Wang Qinru, Yang Xiaofeng, Zang Hu, Chen Feiran, Wang Chao, Yu Nan, Geng Baoyou
College of Chemistry and Materials Science, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, Anhui Provincial Engineering Laboratory for New-Energy Vehicle Battery Energy-Storage Materials, Anhui Normal University, Wuhu 241002, China.
Institute of Energy, Hefei Comprehensive National Science Center, Hefei, 230031 Anhui, China.
Inorg Chem. 2022 Aug 1;61(30):12003-12011. doi: 10.1021/acs.inorgchem.2c01961. Epub 2022 Jul 15.
Bismuth-based catalysts exhibit excellent activity and selectivity for the electroreduction of carbon dioxide (CO). However, single-component bismuth-based catalysts are not satisfactory for the electrochemical reduction of CO to formic acid, mainly due to their high hydrogen production, low electrical conductivity, and small catalytic current density. Herein, we used a coordination strategy to recombine Bi and In at the molecular level to form Bi/In bimetallic metal-organic frameworks (MOFs), which were then calcined to obtain MOF-derived Bi/In bimetallic oxide nanoparticles embedded in carbon networks. Thanks to the synergistic effect of bimetallic components, high specific surface area, suitable pore size distribution, and high electrical conductivity of the carbon network, the material exhibits excellent activity and selectivity for electroreduction of CO to formate. In H-type electrolyzers, the formate Faradaic efficiency reaches 91% at -0.9 V (vs RHE) and does not decrease significantly within 48 h. In situ Fourier transform infrared spectroscopy confirms the reaction intermediates and reveals that CO electroreduction is dominant by the *OCHO pathway.
铋基催化剂对二氧化碳(CO)的电还原表现出优异的活性和选择性。然而,单组分铋基催化剂对于将CO电化学还原为甲酸并不令人满意,主要是因为它们析氢量高、电导率低以及催化电流密度小。在此,我们采用配位策略在分子水平上使Bi和In重组,形成Bi/In双金属金属有机框架(MOF),然后将其煅烧,以获得嵌入碳网络中的MOF衍生的Bi/In双金属氧化物纳米颗粒。由于双金属组分的协同效应、高比表面积、合适的孔径分布以及碳网络的高电导率,该材料对CO电还原为甲酸盐表现出优异的活性和选择性。在H型电解槽中,在-0.9 V(相对于可逆氢电极)下甲酸盐法拉第效率达到91%,并且在48小时内没有显著下降。原位傅里叶变换红外光谱证实了反应中间体,并揭示CO电还原主要通过*OCHO途径进行。