Electrocatalysis is key to sustainable energy conversion and storage, but its efficiency is limited by scaling laws between reactant adsorption and desorption. Multisite catalysts promises to overcome these limits, but challenges in fabrication and characterization hinder its validation. We present a platform to study and optimize multisite electrocatalysis. Leveraging van der Waals stacked 2D materials, we create catalytic edge assemblies with precise activity variations, enabling atomically engineered site separation and interaction. This approach enables the identification of multisite catalysts that enhance the hydrogen evolution reaction (HER) beyond single-site Sabatier scaling. Altering atomic-scale site separations reverts the system to single-site mechanisms, highlighting the importance of intermediate transport. Direct evidence of intermediate exchange is provided by electrostatic control of the sites, supported by ab initio simulations. We further engineer bifunctional catalysts for the oxygen evolution reaction (OER) and HER, achieving superior neutral water splitting. These findings enable the catalytic cascade design and complex electrochemical synthesis.

Department of Electrical Engineering and Computer Science Massachusetts Institute of Technology Cambridge Massachusetts 02139 United States

Department of Electronic Engineering Chung Yuan Christian University Taoyuan 320 Taiwan

Department of Low Dimensional Systems J Heyrovský Institute of Physical Chemistry Prague 18223 Czech Republic

Department of Physics National Taiwan University Taipei 10617 Taiwan

Institute of Atomic and Molecular Sciences Academia Sinica Taipei 10617 Taiwan

International Graduate Program of Molecular Science and Technology National Taiwan University Taipei 10617 Taiwan

Molecular Science and Technology Program Taiwan International Graduate Program Academia Sinica Taipei 10617 Taiwan

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