The splitting of water through electrocatalysis offers a sustainable method for the production of hydrogen. In alkaline electrolytes, the lack of protons forces water dissociation to occur before the hydrogen evolution reaction (HER). While pure Pt is the gold standard electrocatalyst in acidic electrolytes, since the 5d orbital in Pt is nearly fully occupied, when it overlaps with the molecular orbital of water, it generates a Pauli repulsion. As a result, the formation of a Pt-H* bond in an alkaline environment is difficult, which slows the HER and negates the benefits of using a pure Pt catalyst. To overcome this limitation, Pt can be alloyed with transition metals, such as Fe, Co, and Ni. This approach has the potential not only to enhance the performance but also to increase the Pt dispersion and decrease its usage, thus overall improving the catalyst's cost-effectiveness. The excellent water adsorption and dissociation ability of transition metals contributes to the generation of a proton-rich local environment near the Pt-based alloy that promotes HER. Significant progress has been achieved in comprehending the alkaline HER mechanism through the manipulation of the structure and composition of electrocatalysts based on the Pt alloy. The objective of this review is to analyze and condense the latest developments in the production of Pt-based alloy electrocatalysts for alkaline HER. It focuses on the modified performance of Pt-based alloys and clarifies the design principles and catalytic mechanism of the catalysts from both an experimental and theoretical perspective. This review also highlights some of the difficulties encountered during the HER and the opportunities for increasing the HER performance. Finally, guidance for the development of more efficient Pt-based alloy electrocatalysts is provided.
Keywords: Alkaline electrolyte; Electrocatalysis; Heterojunction; High-entropy alloy; Hydrogen; Hydrogen evolution reaction; Platinum; Pt-based alloy; Strong metal−support interaction; doping.