TY - JOUR
T1 - Low-temperature selective synthesis of metastable α-MoC with electrochemical properties
T2 - Electrochemical co-reduction of CO2 and MoO3 in molten salts
AU - Zhu, Longtao
AU - Zhao, Yinan
AU - Yang, Wenhao
AU - Hsu, Hsien-Yi
AU - Peng, Ping
AU - Li, Fang-Fang
PY - 2024/1
Y1 - 2024/1
N2 - Metastable molybdenum carbide (α-MoC), as a catalyst and an excellent support for metal catalysts, has been widely used in thermo/electro-catalytic reactions. However, the selective synthesis of α-MoC remains a great challenge. Herein, a simple one-pot synthetic strategy for the selective preparation of metastable α-MoC is proposed by electrochemical co-reduction of CO2 and MoO3 in a low-temperature eutectic molten carbonate. The synthesized α-MoC shows a reed flower-like morphology. By controlling the electrolysis time and monitoring the phase and morphology of the obtained products, the growth process of α-MoC is revealed, where the carbon matrix is deposited first followed by the growth of α-MoC from the carbon matrix. Moreover, by analyzing the composition of the electrolytic products, the formation mechanism for α-MoC is proposed. In addition, through this one-pot synthetic strategy, S-doped α-MoC is successfully synthesized. Density functional theory (DFT) calculations reveal that S doping enhanced the HER performance of α-MoC by facilitating water absorption and dissociation and weakening the bond energy of Mo-H to accelerate H desorption. The present work not only highlights the valuable utilization of CO2 but also offers a new perspective on the design and controllable synthesis of metal carbides and their derivatives. © 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
AB - Metastable molybdenum carbide (α-MoC), as a catalyst and an excellent support for metal catalysts, has been widely used in thermo/electro-catalytic reactions. However, the selective synthesis of α-MoC remains a great challenge. Herein, a simple one-pot synthetic strategy for the selective preparation of metastable α-MoC is proposed by electrochemical co-reduction of CO2 and MoO3 in a low-temperature eutectic molten carbonate. The synthesized α-MoC shows a reed flower-like morphology. By controlling the electrolysis time and monitoring the phase and morphology of the obtained products, the growth process of α-MoC is revealed, where the carbon matrix is deposited first followed by the growth of α-MoC from the carbon matrix. Moreover, by analyzing the composition of the electrolytic products, the formation mechanism for α-MoC is proposed. In addition, through this one-pot synthetic strategy, S-doped α-MoC is successfully synthesized. Density functional theory (DFT) calculations reveal that S doping enhanced the HER performance of α-MoC by facilitating water absorption and dissociation and weakening the bond energy of Mo-H to accelerate H desorption. The present work not only highlights the valuable utilization of CO2 but also offers a new perspective on the design and controllable synthesis of metal carbides and their derivatives. © 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
KW - CO2 electroreduction
KW - Hydrogen evolution reaction
KW - Molten salt
KW - Sulfur doping
KW - α-MoC
UR - http://www.scopus.com/inward/record.url?scp=85174454278&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85174454278&origin=recordpage
U2 - 10.1016/j.cclet.2023.108583
DO - 10.1016/j.cclet.2023.108583
M3 - RGC 21 - Publication in refereed journal
SN - 1001-8417
VL - 35
JO - Chinese Chemical Letters
JF - Chinese Chemical Letters
IS - 1
M1 - 108583
ER -