武汉大学定明月团队建立了非化学计量Ti₄O₇辅助的不对称C-C耦合实现一氧化碳高能效电还原。相关研究成果于2024年10月22日发表在国际顶尖学术期刊《德国应用化学》。

开发合适的铜基电催化剂载体材料有利于一氧化碳电还原稳定生产多碳化学品。然而，金属载体适应性不足和载体电导率低会阻碍C-C耦合容量和能量效率。在此，非化学计量比的Ti₄O₇被掺入Cu电催化剂（Cu-Ti₄O₇）中，并作为CO高效电化学转化的高导电性和稳定的载体。

Ti₄O₇中有序晶格缺陷产生的丰富氧空位有助于水解离和CO吸附，加速氢化成*COH。Cu-Ti₄O₇的高度适应性的金属-载体界面，使Cu上的*CO和Ti₄O₇上的*COH之间能够直接不对称的C-C耦合，这大大降低了C2+产物形成的反应能垒。

此外，Ti₄O₇的优异导电性有利于通过坚固的Cu/Ti₄O₇界面进行反应电荷转移，从而最大限度地减少能量损失。因此，优化的20Cu-Ti₄O₇催化剂对多碳产品，表现出令人印象深刻的96.4%的选择性和45.1%的超高能效，以及432.6 mA cm^-2的显著局部电流密度。

该研究强调了铜和载体材料之间的一种新的C-C偶联策略，推动了铜负载催化剂在一氧化碳高效电还原中的发展。

附：英文原文

Title: Establishing Non-stoichiometric Ti4O7 Assisted Asymmetrical C-C Coupling for Highly Energy-Efficient Electroreduction of Carbon Monoxide

Author: Xuli Hu, Junchen Xu, Yunchen Gao, Zhenyao Li, Jun Shen, Wei Wei, Yangshun Hu, Yushan Wu, Yao Wang, Mingyue Ding

Issue&Volume: 2024-10-22

Abstract: Exploring an appropriate support material for Cu-based electrocatalyst is conducive for stably producing multi-carbon chemicals from electroreduction of carbon monoxide. However, the insufficient metal-support adaptability and low conductivity of the support would hinder the C-C coupling capacity and energy efficiency. Herein, non-stoichiometric Ti4O7 was incorporated into Cu electrocatalysts (Cu-Ti4O7), and served as a highly conductive and stable support for highly energy-efficient electrochemical conversion of CO. The abundant oxygen vacancies originated from ordered lattice defects in Ti4O7 facilitate the water dissociation and the CO adsorption to accelerate the hydrogenation to *COH. The highly adaptable metal-support interface of Cu-Ti4O7 enables a direct asymmetrical C-C coupling between *CO on Cu and *COH on Ti4O7, which significantly lowers the reaction energy barrier for C2+ products formation. Additionally, the excellent electroconductivity of Ti4O7 benefits the reaction charge transfer through robust Cu/Ti4O7 interface for minimizing the energy loss. Thus, the optimized 20Cu-Ti4O7 catalyst exhibits an impressive selectivity of 96.4% and ultrahigh energy efficiency of 45.1% for multi-carbon products, along with a remarkable partial current density of 432.6 mA cm-2. Our study underscores a novel C-C coupling strategy between Cu and the support material, advancing the development of Cu-supported catalysts for highly efficient electroreduction of carbon monoxide.

DOI: 10.1002/anie.202414416

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202414416