近日，深圳大学何传新团队发现通过第一壳层配位调节孤立镍位点的局部微环境，以调控CO₂电还原反应途径。该项研究成果发表在2025年5月6日出版的《国家科学评论》杂志上。

操纵单原子催化剂的局部微环境对于CO₂电还原的产物选择性至关重要。尽管理论研究表明，改变孤立镍位点的配位结构可以促进二氧化碳还原为甲烷，但迄今为止还没有实验证据。在此，通过调节镍中心原子周围硼（B）的配位壳，研究组实现了还原产物从CO到CH₄的转化。

原位技术和密度泛函理论计算表明，Ni-N-C基序第二壳层（Ni-N₄-B/C）中的B配位有助于CO的形成，而将B掺入第一壳层（Ni-N₃B₁/C）会显著调整Ni原子的电子结构，导致电子离域，从而增强*CO中间吸附强度，使CH₄成为主要产物。这项研究标志着在孤立的镍位点实现了电化学CO₂到CH₄的转化，并强调了局部配位环境调节在指导单原子催化剂反应途径中的重要性。 

附：英文原文

Title: Modulating the local microenvironment over isolated nickel sites through first-shell coordination to regulate the reaction pathway of CO2 electroreduction

Author: Kong, Yan, Jia, Xinmei, Chai, Xiaoyan, Chen, Zhi, Shang, Chunyan, Jiang, Xingxing, Cai, Huizhu, Jing, Lingyan, Hu, Qi, Yang, Hengpan, Zhang, Xue, He, Chuanxin

Issue&Volume: 2025-05-06

Abstract: Manipulating the local microenvironments of single-atom catalysts is crucial for the product selectivity of CO2 electroreduction. Although theoretical research suggests that modifying the coordination structure of isolated Ni sites can promote the reduction of CO2 to CH4, there is still no experimental evidence to date. Herein, by regulating the coordination shell of boron (B) surrounding the Ni central atom, we have achieved the transformation of the reduction product from CO to CH4. In situ techniques and density functional theory calculations reveal that B coordination in the second shell of the Ni–N–C motifs (Ni-N4-B/C) facilitates CO formation, whereas incorporating B into the first shell (Ni-N3B1/C) significantly tunes the electronic structure of the Ni atoms, leading to electron delocalization, which enhances the *CO intermediate adsorption strength and makes CH4 the dominant product. This study marks the experimental realization of electrochemical CO2-to-CH4 conversion at isolated Ni sites and underscores the importance of local coordination environment regulation in steering the reaction pathways of single-atom catalysts.

DOI: 10.1093/nsr/nwaf173

Source: https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwaf173/8126098searchresult=1