Unlocking the Potential of Mn‐based Catalyst for Durable Two‐electron Oxygen Reduction in Acid at High Current Densities

H Helai Huang (State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China) M Mingze Sun K Kai Chen Y Yizhen Che (State Key Laboratory of Chemical Engineering, Department of Chemical Engineering) X Xin Tang Z Zhengwen Li (Department of Chemical Engineering) K Kaiqi Nie (Department of Chemical Engineering) S Shuairen Qian (Department of Chemical Engineering) J Jinjie Fang (State Key Lab of Organic−Inorganic Composites, Beijing University of Chemical Technology, 100029 Beijing, China) H Haiyong Wang (State Key Laboratory of Organic−Inorganic Composites and Beijing Advanced Innovation Center for Soft Matter Science and Engineering Beijing University of Chemical Technology Beijing 100084 P.R. China) Y Yanfen Wu Q Qikun Hu (State Key Laboratory of Chemical Engineering, Department of Chemical Engineering) Y Yuqi Wang X Xiaohang Sun J Junliang He (State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China) Y Yu‐Xiao Zhang (State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China) Z Zhongbin Zhuang L Liang Zhang Z Zhiqiang Niu (State Key Laboratory of Chemical Engineering, Department of Chemical Engineering)

Abstract

Abstract Electrochemical synthesis of H 2 O 2 by two‐electron oxygen reduction (2e − ORR) often shows limited stability at high current densities in acidic media. Mn‐based catalysts have been demonstrated highly stable for four‐electron ORR thanks to their intrinsically low rate constant for Fenton‐like reactions. However, their activity toward acidic 2e − ORR remains low because of too strong adsorption to *OOH. Here, we report a diatomic Mn catalyst with high‐spin Mn II centers to enable high onset potential (0.69 V), high selectivity (>90%), and outstanding stability (240 h under 300 mA cm −2 ) toward H 2 O 2 electrosynthesis in acid. Theoretical calculations and in situ spectroscopies reveal that the diatomic Mn sites have downshifted d ‐band center and thus weakened adsorption strength for *OOH. Moreover, the inertia of the Mn II sites toward the troublesome Fenton‐like reactions leads to the long‐term stability at high current densities. We further demonstrate the functionalization of waste polyethylene (PE) using the high‐concentration H 2 O 2 as produced, which provides a sustainable route toward on‐site upcycling of plastic waste.

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 (19)

H

Helai Huang

State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China

M

Mingze Sun

K

Kai Chen

Y

Yizhen Che

State Key Laboratory of Chemical Engineering, Department of Chemical Engineering

X

Xin Tang

Z

Zhengwen Li

Department of Chemical Engineering

K

Kaiqi Nie

Department of Chemical Engineering

S

Shuairen Qian

Department of Chemical Engineering

J

Jinjie Fang

State Key Lab of Organic−Inorganic Composites, Beijing University of Chemical Technology, 100029 Beijing, China

H

Haiyong Wang

State Key Laboratory of Organic−Inorganic Composites and Beijing Advanced Innovation Center for Soft Matter Science and Engineering Beijing University of Chemical Technology Beijing 100084 P.R. China

Y

Yanfen Wu

Q

Qikun Hu

State Key Laboratory of Chemical Engineering, Department of Chemical Engineering

Y

Yuqi Wang

X

Xiaohang Sun

J

Junliang He

State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China

Y

Yu‐Xiao Zhang

State Key Laboratory of Chemical Engineering Department of Chemical Engineering Tsinghua University Beijing 100084 P.R. China

Z

Zhongbin Zhuang

L

Liang Zhang

Z

Zhiqiang Niu

State Key Laboratory of Chemical Engineering, Department of Chemical Engineering