ACS_Catalysis
February 20, 2026
Volume 16, Issue 4
Pages 2925-4065
Low-Temperature Electrocatalytic Ammonia Production: Study on the Nitrogen-Reducing Activity of Vanadium Sulfide Catalysts
Several transition metal dichalcogenides (TMDs) that are active for electrochemical nitrogen reduction (e-NRR) remain underexplored, particularly regarding the correlation between their surface electronic states and e-NRR activity. For example, π-backdonation supposedly occurs in the associative e-NRR at the V2+ active sites in vanadium sulfides (VSx); but the hypothesis was not experimentally validated with the reaction-oriented surfaces remained under debate (V2+ vs V4+). To resolve these issues, we synthesized several metal sulfides, including VSx specimens with controlled oxidation states and studied the effects of electronic structure modulation on the e-NRR activity. The incorporation of Cu into VSx resulted in enhanced e-NRR activity (131.24 μg mgcat–1 h–1 or 0.62 mA cmgeo–2 in 0.5 M Na2SO4, pH7), primarily owing to the increased V2+ content (51%) and improved binding of e-NRR intermediates through π-backdonation. This π-backdonation-induced enhancement of e-NRR activity was further observed in other transition metal sulfides, including Cu, Ni, Co, and Mn sulfides. Our findings underscore the significance of enabling electric charge control of catalysts and establish a foundation for further enhancing e-NRR activity.
- Jihyun Choi
- Myeong-Geun Kim
- Hyun Ju Lee
- Dong Wook Lee
- Hyo Sang Jeon
- Chaekyung Baik
- Jong-Seok Park
- Suji Lee
- Chaeyeon Yang
- Hyung Chul Ham
- Yung-Eun Sung
- Sung Jong Yoo
- Hyun S. Park
https://pubs.acs.org/doi/10.1021/acscatal.5c08588
Image created by minjeong Kim / Nanosphere
ACS_Catalysis
February 20, 2026
Volume 16, Issue 4
Pages 2925-4065
Low-Temperature Electrocatalytic Ammonia Production: Study on the Nitrogen-Reducing Activity of Vanadium Sulfide Catalysts
Several transition metal dichalcogenides (TMDs) that are active for electrochemical nitrogen reduction (e-NRR) remain underexplored, particularly regarding the correlation between their surface electronic states and e-NRR activity. For example, π-backdonation supposedly occurs in the associative e-NRR at the V2+ active sites in vanadium sulfides (VSx); but the hypothesis was not experimentally validated with the reaction-oriented surfaces remained under debate (V2+ vs V4+). To resolve these issues, we synthesized several metal sulfides, including VSx specimens with controlled oxidation states and studied the effects of electronic structure modulation on the e-NRR activity. The incorporation of Cu into VSx resulted in enhanced e-NRR activity (131.24 μg mgcat–1 h–1 or 0.62 mA cmgeo–2 in 0.5 M Na2SO4, pH7), primarily owing to the increased V2+ content (51%) and improved binding of e-NRR intermediates through π-backdonation. This π-backdonation-induced enhancement of e-NRR activity was further observed in other transition metal sulfides, including Cu, Ni, Co, and Mn sulfides. Our findings underscore the significance of enabling electric charge control of catalysts and establish a foundation for further enhancing e-NRR activity.
https://pubs.acs.org/doi/10.1021/acscatal.5c08588
Image created by minjeong Kim / Nanosphere