Aqueous pH influence on the electrocatalytic hydrogen evolution reaction with carbon nanotube-supported diiron dithiolato compound

Insight into wide aqueous pH influence on the electrocatalytic HER activity and stability of carbon nanotube-supported diiron dithiolato compound labeling as hybrid 2Fe2S-f-CNT are studied in this work. [Display omitted] •New diiron dithiolato compounds 1–3 were prepared as a library of [FeFe]-hydrogenase models.•A new CNT-covalently-supported diiron compound labeling as 2Fe2S-f-CNT was constructed.•Electrocatalytic HER activity and stability of 2Fe2S-f-CNT is studied in wide pH aqueous media.•Electrochemical reconstruction of 2Fe2S-f-CNT leads to high HER activity in alkaline medium.•Electrochemical degradation of 2Fe2S-f-CNT results in low HER activity in neutral and acidic media. Biomimetic chemistry on structure, function and external environment of [FeFe]-hydrogenases for hydrogen evolution reaction (HER) has shown a promising way to develop non-precious metal electrocatalysts for H2 production in the current Pt-dominated HER system. Herein, three new diiron dithiolato compounds [{(μ-SCH2)2N(C6H4CH2CO2R)}Fe2(CO)6] (R = H (1), C6H4CHO-p (2), and C6H4Me-m (3)) were first prepared and identified as a library of [FeFe]-hydrogenase models in this work. Subsequently, the as-prepared diiron molecule 2 can be covalently attached onto carbon nanotubes (CNTs), resulting in the obtainment of target CNT-supported [FeFe]-hydrogenase model labeling as covalent hybrid 2Fe2S-f-CNT. Notably, the electrocatalytic HER performance and stability of the resulted hybrid 2Fe2S-f-CNT immobilized respectively on a gassy carbon (GC) electrode are systematically studied and compared in 0.1 M KOH (pH = 13), 0.1 M phosphate buffer (pH = 7), and 0.05 M H2SO4 (pH = 1) aqueous solutions by various spectroscopic and electrochemical techniques. The result has shown that the higher electrocatalytic HER activity is observed in alkaline solution (pH = 13) relative to neutral and acidic solutions (pH = 7, 1), being attributed to the different electrochemical HER processes of diiron cluster in wide pH aqueous media as revealed by post operando analysis.