Wen Yufeng, Zeng Xianshi, Xiao Yanan, Ruan Wen, Xiong Kai, Lai Zhangli
School of Mathematical Sciences and Physics, Jinggangshan University, Ji'an 343009, China.
Materials Genome Institute, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan University, Kunming 650091, China.
Molecules. 2024 May 15;29(10):2320. doi: 10.3390/molecules29102320.
This study investigates the utilisation of organometallic network frameworks composed of fourth-period transition metals and tetrahydroxyquinone (THQ) in electrocatalytic CO reduction. Density functional theory (DFT) calculations were employed in analysing binding energies, as well as the stabilities of metal atoms within the THQ frameworks, for transition metal TM-THQs ranging from Y to Cd. The findings demonstrate how metal atoms could be effectively dispersed and held within the THQ frameworks due to sufficiently high binding energies. Most TM-THQ frameworks exhibited favourable selectivity towards CO reduction, except for Tc and Ru, which experienced competition from hydrogen evolution reaction (HER) and required solution environments with pH values greater than 5.716 and 8.819, respectively, to exhibit CORR selectivity. Notably, the primary product of Y, Ag, and Cd was HCOOH; Mo produced HCHO; Pd yielded CO; and Zr, Nb, Tc, Ru, and Rh predominantly generated CH. Among the studied frameworks, Zr-THQ displayed values of 1.212 V and 1.043 V, corresponding to the highest limiting potential and overpotential, respectively, while other metal-organic frameworks displayed relatively low ranges of overpotentials from 0.179 V to 0.949 V. Consequently, it is predicted that the TM-THQ framework constructed using a fourth-period transition metal and tetrahydroxyquinone exhibits robust electrocatalytic reduction of CO catalytic activity.
本研究考察了由第四周期过渡金属和四羟基醌（THQ）组成的有机金属网络框架在电催化CO还原中的应用。采用密度泛函理论（DFT）计算分析了从Y到Cd的过渡金属TM-THQ的结合能以及THQ框架内金属原子的稳定性。研究结果表明，由于具有足够高的结合能，金属原子能够有效地分散并固定在THQ框架内。除了Tc和Ru之外，大多数TM-THQ框架对CO还原表现出良好的选择性，其中Tc和Ru分别受到析氢反应（HER）的竞争，并且分别需要pH值大于5.716和8.819的溶液环境才能表现出CORR选择性。值得注意的是，Y、Ag和Cd的主要产物是HCOOH；Mo产生HCHO；Pd生成CO；而Zr、Nb、Tc、Ru和Rh主要生成CH。在所研究的框架中，Zr-THQ的极限电位和过电位分别为1.212 V和1.043 V，是最高的，而其他金属有机框架的过电位范围相对较低，为0.179 V至0.949 V。因此，预计使用第四周期过渡金属和四羟基醌构建的TM-THQ框架具有强大的电催化CO还原催化活性。
