In this review, a brief survey is offered on the main nanotechnology synthetic approaches available to heterogeneous catalysis, and a few examples are provided of their usefulness for such applications. We start by discussing the use of colloidal, reverse micelle, and dendrimer chemistry in the production of active metal and metal oxide nanoparticles with well-defined sizes, shapes, and compositions, as a way to control the surface atomic ensembles available for selective catalysis. Next we introduce the use of sol–gel and atomic layer deposition chemistry for the production and modification of high-surface-area supports and active phases. Reference is then made to the more complex active sites that can be created or carved on such supports by using organic structure-directing agents. We follow with an examination of the ability to achieve multiple functionality in catalysis via the design of dumbbells, core@shell, and other complex nanostructures. Finally, we consider the mixed molecular-nanostructure approach that can be used to develop more demanding catalytic sites, by derivatizing the surface of solids or tethering or immobilizing homogeneous catalysts or other chemical functionalities. We conclude with a personal and critical perspective on the importance of fully exploiting the synergies between nanotechnology and surface science to optimize the search for new catalysts and catalytic processes.

Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection–absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are introduced.

Colloidal and sol-gel procedures have been used to prepare heterogeneous catalysts consisting of platinum metal particles with narrow size distributions and well defined shapes dispersed on high-surface-area silica supports. The overall procedure was developed in three stages. First, tetrahedral and cubic colloidal metal particles were prepared in solution by using a procedure derived from that reported by El-Sayed and coworkers [Ahmadi TS, Wang ZL, Green TC, Henglein A, El-Sayed MA (1996) Science 272:1924-1926]. This method allowed size and shape to be controlled independently. Next, the colloidal particles were dispersed onto high-surface-area solids. Three approaches were attempted: (i) in situ reduction of the colloidal mixture in the presence of the support, (ii) in situ sol-gel synthesis of the support in the presence of the colloidal particles, and (iii) direct impregnation of the particles onto the support. Finally, the resulting catalysts were activated and tested for the promotion of carbon-carbon double-bond cis-trans isomerization reactions in olefins. Our results indicate that the selectivity of the reaction may be controlled by using supported catalysts with appropriate metal particle shapes.