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

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.
(© 2022 Wiley-VCH GmbH.)