The copper and zinc complexes of ATSM (diacetyl-bis(N4-methylthiosemicarbazone)) have previously been employed as a homogeneous electrocatalysts for the hydrogen evolution reaction (HER). In this study, Cu(ATSM), Zn(ATSM) and their ATSP derivatives (ATSP = 2,3-benzil bis(N4-phenolthiosemicarbazone) have been applied on glassy carbon electrode surfaces to study their heterogeneous HER electro-catalytic properties. A series of modified electrodes based were fabricated by drop casting methods, yielding catalytically active species with HER overpotentials ranging from 710-1030 mV for ATSM system and 730-870 mV for ATSP system at a current density of 10 mA cm<sup>-2</sup>. The charge transfer resistance of the films were investigated by electrochemical impedance spectroscopy and film morphology as determined by scanning electron microscopy. The HER overpotential for the Cu based films was smaller than the Zn analogs. The largest overpotentials were found with pure ligand films containing no metal. Extended chronopotentiometry studies for both systems indicated that after an initial conditioning period, electrode surfaces were stable. The surfaces of the modified electrodes were analyzed by X-ray photon spectroscopy and electronic spectroscopy to evaluate the identity of the surface species before and after electrolysis.results indicated that both systems are stable on the surface during the electrolysis. Both ligand systems show similar activities with close overpotential and similar Tafel slopes. Catalytic mechanisms will be discussed and compared to homogenous results and density functional theory computations.<br/>

Modification of glassy carbon electrodes with Cu- and Zn-bis(thiosemicarbazones) as heterogeneous HER catalysts

254th National Meeting (2017)

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