(3bv) Design of Catalytic Materials with Targeted Electronic Properties

Catalysis plays an essential role in chemical conversion, energy production and pollution mitigation. Recent development of electronic structure theory leads to an unprecedented mechanistic understanding of molecular transformations at surfaces and the identification of improved catalysts from first-principles. However, the immense phase space of catalytic materials spanned by structural and compositional degrees of freedom precludes thorough screening, even with combinatorial quantum chemical calculations and high-throughput experiments. Development of predictive structure-reactivity relationships for rational design of catalytic materials with targeted electronic properties still remains a great challenge.

During my PhD studies, we have developed a general theoretical framework for the understanding of variations in the surface reactivity of catalytic materials upon a perturbation of their electronic properties. I will discuss our work on three projects: (1) rapid screening of Pt multimetallic electrocatalysts for the oxygen reduction reaction in PEM fuel cells; (2) understanding of alkali promotion mechanisms for oxidation reactions on Ag surfaces; (3) coupling of phonons and energetic electrons for chemical reactions on optically excited nanostructures. Each model system is characterized by one specific type of perturbation of the metal, introduced either by alloying with impurity elements, by doping of substrates with chemical promoters, or by exposing the surface of plasmonic nanostructures to visible photons. The fundamental knowledge-based developed in these studies can be readily applicable to other types of catalytic materials (e.g., oxides, sulfides and carbides) for many energy and environmental applications.