Nanocatalysis: Size- and Shape-dependent Chemisorption and Catalytic Reactivity
This review article focuses on correlating the catalytic reactivity of NPs and their geometry. It illustrated that chemisorption and catalytic properties such as the onset reaction temperature, the activity, and selectivity of a nanocatalyst may be tuned through controlled synthesis of NPs with well-defined sizes and shapes. It has become clear that detailed information on the physical/chemical properties of supported NP systems must be available for the rational design of the next generation of nanosized catalysts. Such NP systems must be representative of active catalysts, and must be sufficiently well-defined ( e.g., with respect to size and shape) to serve as a basis for theoretical modeling. In addition, a synergistic combination of in situ and in operando characterization techniques working under realistic reaction conditions ( e.g. elevated temperatures and high pressure) must be available, since the working state of a NP catalyst might not be the state in which the catalyst was prepared, but a structural and/or chemical isomer that adapted to the particular reaction conditions. In order to address the complexity of real-world catalysts, a synergistic approach taking advantage of a variety of state-of-the-art experimental and theoretical methods must be undertaken. In this review, we have described some of the impressive developments that have been made in these areas. Many serious challenges still remain in the areas of catalyst characterization and design. One such challenge is to design highly active metal NP catalysts using abundant, inexpensive metals which can replace precious metal catalysts. Additionally, there is an increasingly pressing need for catalyst development for energy production applications, such as in fuel cells or for the synthesis of chemicals and fuels. Further work is needed to design more active and selective catalysts for these reactions that are viable at an industrial scale. In the coming years, nanocatalysis research must meet these challenges by building on the work described in this report. Further advancements in developing new synthetic methods will allow increased control over NP structure and stability, allowing for new insights into NP structure-reactivity correlations. In addition, the development of higher resolution in situ and in operando measurement techniques capable of probing catalytic reactions at NP surfaces over an extended range of temperatures and pressures and harsh environmental conditions will give unprecedented insight into NP catalysts in their working state. Single-nanoparticle spectroscopic and catalytic characterization must also be further developed. Advancements in computational modeling of more realistic catalysts will also bring us closer to gaining a molecularlevel view of a reaction at a NP surface when used to complement experimental studies. Such progress will bring us closer to realizing the goal of synthesizing highly effective, tailor-made, tunable nanoparticle catalysts.