Size-induced d band center upshift of copper for efficient nitrate reduction to ammonia

Jincheng Zhang; Chaofan Chen; Rui Zhang; Xu Wang; Yanjiao Wei; Mengjie Sun; Zhanning Liu; Ruixiang Ge; Min Ma; Jian Tian

doi:10.1016/j.jcis.2023.12.129

Size-induced d band center upshift of copper for efficient nitrate reduction to ammonia

J Colloid Interface Sci. 2024 Mar 15:658:934-942. doi: 10.1016/j.jcis.2023.12.129. Epub 2023 Dec 23.

Authors

Jincheng Zhang¹, Chaofan Chen², Rui Zhang¹, Xu Wang¹, Yanjiao Wei¹, Mengjie Sun¹, Zhanning Liu¹, Ruixiang Ge³, Min Ma⁴, Jian Tian⁵

Affiliations

¹ College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China.
² College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
³ College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China.
⁴ College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China. Electronic address: mamin@sdust.edu.cn.
⁵ College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China. Electronic address: jiantian@sdust.edu.cn.

PMID: 38157617
DOI: 10.1016/j.jcis.2023.12.129

Abstract

Electrocatalytic nitrate reduction (NO₃RR) technique has emerged as a hotspot in NH₃ production, for its practicability, and a series of advanced electrocatalysts with high activity and robust stability needed to be constructed in today's era. In this work, size-tunable Cu nanoparticles on porous nitrogen-doped hexagonal carbon nanorods (Cu@NHC) were reasonably designed and served for catalyzing NO₃RR in neutral media. Especially, Cu_30%@NHC demonstrated a remarkable electroactivity for NH₃ production as it showed a suitable grain size with massive catalytic centers and favorable d band structure with faster *NO₃^--to-*NO₂^- catalytic dynamics. As expected, Cu_30%@NHC (3628.28 µg h^-1 mg_cat.^-1) had a much higher NH₃ yield than those for Cu_20%@NHC (1268.42 µg h^-1 mg_cat.^-1) and Cu_40%@NHC (725.03 µg h^-1 mg_cat.^-1). And those collected NH₃ products indeed derived from NO₃RR process revealed by ¹⁵N isotope-labeling and systemic control tests. Moreover, Cu_30%@NHC was also durable for NO₃RR bulk electrolysis with minor loss in activity. This work offered an effective modifying tactics to boost NO₃RR catalysis and could guide the design of other advanced electrocatalysts via size-induced surface engineering.

Keywords: N-doped hexagonal carbon nanorod; NH(3) electrosynthesis; Size-tunable Cu; d band structure.