Operando techniques for identifying real active sites in electrocatalysis

Operando techniques for identifying real active sites in electrocatalysis Full article

Journal

Applied Catalysis A: General
ISSN: 0926-860X , E-ISSN: 1873-3875

Output data

Year: 2026, Volume: 726, Article number : 121183, Pages count : DOI: 10.1016/j.apcata.2026.121183

Authors

Zhang Chunyu ¹ , Zhang Zhirong ¹ , Huang Yuze ¹ , Wang Yuncheng ¹ , Li Chenlei ¹ , Lebedeva Olga ² , Kultin Dmitry ² , Kustov Leonid ^2,3 , Dolati Abolghasem ⁴ , Cui Yi ⁵ , Zeng Jie ^1,6

Affiliations

1	Hefei National Research Center for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, Institute of Advanced Technology, University of Science and Technology of China, Hefei, Anhui 230026, PR China
2	Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia
3	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
4	Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran
5	i-Lab & Vacuum Interconnected NanoTech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China
6	School of Chemistry & Chemical Engineering, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China

Operando characterization techniques have become indispensable for understanding electrocatalysis under operating conditions. In many electrocatalytic systems, catalysts do not remain structurally static during operation, but instead undergo continuous reconstruction. As a result, the real active sites often differ fundamentally from the as-synthesized precatalyst, making conventional ex situ characterization insufficient for establishing reliable structure-performance relationships. In this review, we focus on how operando/in situ characterization reveals real active sites formed during electrocatalytic reconstruction. Particular attention is given to the role of reconstruction in electrocatalysis and to the limitations of characterization techniques in capturing transient operating structures. The review also highlights how operando/in situ techniques resolve reconstruction across multiple time and length scales, including advanced platforms such as the vacuum interconnected NanoTech workstation for preserving and probing sensitive surface chemistry. Using the CO2 reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction as representative examples, we show how operando/in situ studies have reshaped current understanding of active-phase evolution, catalytic mechanisms, and real structure-performance relationships. Finally, we discuss current challenges in this field, including limited temporal and spatial resolution, the complexity of solid-liquid interfacial microenvironments, and the difficulty of correlating multimodal signals under operating conditions.

Zhang C. , Zhang Z. , Huang Y. , Wang Y. , Li C. , Lebedeva O. , Kultin D. , Kustov L. , Dolati A. , Cui Y. , Zeng J.
Operando techniques for identifying real active sites in electrocatalysis
Applied Catalysis A: General. 2026. V.726. 121183 . DOI: 10.1016/j.apcata.2026.121183 WOS Scopus OpenAlex

Submitted:	Jun 11, 2026
Published online:	Aug 17, 2026

≡ Web of science:	WOS:001852321800001
≡ Scopus:	2-s2.0-105047668315
≡ OpenAlex:	W7202346058