Journal article
"Beyond Adsorption" Descriptors in Hydrogen Electrocatalysis
ACS catalysis, v 10(24), pp 14747-14762
18 Dec 2020
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Although electrochemical hydrogen evolution and oxidation are arguably the best-understood reactions in electrocatalysis, the anomalous effect of pH on hydrogen reaction kinetics has defied simple explanation for decades. This longstanding puzzle exposes gaps in the fundamental understanding of electrocatalysis by showing that singular adsorption descriptors (e.g., the hydrogen binding energy) cannot describe kinetic effects across electrolytes. In this Perspective, we discuss the strengths and shortcomings of binding energies as HER/HOR activity descriptors across different electrolytes and catalyst surfaces, with a special emphasis on the bifunctional mechanism, and identify several "beyond adsorption" descriptors for chemical dynamics in the double layer, including the potential of zero (free/total) charge, the binding energy of coadsorbed spectator species, transition state barrier heights, and the solvation strength of electrolyte cations. Recent evidence for and against the importance of these phenomena is assessed in the context of hydrogen electrocatalysis to determine their feasibility to accurately predict catalyst behavior. Finally, we propose paths forward for improving the mechanistic understanding of how specific interactions between the surface and species in solution affect macroscopic rates, which include combining single-crystal voltammetry, electroanalytical chemistry, in-operando spectroscopy, atomic-scale DFT calculations, and molecular "double-layer dopants".
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Details
- Title
- "Beyond Adsorption" Descriptors in Hydrogen Electrocatalysis
- Creators
- Luis Rebollar - Drexel UniversitySaad Intikhab - Drexel UniversityNicholas J. Oliveira - University of DelawareYushan Yan - University of DelawareBingjun Xu - University of DelawareIan T. McCrum - Clarkson UniversityJoshua D. Snyder - Drexel UniversityMaureen H. Tang - Drexel UniversityUniv. of Delaware, Newark, DE (United States)
- Publication Details
- ACS catalysis, v 10(24), pp 14747-14762
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 16
- Grant note
- NSF-1602886 / National Science Foundation; National Science Foundation (NSF) CBET-1651625 / National Science Foundation CAREER Program; National Science Foundation (NSF) DE-AR0001034 / U.S. Department of Energy ARPA-E; United States Department of Energy (DOE)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Web of Science ID
- WOS:000608850500032
- Scopus ID
- 2-s2.0-85097740025
- Other Identifier
- 991019168699904721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Physical