Defect Engineered Metal-Organic Framework with Accelerated Structural Transformation for Efficient Oxygen Evolution Reaction

Metal-organic frameworks (MOFs) have been increasingly applied in oxygen evolution reaction (OER), and the surface of MOFs usually undergoes structural transformation to form metal oxyhydroxides to serve as catalytically active sites. However, the controllable regulation of the reconstruction process of MOFs remains as a great challenge. Here we report a defect engineering strategy to facilitate the structural transformation of MOFs to metal oxyhydroxides during OER with enhanced activity. Defective MOFs (denoted as NiFc & PRIME;xFc1-x) with abundant unsaturated metal sites are constructed by mixing ligands of 1,1 & PRIME;-ferrocene dicarboxylic acid (Fc & PRIME;) and defective ferrocene carboxylic acid (Fc). NiFc & PRIME;xFc1-x series are more prone to be transformed to metal oxyhydroxides compared with the non-defective MOFs (NiFc & PRIME;). Moreover, the as-formed metal oxyhydroxides derived from defective MOFs contain more oxygen vacancies. NiFc & PRIME;Fc grown on nickel foam exhibits excellent OER catalytic activity with an overpotential of 213 mV at the current density of 100 mA cm-2, superior to that of undefective NiFc & PRIME;. Experimental results and theoretical calculations suggest that the abundant oxygen vacancies in the derived metal oxyhydroxides facilitate the adsorption of oxygen-containing intermediates on active centers, thus significantly improving the OER activity. The fabrication of unsaturated metal sites in MOFs can accelerate the structural transformation to metal oxyhydroxides with abundant oxygen vacancies, which exhibit much higher OER catalytic activity compared with non-defective MOFs.image