Coupling of Engineered High Entropy Alloys with Semiconducting TiO₂ Nanofilms for Scalable and Ultrafast Alkaline Hydrogen Evolution Reaction
Date
2025
Authors
Zhao, Z.
Zhao, Y.
Wang, W.-Q.
Xin, X.
Jiao, Y.
Abell, A.D.
Law, C.S.
Santos, A.
Editors
Advisors
Journal Title
Journal ISSN
Volume Title
Type:
Journal article
Citation
Advanced Science, 2025; e14558-1-e14558-14
Statement of Responsibility
Zichu Zhao, Yanzhang Zhao, Wen-Qiang Wang, Xiaying Xin, Yan Jiao, Andrew D. Abell, Cheryl Suwen Law, Abel Santos
Conference Name
Abstract
High entropy alloys (HEAs) are a promising class of electrocatalysts because of their high reactivity. However, the development of scalable synthesis strategies and fundamental understanding of their interfacial synergy with metal oxides remains underexplored. Herein, a new approach is reported for the fabrication of hybrid photoelectrocatalysts combining PtFeCoNiCu HEA structures with titanium dioxide (TiO₂) nanofilms via sequential anodization and electrodeposition. The TiO₂ nanofilms function as both a photoactive semiconducting framework and nanostructured substrate, enabling controlled nucleation and growth of HEA nanoparticles through a Volmer–Weber mechanism. The resulting hybrid photoelectrocatalysts exhibit outstanding hydrogen evolution reaction (HER) performance, achieving an ultralow overpotential of –11 mV at 10 mA cm¯² under simultaneous illumination and elevated electrolyte temperature. Mechanistic studies combining in situ Raman spectroscopy and density functional theory simulations reveal that HER occurs through three distinct stages, during which the TiO₂ support undergoes dynamic structural and electronic evolution – from a passive scaffold to an electron-buffering layer. This process involves Ti⁴⁺ reduction, hydrogen intercalation, and accelerated turnover of OH* intermediates, which collectively enhance interfacial charge transfer and broaden active-site availability. These findings provide new insights into the dynamic interplay between HEAs–semiconducting metal oxide substrates, enabling a generalizable design strategy for scalable, high-performance photoelectrocatalysts.
School/Discipline
Dissertation Note
Provenance
Description
Access Status
Rights
© 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.