| Title: |
Spectroscopic and Theoretical Insights Into High-Entropy-Alloy Surfaces and Their Interfaces with Semiconductors for Enhanced Photocatalytic Hydrogen Production |
| Authors: |
Lin, JT; Hsiao, YC; Li, C; Tseng, CY; He, ZY; Gardner, AM; Chen, Y; Yang, CC; Wang, CH; Lin, SC; Lin, XX; Lin, CY; Lin, KH; Cowan, AJ; Yang, TH |
| Publisher Information: |
Wiley |
| Publication Year: |
2025 |
| Collection: |
The University of Liverpool Repository |
| Description: |
Recently, high-entropy alloy (HEA) nanocatalysts have shown outstanding catalytic performance. However, their integration with semiconductors for photocatalytic reactions remains largely unexplored. Here, Pd@HEA core–shell nanocrystals with controlled compositions and facets on TiO 2 supports are synthesized, achieving significantly enhanced photocatalytic hydrogen production. Compared to Pd@Pt/TiO 2 , Pd@Pt 0.4 Pd 0.15 Ir 0.15 Ru 0.15 Rh 0.15 core–shell nanocubes/TiO 2 exhibit superior photoactivity, driven by optimized Schottky junctions and synergistic multimetallic interactions that enhance photocatalysis. UV photoelectron spectroscopy reveals a high work function of 4.81 eV for Pd@Pt 0.4 Pd 0.15 Ir 0.15 Ru 0.15 Rh 0.15 , enabling efficient charge separation between Pd@HEA and TiO₂. Meanwhile, transient absorption spectroscopy confirms a significantly prolonged carrier lifetime of 4 ms, far surpassing that of pure TiO 2 ; (65 µs). In addition, in situ X-ray photoelectron spectroscopy confirms that photo-induced electrons preferentially accumulate on Ir and Pt sites, increasing their electron density and identifying them as primary adsorption sites. Furthermore, density functional theory calculations further reveal that Pt-based bridge sites exhibit a more optimal hydrogen binding free energy than Ir-based sites, suggesting that Pt serves as the dominant active site in photocatalysis. This study establishes a framework for the rational design of HEA-semiconductor photocatalysts, providing fundamental insights for solar-driven hydrogen production. |
| Document Type: |
article in journal/newspaper |
| File Description: |
text |
| Language: |
English |
| ISSN: |
1613-6810 |
| Relation: |
https://livrepository.liverpool.ac.uk/3191524/1/accepted%20version-2025-04-22.pdf; https://livrepository.liverpool.ac.uk/3191524/2/Supporting%20Information-2025-04-22.pdf; Collapse authors list. Lin, JT orcid:0009-0003-0824-8369 , Hsiao, YC orcid:0009-0004-6044-5076 , Li, C, Tseng, CY, He, ZY, Gardner, AM orcid:0000-0002-2423-8799 , Chen, Y, Yang, CC, Wang, CH, Lin, SC et al (show 5 more authors) , Lin, XX, Lin, CY, Lin, KH, Cowan, AJ orcid:0000-0001-9032-3548 and Yang, TH orcid:0000-0002-6175-4207 (2025) Spectroscopic and Theoretical Insights Into High-Entropy-Alloy Surfaces and Their Interfaces with Semiconductors for Enhanced Photocatalytic Hydrogen Production Small, 21 (25). e2503512-. ISSN 1613-6810, 1613-6829 |
| DOI: |
10.1002/smll.202503512 |
| Availability: |
https://livrepository.liverpool.ac.uk/3191524/; https://doi.org/10.1002/smll.202503512 |
| Rights: |
cc_by_4 |
| Accession Number: |
edsbas.10D802BA |
| Database: |
BASE |