH production and both of their main facet
evaluated by running 16 consecutive CO2 reduction experiments is (220), demonstrating the increased N content is responsible for
with each run lasting for 3 h at -1.0 V. As shown in Figure 4a, enhanced CH3CH2OH production performance of BND3. As high
Faradaic efficiency for CH3CH2OH keeps around 93.2% during 16 N content will also promote H2 evolution, a balance between N
sequential CO2 reduction experiments, which illustrates the high content and H2 evolution is crucial for achieving good CO2
durability of BND for electrocatalytic reduction of CO2. reduction performance on BND. Meanwhile, DFT computation is
employed to probe the impact of (111) and (220) facets for the
-
100 a b HCOO CH OH C H OH 3preferential production of CH3CH2OH. As shown in Figure S7,
2 5
100
Faradaic efficiency (%)
HCHO CH COOH
Faradaic efficiency (%)
COMMUNICATION
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Acknowledgements
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[11] Y. M. Liu, S. Chen, X. Quan, H. T. Yu, J. Am. Chem. Soc. 2015, 137, 11631-
This work was supported by National Natural Science Foun- 11636.
dation of China (NO. 21590813 and NO. 21437001) and the Pro- [12] Y. Zheng, Y. Jiao, L. Ge, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed.
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(B13012). [13] a) J. Wu, S. Ma, J. Sun, J. I. Gold, C. Tiwary, B. Kim, L. Zhu, N. Chopra, I.
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Ajayan, Nat. Commun. 2016, 7, 13869; b) D. Raciti, K. J. Livi, C. Wang,
Keywords: CO2 reduction • doped diamond • electrocatalysis •
Nano Lett. 2015, 15, 6829-6835.
ethanol • heterogeneous catalysis
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Efficient and selective electrochemical Y. M. Liu, Y. J. Zhang, K. Chen, X. Quan,*
reduction of CO2 to ethanol was X. F. Fan, Y. Su, S. Chen, H. M. Zhao, Y.
achieved on nonmetallic B and N B. Zhang, H. T. Yu, M. R. Hoffmann
codoped nanodiamond. The
synergistic effect of B/N codoping, N C2H5OH Page No. – Page No.
content and H2 evolution potential were
Selective electrochemical reduction of
used as key factors for tailoring ethanol C2H5OH
CO2 to ethanol on B and N codoped
selectivity. These factors and
nanodiamond
uncovered CO2 reduction mechanism 2CO2 + 9H2O + 12e– → C2H5OH + 12OH−
is valuable for converting CO2 to
multicarbon or high heating value fuels.