Synergetic Dual‐Ion Centers Boosting Metal Organic Framework Alloy Catalysts toward Efficient Two Electron Oxygen Reduction

Abstract Herein, a strategy of synergetic dual‐metal‐ion centers to boost transition‐metal‐based metal organic framework (MOF) alloy nanomaterials as active oxygen reduction reaction (ORR) electrocatalysts for efficient hydrogen peroxide (H 2 O 2 ) generation is proposed. Through a facile one‐pot wet chemical method, a series of MOF alloys with unique Ni–M (M–Co, Cu, Zn) synergetic centers are synthesized, where the strong metallic ions 3d–3d synergy can effectively inhibit O 2 cleavage on Ni sites toward a favorable two‐electron ORR pathway. Impressively, the well‐designed NiZn MOF alloy catalysts show an excellent H 2 O 2 selectivity up to 90% during ORR, evidently outperforming that of NiCo MOF (45%), and NiCu MOF (55%). Moreover, it sustains efficient activity and robust stability under a continuous longterm ORR operation. The correlative in situ synchrotron radiation X‐ray adsorption fine structure and Fourier transform infrared spectroscopy analyses reveal at the atomic level that, the higher Ni oxidation states species, regulated via adjacent Zn 2+ ions, are favorable for optimizing the adsorption energetics of key *OOH intermediates toward fast two electron ORR kinetics.