<br/>Microkinetic modeling involves simulating the rates of chemical reactions at the level of elementary step chemical changes,  which are the smallest molecular level chemical changes in a reaction mechanism. In work led by ORNL that began in 2016, Savara <i>et. al.</i> reported the first micro-kinetic modeling of liquid-solid catalytic benzylic alcohol oxidation over Pd metal nanoparticles, and in 2017 extended this work to AuPd metal nanoparticles to identify which reaction steps led to changes in selectivity after incorporation of Au into the metal nanoparticles. The micro-kinetic modelling was accurate enough to apply the concept of a sticking coefficient in solution, and the 2016 publication may be the first study to show consistency with a realistic sticking coefficient for microkinetic modeling in a liquid-solid heterogeneous catalysis reaction. The microkinetic modelling in the 2017 publication showed that the reason that adding Au  changes the selectivity is due to Au reducing the oxygen adsorption properties, based one the change in 1 out of 11 fitted rate constants.  Density functional theory calculations validated this weaker oxygen interaction with AuPd. The simulations produced all 18 trends observed in the responses of the six products when varying the alcohol concentration, oxygen pressure, and temperature. These studies provide greater mechanistic understanding of the chemical reaction network, and enable prediction of which products will form, and at what rates, for arbitrary conditions.<br/>

Microkinetic modeling and molecular origin of the selectivity differences between palladium and gold–palladium in benzyl alcohol oxidation

254th National Meeting (2017)

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