文献类型：期刊文献

英文题名：Frustrated Lewis Pairs on Zr Single Atoms Supported N-Doped TiO2-x Catalysts for Electrochemical Nitrate Reduction To Ammonia

作者：Yang, Lekuan[1];Wang, Chaochen[1];Li, Yufeng[1];Ge, Wangxin[1];Tang, Lei[2];Shen, Jianhua[1];Zhu, Yihua[1];Li, Chunzhong[2]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Mat Sci & Engn,Key Lab Ultrafine Mat Minist Ed, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：34

期号：36

外文期刊名：ADVANCED FUNCTIONAL MATERIALS

收录：;EI(收录号：20240915663805);WOS:【SCI-EXPANDED(收录号:WOS:001176165800001)】；

基金：This work was supported by the National Natural Science Foundation of China (22278136, 22178106, U22B20143, 52002015, 22275010), the Science and Technology Commission of Shanghai Municipality (23ZR1416400, 22dz1205900), Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutes of High Learning, and the Fundamental Research Funds for the Central Universities (222201718002).

语种：英文

外文关键词：electrochemical nitrate reduction; frustrated Lewis pairs; single atom; TiO2

摘要：The electrochemical reduction of nitrates (NO3RR) for ammonia synthesis at room temperature holds immense potential. One key challenge is the adsorption and activation of NO3-, along with the provision of sufficient active hydrogen to accelerate the hydrogenation process. Here, the study prepares N-doped TiO2-x supported by Zr single atoms (Zr-TiON) with rich oxygen vacancies (Ov), in which unsaturated Zr (Lewis acidic, LA) sites together with oxygen atoms around Ov (Lewis base, LB) form frustrated Lewis acid-base pairs (FLPs). At -60 mA cm(-2), NH3 Faradaic efficiency reaches 94.8%, corresponding to the production rate of 663.15 mu mol h-1 mgcat-1. The yield rate is up to 26.16 mmol h(-1)mg(cat)(-1) at -1 A cm(-2) in flowing electrolyzer. Theoretical calculations and in situ spectroscopy analysis reveal that the interaction between LA and LB sites in FLPs plays a crucial role in facilitating adsorption and activation of electron-rich NO3- and electron-deficient *H. The presence of enhanced FLPs significantly reduces the energy barrier for H2O dissociation, lowering it to 0.20 eV, which facilitates subsequent hydrogenation reactions. The abundance of *H accelerates hydrogenation process, thereby enhancing the activity of NO3RR. This FLP design offers a promising approach for paving the way for the development of highly efficient NO3RR catalysts.