Graphitic nanostructures in a porous carbon framework significantly enhance electrocatalytic oxygen evolution

A hybrid structure, a graphitic nanostructures@porous carbon framework, is developed by utilizing the bimetallic zeolitic imidazolate framework-8 (ZIF-8) as a solid precursor, simultaneously templating porous carbon and growing graphitic nanocarbon in a simplified chemical vapor deposition (CVD) fashion. A ligand, 2-methylimidazolate (2MIM), in the ZIF-8 decomposes above 600 C to yield active carbon/hydrocarbon radicals/vapour. With the idea of using the high catalytic activity of nickel to grow graphitic nanostructures in a CVD process from gaseous carbon feedstocks, a precursor, bimetallic ZIF8, is synthesized by partial substitution of zinc metal centres by nickel. Such nickel centres thus act as nanocatalysts to grow graphitic nanostructures from the carbon radicals arising from the partly decomposed ligand of the framework during the carbonization step. These hybrid structures show a highly enhanced electrocatalytic activity for the water splitting oxygen evolution reaction (OER). Furthermore the catalytic activity for the oxygen reduction and hydrogen evolution reactions (ORR and HER), and gas uptake capacities for H2 and CO2 are enhanced with respect to the increased porosity and nitrogen doping in the samples. We also show that not all the MOF-based precursors with nickel metal centres are suitable for producing nanographitic structures. Our further investigation suggests that the graphitization in the samples plays a critical role in enhancing the catalytic activities.