Structure-Activity Relationships in Ni- Carboxylate-Type Metal-Organic Frameworks’ Metamorphosis for the Oxygen Evolution Reaction

Metal-organic frameworks (MOFs) have been reported to catalyze the oxygen evolution reaction (OER). Despite the established links between the pristine MOFs and their derived metal hydroxide electrocatalysts, several limitations still preclude understanding of the critical factors determining the OER performance. Of prime importance appears the choice of MOF and how its compositions relate to the catalyst stability and in turn to the reconstruction or metamorphosis mechanisms into the active species under OER conditions. An isoreticular series of Ni-carboxylate-type MOFs [Ni₂(OH)₂L] was chosen to elucidate the effects of the carboxylate linker length expansion and modulation of the linker-linker π-π interactions (L = 1,4-benzodicarboxylate, 2,6-napthalenedicarboxylate, biphenyl-4,4′-dicarboxylate, and p-terphenyl-4,4″-dicarboxylate). Degradation and reconstruction of MOFs were systematically investigated. The linker controls the transformation of Ni-MOF into distinct nickel hydroxide phases, and the conversion from α-Ni(OH)₂ to β-Ni(OH)₂, thus correlating the Ni-MOF composition with the OER activity of the Ni-MOF-derived metastable nickel hydroxide phase mixture.