A bis(thiosemicarbazonato)‐zinc complex, an electrocatalyst for hydrogen evolution and oxidation via ligand‐assisted metal‐centered reactivity. (6th January 2022)

• Record Type: Journal Article
• Authors: Du, Juan; Yang, Hao; Wang, Chun‐Li; Zhan, Shu‐Zhong
• Is Part Of: Applied organometallic chemistry. Volume 36:Number 4(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-06
• Subjects: electrocatalyst for hydrogen evolution and oxidation -- hydrogen evolution -- hydrogen oxidation -- zinc complex; Organometallic chemistry -- Periodicals; Organometallic compounds -- Periodicals; 547.05
• DOI: 10.1002/aoc.6572
• Languages: English
• ISSNs: 0268-2605

Abstract

Abstract: Based on that hydrogen energy is widely used in fuel cells, the design and research of new catalysts for both hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs) are becoming increasingly important. A new catalyst for both hydrogen evolution and oxidation, based on a zinc complex, [Zn‐ATSE]2, is designed and provided by the reaction of Zn (CH3 CO2 )2 with diacetyl‐2‐(4‐ N ‐ethyl‐3‐thiosemicarbazone)‐3‐(4‐ N ‐amino‐3‐thiosemicarbazone) (H2 ATSE) in our group. Electrochemical investigations show that [Zn‐ATSE]2 can electro‐catalyze hydrogen evolution from acetic acid with a turnover frequency (TOF) of 64 mol H2 mol catalyst −1 h −1 under an overpotential of 914.6 mV. Moreover, [Zn‐ATSE]2 also can electro‐catalyze hydrogen oxidation with a TOF of 13.52 s −1 . The results can be attributed to the hydrazine group of [Zn‐ATSE]2 that can form a ligand‐based radical species. Possible electrocatalytic cycles for H2 production and oxidation by [Zn‐ATSE]2 are afforded. We hope these findings can afford a new method for the design of electrocatalysts for both H2 evolution and H2 oxidation. Abstract : The reaction of H2 ATSE and Zn (CH3 CO2 )2 affords a new zinc complex, [Zn‐ATSE]2, a new catalyst for both hydrogen evolution and oxidation via ligand‐assisted metal‐centered reactivity.