Directed Dual Charge Pumping Tunes the d‐Orbital Configuration of Pt Cluster Boosting Hydrogen Evolution Kinetic

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-05, Vol.20 (22), p.e2307135-n/a
• Main Authors: Zhang, Zeyi, Wu, Wei, Chen, Suhao, Wang, Zichen, Tan, Yangyang, Chen, Wei, Guo, Fei, Chen, Runzhe, Cheng, Niancai
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Catalytic activity; charge pumping; Chemical synthesis; d‐band theory; Electrolysis; Electron transfer; electronic metal‐support interactions; Electrons; Heterostructures; hydrogen evolution reaction; Hydrogen evolution reactions; Intermetallic compounds; Nanoclusters; Platinum; Pumping; Tin dioxide
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202307135

Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual‐charge pumping strategy to tune the d‐orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal‐support interactions (EMSI) create an effective directional electron transfer channel for the d‐orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual‐charge pumping strategy is validated by elaborating Sb‐doped SnO2 (ATO) supported Fe‐doped PtSn heterostructure catalysts (Fe‐PtSn/ATO). The synthesized 3%Fe‐PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5 mV to reach a current density of 10 mA cm−2), higher mass activity (28.6 times higher than commercial 20 wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading. The Ligand effect combines with electron‐metal‐support interaction (EMSI) as directed dual charge pumping to tune the d‐orbital electronic rearrangement of PtSn nanoclusters for efficient HER catalytic kinetics. This work provides a promising strategy for designing the d‐orbital configuration of Pt‐based catalysts to develop electrocatalysts with high HER activity in the future.