Investigating how to control the carbon affinity and the degrees of activation of olefins and aromatics is of vital interest to the production of fuels and chemicals from petroleum and biomass feedstock. Transition metal ceramics -- oxides, carbides, nitrides, sulfides, phosphides, and selenides -- present interesting and unique surface chemistry that is of catalytic interest in many contemporary reactions. These materials can exhibit surface chemistry similar to noble metals or wholly new reactivity that can provide new avenues for chemical transformations. The aim of these studies is to understand how to promote the scission of a recalcitrant C–O bond and how to control or limit the activation of valuable C=C bonds via a systematic investigation of the surface and catalytic chemistry of transition metal ceramic catalysts. Utilizing a deoxygenation reaction as a probe (i.e. guaiacol and phenol), we have investigated the innate surface chemistry of 1st row transition metal phosphides and Ti and Ni ceramics in promoting recalcitrant phenolic C–O bond cleavage and limiting the unselective activation and hydrogenation of C=C bonds. Clear systematic trends have developed that connect the surface reactivity, surface reaction mechanism energetics, and reaction site composition to the bulk electronic structure and physical properties of the constituent element within the ceramics. In this presentation, we will discuss how the surface termination and the stability of ceramics can be affected under specific reaction conditions; how the oxophilicity of the ceramics trend and contribute to C–O bond dissociation; and how the activation of C=C bonds and van der Waals dispersion interactions can be systematically tuned.

Systematic understandings of surface reactivity of ceramics to promote C–O bond cleavage and control C=C double bond activation

253rd National Meeting (2017)

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