Investigation of critical effects in formic acid decomposition over highly dispersed gold catalysts by means of theoretical chemistry

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This project focuses on dehydrogenation of formic acid on the catalysts based on hybrid Au/oxide systems. This reaction has the high technological potential with respect to H2-technology and sustainableenergy concept on the background.Au subnanometer- and nanometer-sized clusters and particles dispersed on oxide supports decompose selectively formic acid (HCOOH-> CO2 + H2) to provide pure H2 already at low temperatures. Prerequisite for an application of formic acid as a hydrogen source in proton-exchange membrane fuel cells (PEM FCs) is to significantly improve the efficiency of the current catalysts. To rationalize a successful strategy towards remarkably advanced catalysts is difficult, if not impossible, due to limited understanding of mechanistic principles controlling the catalytic behavior. With this respect, mainly to shed more light on the atomic scale level structure-catalytic function relationship is crucial.I propose to use methods of modern quantum chemistry in order to understand key effects operating in gas phase decomposition of formic acid over Au/oxide catalysts. Analysis of these effects will provide a platform on which the progressive strategy for advanced processing of the H2 release within the selective formic acid decomposition will be outlined. Benefits of prospective outcomes will not be limited to only the particular reactions, however, they will also supplement a fundamental understanding of the activity of nanostructured gold as versatile catalysts of redox-oxidation reactions.Optimizations of geometry and electronic structures by first-principles methods mainly based on periodical density functional theory (DFT) will be extended by kinetic Monte Carlo simulations in order to model reaction kinetic under realistic conditions. In addition, specific attention will be given to an establishment of a link between active sites in the models and those on real catalysts. Regarding to this aim I will address a probe molecule approach.A part of the project will be dedicated to methodology evaluation. In particular, capability of the applied first-principles methods to treat weak interactions between molecule and catalysts will be a subject of the examination. Potential corrections will be developed. To accomplish this task high-quality benchmarks relevant for the considered systems is prerequisite. Therefore I will make an attempt to implement high-level wavefunction-based methods into the models.