Uniform Catalytic Nanocrystals: From Model Catalysts to Efficient Catalysts

ConspectusSolid catalysts play a key role in the chemical industry, energy, and the environment. Fundamental understanding of heterogeneous catalysis exerted by solid surfaces is useful for structural designs of efficient catalysts but is challenging due to the complexity. Emerging uniform catalytic nanocrystals (NCs) with controlled and well-defined surface structures have brought new opportunities for fundamental understanding and directed explorations of efficient catalysts. In a previous Account ( Acc. Chem. Res. 2016, 49, 520−527), I postulated and exemplified a concept of oxide nanocrystal model catalysts for the fundamental investigations of oxide catalysis without the “materials gap” and “pressure gap” which are often encountered using the traditional single crystal model catalysts. In this Account, I summarize our effort in fabricating efficient uniform nanocrystal catalysts based on the fundamental understanding of structure–activity relations and reaction mechanisms acquired by oxide nanocrystal model catalyst studies. Directed by the fundamental understanding that the Cu2O{110} facet is active in catalyzing propylene epoxidation with O2 and the fine Cu2O nanocube exposes high densities of Cu2O{110} edge sites, we successfully explore fine Cu2O nanocubes as a highly selective catalyst for propylene epoxidation with O2. Directed by the fundamental understanding that the Cu{100} facet is the active Cu facet in catalyzing the water–gas shift (WGS) reaction, we successfully fabricate a highly active ZnO/fine Cu nanocube WGS catalyst with enhanced ZnO-CuCu{100} active site density. Directed by the fundamental understanding of TiO2 facet effects on the surface band bending and adsorbate–surface interfacial energy level alignment, and consequent photocatalytic performance, we successfully fabricate highly active TiO2{001} NC-based photocatalysts for photocatalytic CH4 conversions. These results adequately exemplify the concept of fundamental understanding-directed explorations of efficient catalysts following a strategy of “identification of active site structure + maximization of active site density”, which, together with the advancement of controlled-synthesis methods, is expected to greatly accelerate the explorations of novel and efficient catalysts in future.