Phosphorus-triggered modification of the electronic structure and surface properties of Pd4S nanowires for robust hydrogen evolution electrocatalysis

Abstract

Rational design and fabrication of alternative, high-performance and robust non-Pt-based electrocatalysts is imperative for hydrogen production by means of the hydrogen evolution reaction (HER). In this work, we propose a synthetic strategy for the construction of P-doped Pd₄S nanowires (P–Pd₄S NWs) by treating the pre-synthesized Pd nanowires (Pd NWs) with triphenylphosphine sulphide under solvothermal conditions. After P-doping, the resultant P–Pd₄S NWs were endowed with modified electronic structures, large electrochemically active surface areas, abundant active sites, and improved electron transport ability, which can trigger highly efficient electrocatalytic performance toward the HER. As a result, the as-obtained P–Pd₄S NWs could achieve a HER activity of 10 mA cm⁻² at a small overpotential of 47 mV, outperforming the Pd₄S NWs and pristine Pd NWs. This study provides a new approach to optimize the performance of electrocatalysts by the rational combination of heteroatom doping and morphology/structure engineering.