Details
| Original language | English |
|---|---|
| Number of pages | 12 |
| Journal | Catalysis letters |
| Early online date | 29 Feb 2024 |
| Publication status | E-pub ahead of print - 29 Feb 2024 |
Abstract
Molybdenum carbides (MoxC) with multiple crystal structures are a group of promising catalysts for low-temperature CO2 reduction to CO. However, the relationship between the C and Mo exposure and the activity is elusive, since control of the C and Mo exposure under the same crystal structures is a difficult task. Herein, the C and Mo exposure at the surface of α-MoC1−x was successfully modulated by control of the S-doped amount in the precursors. It is found that the C exposure was gradually increased with the S doping amount decreasing, and that sole Mo or C exposure will go against CO2 and H2 activation, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. In other words, MoC1−x with moderate exposure ratios of C to Mo is most favorable. As a result, the MoC/SiO2-390 catalyst, whose precursor was obtained by annealing molybdenum sulfide at 390 ℃ in air, has the optimal activity, exhibiting a 1001 μmol gcat−1 h−1 of the CO yield with ~89% selectivity at 150 ℃ under ambient pressure. Additionally, CO2 reduction to CO over α-MoC1−x proceeds mainly through the formate (HCOO*) pathway under current operating condition. The present work supplied further insight into the influence of α-MoC1−x surface structures on CO2 reduction. Graphical Abstract: The moderate exposure ratios of C to Mo at the surface of α-MoC1−x is the most favorable for CO2 reduction to CO, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. (Figure presented.).
Keywords
- CO reduction, Molybdenum carbide, Sulfur doping, Terminated surface
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
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In: Catalysis letters, 29.02.2024.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Modulating the C and Mo Exposure of Molybdenum Carbide for Efficient Low-Temperature CO2 Reduction to CO
AU - Zhao, Jie
AU - Li, Haolong
AU - Zhang, Xiaolong
AU - Bao, Ruixue
AU - Zhang, Tao
AU - Wang, Chuanyi
AU - Bahnemann, Detlef W.
N1 - Funding Information: Financial support by the National Science Foundation of China (Grant No. 21976116), the Natural Science Foundation of Shaanxi Province (Grant No. 2021JM-381), and the Youth Innovation Team Construction Research Program Project of the Shaanxi Provincial Department of Education (Grant No. 21JP015) is gratefully appreciated.
PY - 2024/2/29
Y1 - 2024/2/29
N2 - Molybdenum carbides (MoxC) with multiple crystal structures are a group of promising catalysts for low-temperature CO2 reduction to CO. However, the relationship between the C and Mo exposure and the activity is elusive, since control of the C and Mo exposure under the same crystal structures is a difficult task. Herein, the C and Mo exposure at the surface of α-MoC1−x was successfully modulated by control of the S-doped amount in the precursors. It is found that the C exposure was gradually increased with the S doping amount decreasing, and that sole Mo or C exposure will go against CO2 and H2 activation, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. In other words, MoC1−x with moderate exposure ratios of C to Mo is most favorable. As a result, the MoC/SiO2-390 catalyst, whose precursor was obtained by annealing molybdenum sulfide at 390 ℃ in air, has the optimal activity, exhibiting a 1001 μmol gcat−1 h−1 of the CO yield with ~89% selectivity at 150 ℃ under ambient pressure. Additionally, CO2 reduction to CO over α-MoC1−x proceeds mainly through the formate (HCOO*) pathway under current operating condition. The present work supplied further insight into the influence of α-MoC1−x surface structures on CO2 reduction. Graphical Abstract: The moderate exposure ratios of C to Mo at the surface of α-MoC1−x is the most favorable for CO2 reduction to CO, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. (Figure presented.).
AB - Molybdenum carbides (MoxC) with multiple crystal structures are a group of promising catalysts for low-temperature CO2 reduction to CO. However, the relationship between the C and Mo exposure and the activity is elusive, since control of the C and Mo exposure under the same crystal structures is a difficult task. Herein, the C and Mo exposure at the surface of α-MoC1−x was successfully modulated by control of the S-doped amount in the precursors. It is found that the C exposure was gradually increased with the S doping amount decreasing, and that sole Mo or C exposure will go against CO2 and H2 activation, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. In other words, MoC1−x with moderate exposure ratios of C to Mo is most favorable. As a result, the MoC/SiO2-390 catalyst, whose precursor was obtained by annealing molybdenum sulfide at 390 ℃ in air, has the optimal activity, exhibiting a 1001 μmol gcat−1 h−1 of the CO yield with ~89% selectivity at 150 ℃ under ambient pressure. Additionally, CO2 reduction to CO over α-MoC1−x proceeds mainly through the formate (HCOO*) pathway under current operating condition. The present work supplied further insight into the influence of α-MoC1−x surface structures on CO2 reduction. Graphical Abstract: The moderate exposure ratios of C to Mo at the surface of α-MoC1−x is the most favorable for CO2 reduction to CO, since bent adsorbed CO2 and H2 dissociation require the synergy of surface C and Mo. (Figure presented.).
KW - CO reduction
KW - Molybdenum carbide
KW - Sulfur doping
KW - Terminated surface
UR - http://www.scopus.com/inward/record.url?scp=85186453173&partnerID=8YFLogxK
U2 - 10.1007/s10562-024-04636-8
DO - 10.1007/s10562-024-04636-8
M3 - Article
AN - SCOPUS:85186453173
JO - Catalysis letters
JF - Catalysis letters
SN - 1011-372X
ER -