Zhou Jing, He Bingling, Huang Pu, Wang Dongge, Zhuang Zechao, Xu Jing, Pan Chengsi, Dong Yuming, Wang Dingsheng, Wang Yao, Huang Hongwen, Zhang Jiawei, Zhu Yongfa
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, China.
International Joint Research Center for Photoresponsive Molecules and Materials, Jiangnan University, Wuxi, 214122, China.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202418459. doi: 10.1002/anie.202418459. Epub 2024 Dec 13.
Efficient CO electroreduction (CORR) to ethanol holds promise to generate value-added chemicals and harness renewable energy simultaneously. Yet, it remains an ongoing challenge due to the competition with thermodynamically more preferred ethylene production. Herein, we presented a CO reduction predilection switch from ethylene to ethanol (ethanol-to-ethylene ratio of ~5.4) by inherently implanting Cu sites with perfluorooctane to create interfacial noncovalent interactions. The 1.83 %F-CuO organic-inorganic hybrids (OIHs) exhibited an extraordinary ethanol faradaic efficiency (FE) of ∼55.2 %, with an impressive ethanol partial current density of 166 mA cm and excellent robustness over 60 hours of continuous operation. This exceptional performance ranks our 1.83 %F-CuO OIHs among the best-performing ethanol-oriented CORR electrocatalysts. Our findings identified that CF could strengthen the interfacial hydrogen bonding connectivity, which consequently promotes the generation of active hydrogen species and preferentially favors the hydrogenation of *CHCOH to *CHCHOH, thus switching the reaction from ethylene-preferred to ethanol-oriented. The presented investigations highlight opportunities for using noncovalent interactions to tune the selectivity of CO electroreduction to ethanol, bringing it closer to practical implementation requirements.
将一氧化碳高效电还原（CORR）为乙醇有望同时生成增值化学品并利用可再生能源。然而，由于与热力学上更倾向的乙烯生产存在竞争，这仍然是一个持续的挑战。在此，我们通过将铜位点与全氟辛烷固有地植入以创建界面非共价相互作用，实现了一氧化碳还原偏好从乙烯到乙醇的转变（乙醇与乙烯的比例约为5.4）。1.83%F-CuO有机-无机杂化材料（OIHs）表现出约55.2%的非凡乙醇法拉第效率（FE），令人印象深刻的乙醇分电流密度为166 mA cm，并且在连续运行60小时内具有出色的稳定性。这种卓越的性能使我们的1.83%F-CuO OIHs跻身于性能最佳的面向乙醇的CORR电催化剂之列。我们的研究发现，CF可以增强界面氢键连接性，从而促进活性氢物种的生成，并优先有利于CHCOH加氢生成CHCHOH，从而将反应从乙烯偏好转变为乙醇导向。所呈现的研究突出了利用非共价相互作用来调节一氧化碳电还原为乙醇的选择性的机会，使其更接近实际应用要求。
