Breaking the linear scaling limit in multi-electron-transfer electrocatalysis through intermediate spillover | Nature Catalysis

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The linear scaling relationships between the adsorption energies of multiple intermediates constrain the maximum reaction activity of heterogeneous catalysis. Here we propose an intermediate spillover strategy to decouple the elementary electron-transfer steps in an electrochemical reaction by building a bi-component interface, thereby independently tuning the corresponding intermediate adsorption at an individual catalytic surface. Taking the electrocatalytic oxygen reduction reaction as an example, oxophilic sites are preferable for activating oxygen molecules, then the adsorbed OH* intermediates spontaneously migrate to the adjacent sites with a weaker oxygen binding energy, where OH* intermediates are further reduced and desorbed to complete the overall catalytic cycle. Consequently, the designed Pd/Ni(OH)2 catalyst can remarkably elevate the half-wave potential of the oxygen reduction reaction to ~70 mV higher than that of the Pt/C catalyst, surmounting the theoretical overpotential limit of Pd. This design principle highlights an opportunity for utilizing intermediate spillover to break the ubiquitous scaling relationships in multi-step catalytic reactions.

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The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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This work was supported financially by the City University of Hong Kong startup fund (9020003), an ITF-RTH–Global STEM Professorship (9446006), and the JC STEM lab of Advanced CO2 Upcycling (9228005). S.-F.H. acknowledges financial support from the National Science and Technology Council, Taiwan (contract no. NSTC 111-2628-M-A49-008) and Yushan Young Scholar Program and the Center for Emergent Functional Matter Science, Ministry of Education, Taiwan. H.B.T. acknowledges financial support from the National Key R&D Program of China (2023YFB4004600). H.B.Y. acknowledges support from the National Natural Science Foundation of China under grant no. 22075195. W.L. is grateful for support from the National Natural Science Foundation of China (22427801). Y.X. acknowledges financial support from the National Natural Science Foundation of China (22478348). C.S. is financially supported by the National Key Research and Development Program of China (2021YFA1600800). J.G.C. is sponsored by the US Department of Energy (contract no. DE-SC0012704).

These authors contributed equally: Qilun Wang, Sung-Fu Hung, Kejie Lao.

Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong SAR, China

Qilun Wang, Fuhua Li & Bin Liu

Department of Applied Chemistry and Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, Hsinchu, Taiwan

Sung-Fu Hung

Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan

Sung-Fu Hung

State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

Kejie Lao & Hua Bing Tao

Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, China

Kejie Lao & Hua Bing Tao

School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore, Singapore

Xiang Huang, Liping Zhang & Junming Zhang

School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, China

Hong Bin Yang & Yuhang Liu

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

Wei Liu & Weijue Wang

School of Chemical Engineering, Dalian University of Technology, Dalian, China

Yaqi Cheng

National Synchrotron Radiation Research Center, Hsinchu, Taiwan

Nozomu Hiraoka

Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

Jiazang Chen

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, China

Yinghua Xu

International Collaboration Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China

Chenliang Su

Department of Chemical Engineering, Columbia University, New York, NY, USA

Jingguang G. Chen

Department of Chemistry, Hong Kong Institute for Clean Energy (HKICE) & Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR, China

Bin Liu

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Q.W., H.B.T. and B.L. conceived and designed the project. Q.W., K.L., H.B.T., L.Z., J.Z., Y.C., J.C. and Y.X. performed the catalyst synthesis, structural characterizations and electrochemical measurements. S.-F.H., H.B.Y., N.H. and Y.L. acquired the X-ray absorption spectroscopies and provided expertise for data analysis. W.L. and W.W. obtained the TEM images. X.H. and F.L. carried out the theoretical calculations. Q.W., H.B.T., C.S., J.G.C. and B.L. discussed the results and drafted the paper. All authors reviewed and contributed to this paper.

Correspondence to Hua Bing Tao, Jingguang G. Chen or Bin Liu.

The authors declare no competing interests.

Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

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Table of Contents; Supplementary Figs. 1–31, Tables 1–3 and References.

AIMD simulations for the spillover of adsorbed OH* from Pd sites to the nearby Ag surface.

Atomic coordinates of the optimized computational models, initial and final configurations in AIMD simulations.

Source data Fig. 1

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Wang, Q., Hung, SF., Lao, K. et al. Breaking the linear scaling limit in multi-electron-transfer electrocatalysis through intermediate spillover. Nat Catal (2025). https://doi.org/10.1038/s41929-025-01323-8

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Received: 24 September 2023

Accepted: 11 March 2025

Published: 02 April 2025

DOI: https://doi.org/10.1038/s41929-025-01323-8

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