Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

Qiu, Yang; Ray, Debmalya; Yan, Litao; Li, Xiaohong; Song, Miao; Engelhard, Mark H.; Sun, Junming; Lee, Mal-Soon; Zhang, Xin; Nguyen, Manh-Thuong; Glezakou, Vassiliki-Alexandra; Wang, Yong; Rousseau, Roger; Shao, Yuyan

doi:10.1021/jacs.3c06398

Title: Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

Journal Article · 16 November 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c06398 · OSTI ID:2340810

Qiu, Yang ^[1]; Ray, Debmalya ^[1]; Yan, Litao ^[1]; Li, Xiaohong ^[1]; Song, Miao ^[1];

^[1]; Sun, Junming ^[2];

^[1];

^[3];

^[1];

^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Washington State Univ., Pullman, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Proton transfer is critically important to many electrocatalytic reactions, and directed proton delivery could open new avenues for the design of electrocatalysts. However, although this approach has been successful in molecular electrocatalysis, proton transfer has not received the same attention in heterogeneous electrocatalyst design. Here, in this work, we report that a metal oxide proton relay can be built within heterogeneous electrocatalyst architectures and improves the kinetics of electrochemical hydrogen evolution and oxidation reactions. The volcano-type relationship between activity enhancement and pK_a of amine additives confirms this improvement; we observe maximum rate enhancement when the pK_a of a proton relay matches the pH of the electrolyte solution. Density-functional-theory-based reactivity studies reveal a decreased proton transfer energy barrier with a metal oxide proton relay. These findings demonstrate the possibility of controlling the proton delivery and enhancing the reaction kinetics by tuning the chemical properties and structures at heterogeneous interfaces.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2340810

Alternate ID(s):: OSTI ID: 2397471

Report Number(s):: PNNL-SA--177575

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

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