Atomic Layer Deposition with TiO2 for Enhanced Reactivity and Stability of Aromatic Hydrogenation Catalysts
Hydrogenation of aromatic molecules in fossil- and bio-derived fuels is essential for decreasing emissions of harmful combustion products and addressing growing concerns around urban air pollution. In this work, we used atomic layer deposition to significantly enhance the hydrogenation performance of a conventional supported Pd catalyst by applying an ultrathin coating of TiO2 in a scalable powder coating process. The TiO2-coated catalyst showed substantial gains in the conversion of multiple aromatic molecules, including a 5-fold improvement in turnover frequency versus the uncoated catalyst in the hydrogenation of naphthalene. This activity enhancement was maintained upon scaling the coating synthesis process from 3 to 100 g. Based on the results from Xray photoelectron spectroscopy, X-ray absorption spectroscopy, and computational modeling, the activity enhancement was attributed to ensemble effects resulting from partial TiO2 coverage of the Pd surface rather than fundamental changes to the Pd electronic structure. Additional durability testing confirmed that the TiO2 coating improved the thermal and hydrothermal stability of the catalyst as well as tolerance toward sulfur impurities in the reactant stream. Using an economic model of an industrial deep hydrogenation process, we found that an increase in catalyst activity or lifetime of 2× would justify even a relatively high estimate for the cost of TiO2 atomic layer deposition coatings at scale