American Chemical Society, ACS Nano, 1(7), p. 811-817, 2012
DOI: 10.1021/nn305313q
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The artificial leaf project calls for new materials enabling multi-electron catalysis with minimal overpotential, high turnover frequency and long-term stability. Is graphene a better material than carbon nanotubes to enhance water oxidation catalysis for energy applications? Here we show that functionalized graphene with a tailored distribution of polycationic, quaternized, ammonium pendants provides an sp2 carbon nano-platform to anchor a totally inorganic tetraruthenate catalyst, mimicking the oxygen evolving center of natural PSII. The resulting hybrid material displays oxygen evolution at overpotential as low as 300 mV at neutral pH with negligible loss of performance after 4 hours testing. This multi-layer electroactive asset enhances the turnover frequency by one order of magnitude with respect to the isolated catalyst, and provides a definite up-grade of the carbon nanotube material, with a similar surface functionalization. Our innovation is based on a non-invasive, synthetic protocol for graphene functionalization that goes beyond the ill-defined oxidation-reduction methods, allowing a definite control of the surface properties.