Organic Ligand‐Functionalized CoN ₂ ‐C‐N ₂ Ni Dual‐Atom for Tailored Proton and Non‐Proton Transfer in Hydrogen Evolution and Triiodide Reduction

ABSTRACT

Regulating the sustained transport and local concentration of reactive intermediates is essential for accelerating kinetics; however, constructing effective pathways for transferring both protonic and non‐protonic intermediates remains challenging. Herein, we present organic ligand‐functionalized interfacial engineering by anchoring trimesic acid (TMA) to MXene‐supported Co/Ni dual‐atom sites (TMA‐CoNi _DA ‐MXene) to establish carboxyl‐mediated proton and non‐proton transport channels. By leveraging continuous π–π stacking and deprotonated ─COO ⁻ groups in aromatic frameworks, TMA‐CoNi _DA ‐MXene facilitated the capture and delivery of I ^* /H ^* intermediates toward Co/Ni dual active sites, while also mitigating localized excessive accumulation of I ^* /H ^* . By exploiting the expanded interlayer spacing, stabilized CoN ₂ ‐C‐N ₂ Ni centers, and tailored transport pathways, TMA‐CoNi _DA ‐MXene achieved a photoconversion efficiency of 8.62% as a counter electrode in iodine‐based solar cells and attained 10 mA cm ⁻² with an overpotential of only 71 mV in the alkaline hydrogen evolution reaction (HER). This work provides insightful perspectives on integrating carboxylated organic ligands to jointly transfer protonic and non‐protonic intermediates and offers new approaches for organic–inorganic interfacial design in other complex systems.