Electronic‐Geometric Pre‐Compensation Enables Intermetallic RhSb Bimetallenes for Efficient Nitrite Electroreduction

Abstract

ABSTRACT Sustainable electrochemical synthesis aims to produce high‐value chemicals under mild conditions, but its advancement is hindered by electrocatalyst deactivation caused by the strong adsorption of poisoning intermediates. Strategies that mitigate deactivation by weakening the adsorption of poisoning intermediates are constrained by the linear scaling relationships of adsorption energies, which simultaneously reduce the binding of other key reactive species, leading to insufficient catalytic performance or demanding reaction conditions. In this study, we propose and validate a pre‐compensation strategy between electronic structure and geometric structure specifically toward Rh active sites to mitigate *NO poisoning in the nitrite electroreduction reaction (NO 2 ERR). In the fabricated intermetallic RhSb bimetallenes (RhSb IMMs), Sb boosts the adsorption capacity of Rh toward reactants by modulating the electronic structure, compensating for the geometrically constrained weak adsorption configuration imposed by the ordered alloy structure. Consequently, RhSb IMMs operate stably for over 880 h with an outstanding Faradaic efficiency of over 90% at −0.3 V (vs. RHE) and achieve an average ammonia (NH 3 ) yield rate of 107.5 g h −1 g cat −1 for NO 2 ERR at a current density exceeding 0.45 A cm −2 . This compensation strategy provides a rational design principle for reconciling fundamental trade‐offs in catalysis and beyond.