Liu Xiang, Liu Ting, Ouyang Ting, Deng Jiguang, Liu Zhao-Qing
Key Laboratory of Beijing on Regional Air Pollution Control, Beijing Key Laboratory for Green Catalysis and Separation, Center of Excellence for Environmental Safety and Biological Effects, Beijing University of Technology, Beijing, 100124, China.
School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials/Huangpu Hydrogen Innovation Center, Guangzhou University, Guangzhou, Guangzhou Higher Education Mega Center No. 230 Wai Huan Xi Road, 510006, China.
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419796. doi: 10.1002/anie.202419796. Epub 2024 Dec 9.
The CO electroreduction reaction has advantages in clean and pollution-free carbon conversion, but it still faces challenges in carbon utilization efficiency and improving the selectivity of C products. Although the dynamic Cu state is known to favor the C-C coupling process, the suitable Cu species for electrocatalytic reduction of CO are difficult to maintain under the conditions of strong reduction and large current. Herein, we propose a Ce doping strategy to stabilize the Cu state (Ce/CuO) during the CORR process, which enables a high Faradaic efficiency of 60 % for multi-carbon products (40 % for CH, 14 % for CHCHOH, and 6 % for CHCOOH), and 25 h stability at -1.2 V versus the reversible hydrogen electrode. In situ infrared spectroscopy, in situ X-ray photoelectron spectroscopy combined with density functional theory calculations reveal that the Cu is stabilized by the redox ion pairs of Ce, which reduces the energy barrier of *CO coupling, and improves the Faraday efficiency of electrocatalytic CO reduction of CH. This work provides a new idea to make full use of lanthanide variable value metals for advanced catalysis and clean energy conversion.
CO电还原反应在清洁无污染的碳转化方面具有优势，但在碳利用效率和提高C产物选择性方面仍面临挑战。虽然已知动态Cu状态有利于C-C偶联过程，但在强还原和大电流条件下，用于CO电催化还原的合适Cu物种难以维持。在此，我们提出一种Ce掺杂策略，以在CORR过程中稳定Cu状态（Ce/CuO），这使得多碳产物的法拉第效率高达60%（CH为40%，CHCHOH为14%，CHCOOH为6%），并且相对于可逆氢电极在-1.2 V下具有25小时的稳定性。原位红外光谱、原位X射线光电子能谱结合密度泛函理论计算表明，Cu通过Ce的氧化还原离子对得以稳定，这降低了*CO偶联的能垒，并提高了电催化CO还原生成CH的法拉第效率。这项工作为充分利用镧系可变价金属进行先进催化和清洁能源转化提供了新思路。
