Engineering solar-powered catalyst systems for fuel production is of critical importance to the advancement of the global energy economy. Heterogeneous catalyst manifolds most promising for photocatalysis are those that boast versatile and cheap, stable components. Huisgen's 1,3-dipolar cycloaddition ('click' chemistry) and p-stacking graphene adsorption systems provide a range of facile methods for electrode-surface modification and catalyst binding to build stable photocathode systems. In this work, click chemistry has been made accessible to gallium-based semiconductors for the first time by decorating the semiconductor surface with azide functionalities, opening a whole new world of versatility to semiconductor catalysis. Resilient iron-based dihydrogen production catalysts with customizable ligand systems have been prepared and functionalized with terminal alkynes, and were shown to 'click' onto the azide-functionalized GaP surfaces. X-ray photoelectron spectroscopy (XPS) confirms the presence of the triazole-tethered iron species on the surface. These systems are currently being analyzed for photocatalytic activity for H2 production. Graphene p-stacked catalyst manifolds were demonstrated as heterogeneous electrocatalysts by adsorption of simple cobalt catalysts onto graphene-coated metal oxide surfaces. These catalysts possess impressive catalytic efficiency for dihydrogen production (TOF > 6,000 s-1) at low overpotentials (~0.3 V versus platinum). Design of photocathode systems incorporating these catalysts on graphene-coated GaP is currently under way. These design methods give access to a nearly unlimited variety of substrates and catalyst systems, making graphene and 'click' manifolds the template for a solar-fueled future.                                                         

Rethinking the heterogenization of photocathode systems: Novel methods for catalyst functionalization of semiconductors and applications in photoelectrocatalysis

248th National Meeting (2014)

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