Boosting Electrocatalytic Nitrate Reduction to Ammonia on a Hierarchical Nanoporous Ag,Ni-Codoped Cu Catalyst via Trimetallic Synergistic and Nanopore Enrichment Effects

Yuhuan Cui; Changning Sun; Yuexuan He; Zixuan Feng; Guopeng Ding; Qingqing Dai; Tonghui Wang; Zhili Wang; Qing Jiang

doi:10.1021/acs.nanolett.4c05376

Boosting Electrocatalytic Nitrate Reduction to Ammonia on a Hierarchical Nanoporous Ag,Ni-Codoped Cu Catalyst via Trimetallic Synergistic and Nanopore Enrichment Effects

Nano Lett. 2025 Jan 1. doi: 10.1021/acs.nanolett.4c05376. Online ahead of print.

Authors

Yuhuan Cui¹, Changning Sun², Yuexuan He², Zixuan Feng², Guopeng Ding², Qingqing Dai³, Tonghui Wang², Zhili Wang², Qing Jiang²

Affiliations

¹ College of Chemistry and Materials Science, Hebei University, Baoding 071002, China.
² Key Laboratory of Automobile Materials, Ministry of Education, and School of Materials Science and Engineering, Jilin University, Changchun 130022, China.
³ Key Laboratory of Bionic Engineering, Ministry of Education, Jilin University, Changchun 130022, China.

PMID: 39743827
DOI: 10.1021/acs.nanolett.4c05376

Abstract

The electrochemical nitrate (NO₃^-) reduction reaction (NO₃^-RR) offers a promising route for NO₃^- wastewater treatment and sustainable ammonia (NH₃) synthesis. However, the reaction still faces the challenges of unsatisfactory productivity and selectivity. Herein, we report a hierarchical nanoporous Ag,Ni-codoped Cu (np Ag,Ni-Cu) catalyst that exhibits a high NH₃ Faradaic efficiency of 98.5% with an attractive NH₃ yield rate of 41.1 mg h^-1 mg_cat^-1 at -0.2 V vs RHE for the NO₃^-RR. Density functional theory calculations and molecular dynamics simulations suggest that the excellent performance of np Ag,Ni-Cu results from a trimetallic synergistic effect and nanopore enrichment/confinement effect, in which the codoping of Ni and Ag into Cu can enhance NO₃^- adsorption, prevent *NO₂ desorption, and suppress the hydrogen evolution reaction, while nanopores can promote NO₃^- accumulation on the internal surface of nanopores and confine the reaction intermediates within the nanopores for a deeper NO₃^- electroreduction.

Keywords: ammonia synthesis; nanopore enrichment effect; nanoporous metal; nitrate reduction reaction; synergistic effect.