Selectively Adsorbed p-Aminothiophenol Molecules Improve the Electrocatalytic and Photo-Electrocatalytic Hydrogen Evolution on Au/TiO₂

Electrocatalytic hydrogen evolution reaction (HER) is receiving increasing attention as an effective process to produce clean energy. The commonly used precious metal catalysts can be hybridized with semiconductors to form heterostructures for the improvement of catalytic efficiency and reduction of cost. It will be promising to further improve the efficiency of heterostructure-based nanocatalysts in electrocatalytic and photocatalytic HER using a simple and effective method. Herein, we improve the efficiency of Au/TiO 2 in electrocatalytic and photo-electrocatalytic HER by selectively adsorbing p -aminothiophenol (PATP) molecules. The PATP molecules are adsorbed on the gold surface by using a simple solution-based method and favor the charge separation at the Au–TiO 2 interface. We also compare the PATP molecules with other thiophenol molecules in the enhancement of electrocatalytic HER. The PATP-induced enhancement in electrocatalysis is then further investigated by density functional theory (DFT) calculations, and this enhancement is attributed to a reduction in Gibbs energy of adsorbed hydrogen after surface adsorption of PATP molecules. This work provides a simple, cost-effective, and highly efficient approach to improve the electrocatalytic and photo-electrocatalytic efficiency of Au/TiO 2, and this approach could be easily extended to other heterostructure-based nanocatalysts for performance enhancement and may be used in many other catalytic reactions.