Breaking through the State-of-the-Art Frontier in Oxygen Electrocatalysis: Geometry Adaptive Catalysts (GACs)

Abstract

The grand challenge in oxygen electrocatalysis lies in overcoming scaling relations. The theoretical activity volcano positions the ideal catalyst at the apex. However, the OH–OOH scaling relation determines a linear path on the volcano surface that limits the activity. The current state-of-the-art (SOTA) in modeling confirms this scaling relation, at the same time it hinders the experimental development of novel oxygen reduction reaction (ORR) catalysts, impeding progress in sustainable energy solutions. To address this challenge, we propose to use the geometry effect and introduce the concept of Geometry Adaptive Catalysts (GACs).[1]The geometry effect, based on preliminary research, involves changing catalytic activity by adjusting the adsorption energy of intermediates through the control of catalyst geometry. Our goal is to break through the SOTA frontier for ORR by synthesizing GACs and supporting our efforts with theoretical and computational modeling of the geometric effect. In this work we aimed to utilize the geometry effect by synthesizing GACs with various controlled structures, including specific intersite distances, and variable curvature. This enables precise control of catalyst geometry, allowing manipulation of catalytic activity and overcoming scaling relations. Key geometric parameters, namely inter-site distance, curvature, and specific stabilizations of ORR intermediates, are explored to test our hypothesis: Controlling catalyst geometry adjusts the ORR mechanism and adsorption energies of intermediates, enabling the switching, pushing, and even bypassing of scaling relations.This approach holds promise for substantial improvements in environmental sustainability and human life quality, with broad applicability to various electrocatalytic reactions beyond ORR.