Deciphering the Role of Lattice Selenium in Electrocatalytic Self‐Reconstruction for Boosting Alkaline Hydrogen Evolution

X Xiao‐Han Zhang (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) M Meng‐Tian Zhang (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) H Hong‐Gang Du (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) H Hai‐Hua Huang (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) X Xue‐Feng Zhang (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China) X Xia Wen L Li‐Dong Wang (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China) W Wei‐Zhen Deng (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) Y Yu‐Mei He (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) J Jie Bai (State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Institute of Artificial Intelligence & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)) L Li‐Wen Ding (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China) C Chun‐Ting He (Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China)

Abstract

Abstract Cathode reconstruction is equally crucial for water electrolysis, yet it has received less attention than anode. Lattice selenium (Se) doping is an effective strategy to improve hydrogen evolution reaction (HER) of metal‐based electrocatalysts in cathodes, but many fundamental questions concerning the actual role of Se on the active species as well as catalytic kinetics remain to be clarified, especially in those electrocatalytic self‐reconstruction systems. Here, we showcase the accelerated two‐stage structural evolution of Se‐doped cobalt phosphide (Se‐CoP) during alkaline HER by operando X‐ray absorption spectroscopy and powder X‐ray diffraction, combined with high‐resolution transmission electron microscopy (HRTEM) analysis. Further density functional theory (DFT) calculations suggest that the in situ formed dual‐component heterostructure of highly crystalline Co(OH) 2 and robust Co nanoclusters, which are decorated with residual Se, is responsible for the high HER performance. The reconstructed Se‐CoP on carbon cloth delivers a low overpotential of 79 ± 2 mV at 100 mA · cm −2 and achieves an impressive charge transfer amount of 6.3 × 10 5 C cm −2 operating at 500 mA cm −2 , surpassing the reported electrocatalysts constructed by non‐noble metal phosphides. This work provides brand‐new perspectives on the self‐reconstruction perturbed by heteroatoms for well‐designed composite electrocatalysts.

Article Details

Volume / Issue Vol. 64, Issue 33
Published August 11, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (12)

X

Xiao‐Han Zhang

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

M

Meng‐Tian Zhang

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

H

Hong‐Gang Du

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

H

Hai‐Hua Huang

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

X

Xue‐Feng Zhang

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China

X

Xia Wen

L

Li‐Dong Wang

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China

W

Wei‐Zhen Deng

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

Y

Yu‐Mei He

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

J

Jie Bai

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Institute of Artificial Intelligence & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)

L

Li‐Wen Ding

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 China

C

Chun‐Ting He

Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China