Metal Nanoparticle Catalysts Beginning to Shape-up
Abbreviated Journal Title
Accounts Chem. Res.
HIGH-INDEX FACETS; HETEROGENEOUS CATALYSIS; PLATINUM NANOCRYSTALS; PALLADIUM NANOCRYSTALS; STRUCTURE SENSITIVITY; PD NANOPARTICLES; ACTIVE-SITE; OXIDATION; HYDROGENATION; SIZE; Chemistry, Multidisciplinary
The field of heterogeneous catalysis has received a remarkable amount of interest from scientific and industrial perspectives because of its enormous impact on the world's economy: more than 90% of chemical manufacturing processes use catalysts. Catalysts are also essential in converting hazardous waste into less harmful products (car exhaust) and in generating power (fuel cells). Yet in all applications, it remains a challenge to design long lasting, highly active, selective, and environmentally friendly catalytic materials and processes, ideally based on Earth-abundant elements. In addition, the field needs more satisfactory experimental and theoretical approaches to minimize trial and error experiments in catalyst development. Nanocatalysis is one area that is developing rapidly. Researchers have reported striking novel catalytic properties, including greatly enhanced reactivities and selectivities, for nanocatalysts compared to their bulk counterparts. Fully harnessing the power of nanocatalysts requires detailed understanding of the origin of their enhanced performance at the atomic level, which in turn requires fundamental knowledge of the geometric and electronic structures of these complex systems. Numerous studies report on the properties that affect the catalytic performance of metal naoparticles (NPs) such as their size, interaction with their support, and their oxidation state. Much less research elucidates the role played by the NP shape. Complicating the analysis is that the preceding parameters are not independent, since NP size and support will affect which NP shapes are most stable. In addition, we must consider the dynamic nature of NP catalysts and their response to the environment, since the working state of a NP catalyst might not be the state in which the catalyst was prepared, but rather a structural and/or chemical isomer that responded to the particular reaction conditions. In order to address the complexity of real-world catalysts, researchers must undertake a synergistic approach, taking advantage of a variety of in situ and operando experimental methods. With the continuous shrinking of the scale of material systems, researchers require more sensitive experimental probes and computational approaches that work across a wide range of temperatures and chemical environments. This Account provides examples of recent advances in the preparation and characterization of NP catalysts with well-defined shapes. It discusses how to resolve the shape of nanometer-sized catalysts via a combination of microscopy and spectroscopic approaches, and how to follow their evolution in the course of a chemical reaction. Finally, it highlights that, for structure-sensitive reactions, controlled synthesis can tune catalytic properties such as the reaction rates, onset reaction temperature, activity, and selectivity.
Accounts of Chemical Research
"Metal Nanoparticle Catalysts Beginning to Shape-up" (2013). Faculty Bibliography 2010s. 3846.