Zhang Han, Yang Yu, Liang Yongxiang, Li Jun, Zhang An, Zheng Han, Geng Zhigang, Li Fengwang, Zeng Jie
Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia.
ChemSusChem. 2022 Jan 10;15(1):e202102010. doi: 10.1002/cssc.202102010. Epub 2021 Dec 2.
Electrochemical CO methanation powered by renewable electricity provides a promising approach to utilizing CO in the form of a high-energy-density, clean fuel. Cu nanoclusters have been predicted by theoretical calculations to improve methane selectivity. Direct electrochemical reduction of Cu-based metal-organic frameworks (MOFs) results in large-size Cu nanoparticles which favor multi-carbon products. This study concerns an electrochemical oxidation-reduction method to prepare Cu clusters from MOFs. The derived Cu clusters exhibit a faradaic efficiency of 51.2 % for CH with a partial current density of >150 mA cm . High-resolution microscopy, in situ X-ray absorption spectroscopy, in situ Raman spectroscopy, and a range of ex situ spectroscopies indicate that the distinctive CH selectivity is due to the sub-nanometer size of the derived materials, as well as stabilization of the clusters by residual ligands of the pristine MOF. This work offers a new insight into steering product selectivity of Cu by an electrochemical processing method.
由可再生电力驱动的电化学CO甲烷化提供了一种利用CO生成高能量密度清洁燃料的有前景的方法。理论计算预测，铜纳米团簇可提高甲烷选择性。基于铜的金属有机框架（MOF）的直接电化学还原会产生有利于多碳产物生成的大尺寸铜纳米颗粒。本研究涉及一种从MOF制备铜团簇的电化学氧化还原方法。所得铜团簇对CH的法拉第效率为51.2%，其分电流密度>150 mA cm 。高分辨率显微镜、原位X射线吸收光谱、原位拉曼光谱以及一系列非原位光谱表明，独特的CH选择性归因于所得材料的亚纳米尺寸以及原始MOF的残留配体对团簇的稳定作用。这项工作为通过电化学处理方法控制铜的产物选择性提供了新的见解。
