Synthesis of Holey Graphene Nanoparticle Compounds.

Bulk scale syntheses of sp2 nanocarbon have typically been generated by extensive chemical oxidation to yield graphite oxide from graphite followed by a reductive step. Materials generated via harsh random processes lose desirable physical characteristics. Loss of sp2 conjugation inhibits long range electronic transport and the potential for electronic band manipulation. Here we present a nanopatterned holey graphene (HG) material electronically hybridized with metal containing nanoparticles. Oxidative plasma etching of highly ordered pyrolytic graphite (HOPG) via previously developed COF-5 templated patterning yields bulk scale material for electrocatalytic applications and fundamental investigations into band structure engineering of nanocomposites. We establish broad ability (Ag, Au, Cu, and Ni) to grow metal containing nanoparticles in patterned holes in a metal precursor dependent manner without reducing agent. Graphene nanoparticle compounds (GNCs) show metal contingent changes in valence band structure. Density functional theory (DFT) investigations reveal preferences for uncharged metal states, metal contributions to the valence band, and embedding of nanoparticles over surface incorporation. Ni-GNCs show activity for oxygen evolution reaction (OER) in alkaline media (1 M KOH). Electrocatalytic activity exceeds 10,000 mA/mg of Ni, stability for two hours of continuous operation, and is kinetically consistent via Tafel slope with Ni(OH)2 based catalysis.