Modulating crystal and electronic structure of NiFe-MOFs by inorganic acid for highly efficient electrochemical water oxidation

Abstract

Seeking new methods to modulate the structure of metal–organic frameworks (MOFs) for diverse applications, particularly for water splitting, is intensively urgent but challenging. Herein, a simple hydrothermal method employing HCl as the modulator is developed to synthesize a series of NiFe-MOF-n/NF. The amount of HCl modulator not only changes the elemental composition and crystal structure but also modulates the electronic structure of NiFe-MOF-n/NF, thus improving intrinsic activity. Owing to the synergetic interactions between Ni and Fe atoms, free-standing feature, the optimized NiFe-MOF-2/NF yields excellent OER activity with overpotentials of 209 and 260 mV at 10 and 100 mA cm⁻², respectively, a small Tafel slope of 36.4 mV dec⁻¹ and excellent OER stability for 24 h at 100 mA cm⁻² in 1 M KOH. This demonstrates that NiFe-MOF-2/NF are in situ converted into metal oxide/oxyhydroxide after OER, thereby serving as the real active sites. This study offers a feasible way to fabricate low-cost, efficient MOF-based electrocatalysts.