During the past few years, substantial effort has been devoted to developing new experimental techniques capable of delivering atomic-scale information on surfaces and nanoparticles under catalytic reaction conditions. Since the advent of surface science, pioneering experiments under highly idealized conditions have been performed (at very low gas pressures, <10−6 mbar), and idealized model material systems (e.g., single crystals) have been investigated. However, understanding chemical reactions on singlecrystal surfaces close to ultrahigh vacuum does not always enable prediction of the performance of nanoparticles operating at gas pressures near or above atmospheric pressure. Therefore, this MRS Bulletin issue focuses on the capabilities of atomic-scaleresolution, high-gas-pressure- and high-temperature-compatible in situ probes sensitive to the structure, chemical composition, and dynamical properties of nanomaterials. It will be demonstrated how novel in situ techniques enable one to bridge the combined pressure and materials gaps from ultrahigh vacuum to atmospheric pressures and from metal single-crystal surfaces to nanoparticles or oxides.

Catalytic reactions occurring at metal surfaces and nanoparticles have been an established research field for decades, yielding information on adsorption sites and reaction pathways under ultrahigh-vacuum conditions. Recent experimental developments have made it possible to perform well-controlled in situ surface x-ray diffraction measurements from single-crystal surfaces and nanoparticles under industrially relevant conditions. In this way, a new understanding of atomic-scale processes at surfaces and nanoparticles occurring during catalytic reactions under realistic conditions has been gained. In particular, the identification of the formation of thin oxides on model catalysts and their role in oxidation reactions demonstrates the importance of in situ probes under relevant conditions.

“Looking” on the other side of the pressure gap in heterogeneous catalysis is an essential step in identifying and understanding differences and similarities between the behavior of catalysts under actual operation conditions (operando) and under the nearvacuum conditions of traditional laboratory experiments. In this article, we demonstrate that real-space, atomic-scale imaging of active catalyst surfaces is possible under realistic or semirealistic reaction conditions with the reactor-STM, a scanning tunneling microscope that is fully integrated with a miniature flow reactor and housed inside an ultrahigh-vacuum system. This special-purpose instrument combines the merits of standard surface-science methods with operando STM observations of model catalysts in action. We illustrate the strength of this microscope with examples of CO oxidation on platinum surfaces.

X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst's chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, that is, in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces.

The surface specificity of vibrational sum frequency generation (VSFG) spectroscopy allows one to characterize adsorbed and reacting molecules on catalyst surfaces while the catalyst functions at high pressure and high temperature. VSFG spectroscopy can be carried out in different modes, including scanning, broadband, time-resolved, and polarization-dependent, and has been applied to various active surfaces. Single-crystal and nanoparticle model catalysts have mostly been used, which are typically prepared under ultrahigh vacuum, but applications to powder materials have been reported recently. In this article, the fundamentals and technical aspects of VSFG are summarized, and its benefits are illustrated by case studies of elementary processes of heterogeneous catalysis.

X-ray absorption fine structure (XAFS) spectroscopy probes the structure and electronic properties of metal centers. Because it can be applied to noncrystalline materials, it is a key technique for probing nanoparticulate materials, such as colloidal and heterogeneous metal catalysts. The high brilliance of modern synchrotron radiation x-ray sources facilitates in situ studies, which provide direct structure–function relationships with both spatial and time resolution; this is especially effective when applied in combination with complementary techniques such as x-ray diffraction, mass spectrometry, and optical or vibrational spectroscopies. Tracking the particle formation of platinum-group metal catalysts, their behavior under reaction conditions, and the distribution of sites within a catalyst bed shows that this approach is essential for understanding the chemistry of these nanoparticles. Rather than behave as monolithic entities, nanoparticulate catalysts undergo rapid structural transformations induced by the gas environment and reaction conditions, and their lifetimes as catalysts depend on the reversibility of these changes.

Advances in atomic-resolution environmental transmission electron microscopy (ETEM) and related techniques for probing gas–solid reactions in situ are described. The capabilities of ETEM allow the dynamic nanostructure of heterogeneous catalysts in their functioning states to be directly monitored in real time. Applications of ETEM in catalysis are outlined, and they illustrate significant new insights into the dynamic nanostructure of the catalyst materials and their modes of operation.