Wu Mengchen, Yang Yang, Zhao Jing, Liu Rui
Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China.
Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China.
J Colloid Interface Sci. 2025 Jan;677(Pt B):452-461. doi: 10.1016/j.jcis.2024.08.077. Epub 2024 Aug 13.
In CO electroreduction, mutative intermediates and the challenging CC coupling necessitate the spatial interplay between active sites and through dynamically optimizing configurations. Herein, we anchor ethylenediaminetetraacetic acid (EDTA)-bonded Cu/Bi pair within UiO-66 for a spontaneous spatial-optimizing CO-to-CH electroreduction. Ab initio molecular dynamic (AIMD) simulation visualizes that such metal pair adaptively interacts with intermediates. Density functional theory (DFT) elicits the componential synergy, in which an upshift d-band of Cu activates CO being protonated into *COOH while Bi site stabilizes oxygenated dimers for deep hydrogenation. The dynamic feature of such pair affords large freedom for sorption and migration of various intermediates, which consequently bestows UiO-66-EDTA/CuBi a maximal [Formula: see text] of 47 % and a total current density over 100 mA cm in the flow cell.
在CO电还原过程中，变化的中间体和具有挑战性的C-C偶联需要活性位点之间的空间相互作用，并通过动态优化构型来实现。在此，我们将乙二胺四乙酸（EDTA）键合的Cu/Bi对锚定在UiO-66中，以实现自发的空间优化CO到CH的电还原。从头算分子动力学（AIMD）模拟表明，这种金属对与中间体发生自适应相互作用。密度泛函理论（DFT）揭示了组分协同作用，其中Cu的d带向上移动激活CO质子化为*COOH，而Bi位点稳定氧化二聚体以进行深度氢化。这种金属对的动态特性为各种中间体的吸附和迁移提供了很大的自由度，从而使UiO-66-EDTA/CuBi在流动池中具有47%的最大[公式：见原文]和超过100 mA cm的总电流密度。
