文献类型：期刊文献

英文题名：Enhancement of Nitrate-to-Ammonia on Amorphous CeOx-Modified Cu via Tuning of Active Hydrogen Supply

作者：Li, Yufeng[1];Wang, Chaochen[1];Yang, Lekuan[1];Ge, Wangxin[1];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,Minist Educ,Key Lab Ultrafine M, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：14

期号：7

外文期刊名：ADVANCED ENERGY MATERIALS

收录：;EI(收录号：20235215270459);WOS:【SCI-EXPANDED(收录号:WOS:001129138300001)】；

基金：This work was supported by the National Natural Science Foundation of China (22278136, 21978087, 22178106, and U22B20143), the Science and Technology Commission of Shanghai Municipality (23ZR1416400 and 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：active hydrogen; ammonia synthesis; heterostructure; in situ electroreduction; nitrate reduction reaction

摘要：The electrochemical nitrate reduction reaction (NO3RR) is an environment-friendly and promising alternative to the conventional Haber-Bosch ammonia synthesis process, which is a complex process of proton-coupled electron transfer. Hereon, the amorphous CeOx support introduced to construct Cu/a-CeOx heterostructure is prepared to provide sufficient *H and synergistically catalyze the NO3RR. Cu/a-CeOx achieves a maximum ammonia yield of 1.52 mmol h(-1) mg(cat)(-1). In the flow cell, the NH3 yield reaches 17.93 mmol h(-1) mg(cat)(-1) at 1 A cm(-2), which exceeds most of the state-of-the-art catalysts. In situ X-ray diffraction (XRD) and in situ Raman observe that the catalyst undergoes structural reconfiguration under operating conditions, thus confirming that Cu2O is not the true active center in the catalytic process. Furthermore, in situ characterizations and density functional theory (DFT) calculations demonstrate that the amorphous CeOx in Cu/a-CeOx modulates the electronic structure of Cu and overcomes the higher potential barrier required for the decomposition of water on Cu, which greatly facilitates the hydrolysis process and provides a higher H-coverage rate for the hydrogenation of NO3-, realizing a dynamic equilibrium between the production and consumption of active hydrogen. This component design strategy centered on the amorphous structure opens up a new pathway for the electrochemical NO3RR.