Customizing multi‐metal site catalysts for achieving controllable CO2 reduction reaction (CO2RR) product tuning holds immense promise yet poses formidable challenges. The traditional synthesis method of multi‐metal sites is the pyrolysis of metal‐containing precursors, which is inherently uncontrollable. Herein, a bottom‐up strategy is employed to customize and synthesize multi‐metal sites in covalent organic frameworks (COFs), aiming to controllably switch the CO2 reduction selectivity by regulating the electronic structure of active sites. Briefly, La element provides chances for manipulating and finetuning the electronic structure of the customized dual Cu sites, and converts the main catalytic product of CO2RR from ethylene to methane. Density functional theory calculations show that the introduction of La alters the electronic structure around Cu, enhances CO2 and H2O activation, and changes the formation of energy barriers of key intermediates. To the best of the author's knowledge, this study constructed the first example of customized multi‐metal site COF catalysts and provided new ideas for controllable modulation of products.

中文翻译：

---

将 La 引入定制的双铜共价有机框架中，以将 CO2 电还原选择性从 C2H4 控制到 CH4


定制多金属位点催化剂以实现可控的 CO2 还原反应 （CO2RR） 产品调整具有巨大的前景，但也带来了艰巨的挑战。传统的多金属位点合成方法是含金属前驱体的热解，这本身就是不可控的。本文采用自下而上的策略在共价有机框架 （COFs） 中定制和合成多金属位点，旨在通过调节活性位点的电子结构来可控地切换 CO2 还原选择性。简而言之，La 元素为操纵和微调定制的双 Cu 位点的电子结构提供了机会，并将 CO2RR 的主要催化产物从乙烯转化为甲烷。密度泛函理论计算表明，La 的引入改变了 Cu 周围的电子结构，增强了 CO2 和 H2O 的活化，并改变了关键中间体的能垒形成。据作者所知，本研究构建了第一个定制的多金属位 COF 催化剂的例子，并为产物的可控调制提供了新思路。