文献类型：期刊文献

英文题名：Steering CO2 electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction

作者：Zhang, Jiawei[1];Zeng, Gangming[1];Zhu, Shangqian[2,3,4];Tao, Haolan[5];Pan, Yue[6];Lai, Wenchuan[1];Bao, Jun[7,8];Lian, Cheng[5];Su, Dong[6];Shao, Minhua[2,3,4];Huang, Hongwen[1,9]

机构：[1]Hunan Univ, Adv Catalyt Engn Res Ctr, Coll Mat Sci & Engn, Minist Educ, Changsha 410082, Hunan, Peoples R China;[2]Hong Kong Univ Sci & Technol, Dept Chem & Biol Engn, Kowloon, Hong Kong, Peoples R China;[3]Hong Kong Univ Sci & Technol, Energy Inst, Kowloon, Hong Kong, Peoples R China;[4]Hong Kong Univ Sci & Technol, Chinese Natl Engn Res Ctr Control & Treatment Hea, Kowloon, Hong Kong, Peoples R China;[5]East China Univ Sci & Technol, Sch Chem & Mol Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[6]Chinese Acad Sci, Beijing Natl Lab Condensed Matter Phys, Inst Phys, Beijing 100190, Peoples R China;[7]Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China;[8]Univ Sci & Technol China, Collaborat Innovat Ctr Chem Energy Mat, Hefei 230029, Anhui, Peoples R China;[9]Hunan Univ, Shenzhen Res Inst, Shenzhen 518055, Guangdong, Peoples R China

年份：2023

卷号：120

期号：11

外文期刊名：PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001103764100003)】；

基金：This work was supported by the National Key Research and Development Program of China (No. 2021YFA1502000), National Natural Science Foundation of China (No. U2032149, No. U21A20328, U22A20396 and 21905089), the Science and Technology Innovation Program of Hunan Province (No. 2021RC3065), Shenzhen Science and Technology Program (No. JCYJ20210324120800002), and Research Grants Council of Hong Kong (16304821, 16310419 and 16309418), Innovation and Technology Commission (grant no. ITC-CNERC14EG03), and through Hong Kong Branch of National Precious Metals Material Engineering Research Centre of the Hong Kong Special Administrative Region.

语种：英文

外文关键词：CO2 electroreduction; non-covalent interaction; *OH coverage; ethanol selectivity; surface-bounded hydroxyl species

摘要：Selective electroreduction of carbon dioxide (CO2RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 +/- 1.0% and an ethanol-to- ethylene ratio of 1.2 at a large ethanol partial current density of 501.0 +/- 15.0 mA cm(-2), in addition to an extraordinary FE of 90.6 +/- 3.4% for multicarbon products. Intriguingly, we found a volcano-shaped relationship between ethanol selectivity and nanocavity size of porous CuO catalyst in the range of 0 to 20 nm. Mechanistic studies indicate that the increased coverage of surface-bounded hydroxyl species (*OH) associated with the nanocavity size-dependent confinement effect contributes to the remarkable ethanol selectivity, which preferentially favors the *CHCOH hydrogenation to *CHCHOH (ethanol pathway) via yielding the noncovalent interaction. Our findings provide insights in favoring the ethanol formation pathway, which paves the path toward rational design of ethanol-oriented catalysts.