Synthesis and electrochemical properties of a nickel(II) thiacalix[4]arene-based electrocatalyst for the hydrogen evolution reaction

Abstract

Thiacalix[4]arene with four sulfur-bridging atoms and four hydroxy coordinating groups in the lower rim is a promising candidate for powerful electrocatalytic hydrogen production. However, there are only a few examples reported in the literature where conjugated thiacalix[4]arene is used as a pre-catalyst for the hydrogen evolution reaction. The present work evaluates the electrocatalytic performance of a nickel(II) coordination complex based on generic thiacalix[4]arene. The coordination complex is characterized by cyclic voltammetry, where two reduction peaks are observed at −0.57 and −1.33 V for the two redox couples Ni2+/Ni+ and Ni+/Ni, respectively. The proton reduction occurs at the second peak potential with a slight shift at about −1.0 V, with increasing peak currents directly related to the number of acetic acid equivalents. The maximum peak current was observed to be at about 67 µA for 20 equiv. of acetic acid.