Single-zinc vacancy unlocks high-rate HO electrosynthesis from mixed dioxygen beyond Le Chatelier principle.

Nat Commun

Key Laboratory for Soft Chemistry and Functional Materials, School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Ministry of Education, Nanjing, 210094, China.

Published: May 2024

Le Chatelier's principle is a basic rule in textbook defining the correlations of reaction activities and specific system parameters (like concentrations), serving as the guideline for regulating chemical/catalytic systems. Here we report a model system breaking this constraint in O electroreduction in mixed dioxygen. We unravel the central role of creating single-zinc vacancies in a crystal structure that leads to enzyme-like binding of the catalyst with enhanced selectivity to O, shifting the reaction pathway from Langmuir-Hinshelwood to an upgraded triple-phase Eley-Rideal mechanism. The model system shows minute activity alteration of HO yields (25.89~24.99 mol g h) and Faradaic efficiencies (92.5%~89.3%) in the O levels of 100%~21% at the current density of 50~300 mA cm, which apparently violate macroscopic Le Chatelier's reaction kinetics. A standalone prototype device is built for high-rate HO production from atmospheric air, achieving the highest Faradaic efficiencies of 87.8% at 320 mA cm, overtaking the state-of-the-art catalysts and approaching the theoretical limit for direct air electrolysis (~345.8 mA cm). Further techno-economics analyses display the use of atmospheric air feedstock affording 21.7% better economics as comparison to high-purity O, achieving the lowest HO capital cost of 0.3 $ Kg. Given the recent surge of demonstrations on tailoring chemical/catalytic systems based on the Le Chatelier's principle, the present finding would have general implications, allowing for leveraging systems "beyond" this classical rule.

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11098813PMC
http://dx.doi.org/10.1038/s41467-024-48256-7DOI Listing

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