Kim, Min-Cheol Nam, Hyunji Choi, Jihyun Kim, Hee Soo Lee, Hong Woo Kim, Donghun Kong, Jimin Han, Sang Soo Lee, Seung Yong Park, Hyun S. 2024-01-19T16:33:18Z 2024-01-19T16:33:18Z 2022-01-10 2020-09-18 2155-5435 https://pubs.kist.re.kr/handle/201004/118112 The electrochemical nitrogen reduction reaction (NRR) has been regarded as a promising alternative to the conventional Haber-Bosh process for NH3 synthesis. Inspired by the Fe-Mo-S cofactor in the enzyme nitrogenase, metal sulfide catalysts, mostly Fe- or Mo-based sulfides, have recently received great interest. Here, we propose Cu2-xS (0 <= x < 1) as an efficient NRR electrocatalyst. Electrochemical tests at room temperature and atmospheric pressure reveal that Cu1.81S achieves a high NH3 yield of 2.19 mu mol h(-1) cm(-2) along with a Faradaic efficiency of 14.1% at -0.1 V versus reversible hydrogen electrode in an aqueous electrolyte. According to our first-principles calculations, the superior NRR properties originate from the threefold-coordinate Cu sites in Cu1.81S. These sites enable N-H center dot center dot center dot S hydrogen bonding during N2Hy adsorption and stabilize the intermediates on the Cu2-xS surfaces, leading to a significant decrease in the overpotential limit for the NRR. Moreover, the threefold sites not only provide a bioinspired NRR pathway similar to that of nitrogenase but also enable both distal and alternating pathways, increasing the efficiency for the NRR. This study presents an attractive electrocatalyst for the NRR and opens an alternative route to explore chalcogenides and halides as NRR catalysts where the hydrogen-bonding mediation can similarly operate. English AMER CHEMICAL SOC AMMONIA-SYNTHESIS ELECTROREDUCTION ELECTROCATALYST HYBRID Hydrogen Bonding-Mediated Enhancement of Bioinspired Electrochemical Nitrogen Reduction on Cu2-xS Catalysts Article 10.1021/acscatal.0c01730 1 ACS CATALYSIS, v.10, no.18, pp.10577 - 10584 ACS CATALYSIS 10 18 10577 10584 scie scopus 000574920200029 2-s2.0-85095460478 Chemistry, Physical Chemistry Article AMMONIA-SYNTHESIS ELECTROREDUCTION ELECTROCATALYST HYBRID nitrogen reduction reaction electrocatalysis bioinspired nitrogenase mechanism copper sulfide density functional theory