Operando Elucidation of Electrocatalytic and Redox Mechanisms on a 2D Metal Organic Framework Catalyst for Efficient Electrosynthesis of Hydrogen Peroxide in Neutral Media

The practical electrosynthesis of hydrogen peroxide (H₂O₂) is hindered by the lack of inexpensive and efficient catalysts for the two-electron oxygen reduction reaction (2e^- ORR) in neutral electrolytes. Here, we show that Ni₃HAB₂ (HAB = hexaaminobenzene), a two-dimensional metal organic framework (MOF), is a selective and active 2e^- ORR catalyst in buffered neutral electrolytes with a linker-based redox feature that dynamically affects the ORR behaviors. Rotating ring-disk electrode measurements reveal that Ni₃HAB₂ has high selectivity for 2e^- ORR (>80% at 0.6 V vs RHE) but lower Faradaic efficiency due to this linker redox process. Operando X-ray absorption spectroscopy measurements reveal that under argon gas the charging of the organic linkers causes a dynamic Ni oxidation state, but in O₂-saturated conditions, the electronic and physical structures of Ni₃HAB₂ change little and oxygen-containing species strongly adsorb at potentials more cathodic than the reduction potential of the organic linker (E_redox ∼ 0.3 V vs RHE). We hypothesize that a primary 2e^- ORR mechanism occurs directly on the organic linkers (rather than the Ni) when E > E_redox, but when E < E_redox, H₂O₂ production can also occur through Ni-mediated linker discharge. By operating the bulk electrosynthesis at a low overpotential (0.4 V vs RHE), up to 662 ppm of H₂O₂ can be produced in a buffered neutral solution in an H-cell due to minimized strong adsorption of oxygenates. This work demonstrates the potential of conductive MOF catalysts for 2e^- ORR and the importance of understanding catalytic active sites under electrochemical operation.