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Polydisperse Pt Deposits Over TiO 2 ‐Nanotube‐Array‐Supported Ru Nanoparticles: Harnessing the Interfacial Synergy for Efficient Hydrogen Evolution Electrocatalysis
Author(s) -
Krstajić Pajić Mila N.,
Dobrota Ana S.,
Mazare Anca,
Đurđić Slađana,
Zhou Xin,
Denisov Nikita,
Skorodumova Natalia V.,
Manojlović Dragan,
Vasilić Rastko,
Pašti Igor A.,
Schmuki Patrik,
Lačnjevac Uroš
Publication year - 2025
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202411870
Abstract Developing cost‐effective precious metal electrocatalysts for the hydrogen evolution reaction (HER) is key to realizing the economic viability of acidic water electrolysis. Herein, galvanic displacement is employed for in situ formation of bimetallic Pt/Ru deposits on H‐intercalated TiO 2 nanotube arrays. It is found that a two‐step procedure yields polydisperse deposits with a dominant fraction of Ru nanoparticles coated with atomic and subnanometric Pt islands. These Pt|Ru nanointerfaces induce charge transfer from Pt to Ru, which modulates the electronic structure of Pt sites for accelerated HER kinetics. By varying the platinization time in the second step, a balance between the exposure of catalytically active Pt|Ru nanointerfaces and the total number of Pt surface sites is achieved. The optimized composite, termed Ru‐30min@Pt‐30min, requires an overpotential of 58 mV to deliver a current density of 100 mA cm −2 in 1.0 m HClO 4 and maintains performance stability and structure integrity under prolonged operation. Moreover, it presents a 3.5‐fold increase in precious metal mass activity over Pt/C at η = 80 mV. Theoretical calculations reveal that the electronic interactions generated by Pt‐modification of Ru and hydrogenated TiO 2 surfaces provide multiple active sites with improved H ads energetics compared to pure Pt and Ru.