Breaking the Intermediate Solvation Shell on Single‐Atom Catalysts With a Proximal Group Perturber for Enhanced Oxygen Reduction
Abstract
ABSTRACT The electrocatalytic performance is governed by the immediate microenvironment surrounding the active site, particularly the hydrogen‐bond network that stabilizes reaction intermediates. While cation effects in aqueous electrolytes allow tuning of this network, this powerful leveraging is absent in proton‐exchange membrane fuel cells (PEMFCs), where proton is the sole cation. Here, we demonstrate a general strategy of “immobilized molecular perturbation” for single‐atom catalysts, which moves the tuning function from the electrolyte to the catalyst's second coordination sphere. Using the oxygen reduction reaction (ORR) on Fe─N─C as a model, we demonstrate that proximal P─O groups act as steric and hydrogen‐bonding perturbers. This engineered microenvironment selectively weakens the solvation shell of key * OH intermediates, as confirmed by spectroscopy and computations, thereby facilitating the rate‐determining step of * OH desorption. This regulation endows the catalyst with exceptional performance, achieving a half‐wave potential of 0.861 V in 0.5 m H 2 SO 4 and a peak power density of 1024 mW cm −2 in a H 2 /O 2 PEMFC. Furthermore, it exhibits outstanding stability with 72 % current retention after 253 h at 0.65 V, positioning it among the best‐reported non‐precious metal catalysts. This work shifts the paradigm from exclusive active‐center optimization to deliberate local microenvironment engineering, enabling accelerated electrocatalysis in device‐relevant environments.
Article Details
Authors (13)
Zhaoyang Han
Ruihui Gan
Institute of Technology for Carbon Neutrality Shenzhen Institute of Advanced Technology Chinese Academy of Sciences Shenzhen P. R. China
Tao Gong
Longji Yuan
Institute of Technology for Carbon Neutrality Shenzhen Institute of Advanced Technology Chinese Academy of Sciences Shenzhen P. R. China
Wenliang Feng
Shenzhen Key Laboratory of Special Functional Materials Shenzhen Engineering Laboratory For Advance Technology of Ceramics Guangdong Research Center For Interfacial Engineering of Functional Materials Guangdong Provincial Key Laboratory of New Energy Materials Service Safety College of Materials Science and Engineering Shenzhen University Shenzhen China
Huici Qiao
Shenzhen Key Laboratory of Special Functional Materials Shenzhen Engineering Laboratory for Advance Technology of Ceramics Guangdong Research Center for Interfacial Engineering of Functional Materials Guangdong Provincial Key Laboratory of New Energy Materials Service Safety College of Materials Science and Engineering Shenzhen University Shenzhen P. R. China
Yuzhe Liu
Jinzhu Zhu
Shenzhen Key Laboratory of Special Functional Materials Shenzhen Engineering Laboratory for Advance Technology of Ceramics Guangdong Research Center for Interfacial Engineering of Functional Materials Guangdong Provincial Key Laboratory of New Energy Materials Service Safety College of Materials Science and Engineering Shenzhen University Shenzhen P. R. China
Ruisong Li
Shenzhen Key Laboratory of Special Functional Materials Shenzhen Engineering Laboratory for Advance Technology of Ceramics Guangdong Research Center for Interfacial Engineering of Functional Materials Guangdong Provincial Key Laboratory of New Energy Materials Service Safety College of Materials Science and Engineering Shenzhen University Shenzhen P. R. China
Xulei Sui
Shenzhen Key Laboratory of Special Functional Materials Shenzhen Engineering Laboratory For Advance Technology of Ceramics Guangdong Research Center For Interfacial Engineering of Functional Materials Guangdong Provincial Key Laboratory of New Energy Materials Service Safety College of Materials Science and Engineering Shenzhen University Shenzhen China
Yongping Zheng
Guangjie Shao
State Key Laboratory of Metastable Materials Science and Technology Hebei Key Laboratory of Applied Chemistry School of Environmental and Chemical Engineering Yanshan University Qinhuangdao China
Zhenbo Wang
Key Laboratory of Regional Sustainable Development Modeling, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences