Approaches for tuning selectivity in catalytic reactions at surfaces will be described using the examples of deoxygenation and olefin-metathesis on Mo2C, and asymmetric hydrogenation on Pt. Results of surface spectroscopy investigations of the selective deoxygenation of ketones and aldehydes on bulk molybdenum carbide will be presented. Selective deoxygenation of carbonyl groups on Mo2C leads to the formation of isolated akylidene groups and these in turn are active olefin metathesis initiating sites. Recent advances in experimental techniques and theoretical approaches, such as scanning tunneling microscopy (STM) and density functional theory (DFT), are now providing much needed insight on chemistry occuring at individual catalytic sites. We will present results from a combined STM and DFT study revealing sub-molecularly resolved regiospecific and stereospecific data for isolated bimolecular and termolecular assemblies formed between enantiopure naphthylethylamine and a-ketoesters and a-phenyl ketones on a platinum surface. A hierarchy of metal-molecule and molecule-molecule interactions is found to control the stereochemistry of modifier-substrate complexation.

Single catalytic site studies of selective chemistry on metal catalyst surfaces

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.