Visualizing Dynamic Single Atom Catalysis.

Many industrial chemical processes, including for producing fuels, foods, pharmaceuticals, chemicals and environmental controls, employ heterogeneous solid state catalysts at elevated temperatures in gas or liquid environments. Dynamic reactions at the atomic level play a critical role in catalyst stability and functionality. In situ visualization and analysis of atomic-scale processes in real time under controlled reaction environments can provide important insights into practical frameworks to improve catalytic processes and materials.

Environmental STEM Study of the Oxidation Mechanism for Iron and Iron Carbide Nanoparticles.

The oxidation of solution-synthesized iron (Fe) and iron carbide (FeC) nanoparticles was studied in an environmental scanning transmission electron microscope (ESTEM) at elevated temperatures under oxygen gas. The nanoparticles studied had a native oxide shell present, that formed after synthesis, an ~3 nm iron oxide (FeO) shell for the Fe nanoparticles and ~2 nm for the FeC nanoparticles, with small void areas seen in several places between the core and shell for the Fe and an ~0.8 nm space between the core and shell for the FeC.

Visualizing single atom dynamics in heterogeneous catalysis using analytical environmental scanning transmission electron microscopy.

Progress is reported in analytical environmental scanning transmission electron microscopy (ESTEM) for visualizing and analysing in real-time dynamic gas-solid catalyst reactions at the single-atom level under controlled reaction conditions of gas environment and temperature. The recent development of the ESTEM advances the capability of the established ETEM with the detection of fundamental single atoms, and the associated atomic structure of selected solid-state heterogeneous catalysts, in catalytic reactions in their working state. The new data provide improved understanding of dynamic atomic processes and reaction mechanisms, in activity and deactivation, at the fundamental level; and in the chemistry underpinning important technological processes.

Atom-by-atom analysis of sintering dynamics and stability of Pt nanoparticle catalysts in chemical reactions.

Supported Pt nanoparticles are used extensively in chemical processes, including for fuel cells, fuels, pollution control and hydrogenation reactions. Atomic-level deactivation mechanisms play a critical role in the loss of performance. In this original research paper, we introduce real-time in-situ visualization and quantitative analysis of dynamic atom-by-atom sintering and stability of model Pt nanoparticles on a carbon support, under controlled chemical reaction conditions of temperature and continuously flowing gas.

Single Atom Dynamics in Chemical Reactions.

Many heterogeneous chemical reactions involve gases catalyzed over solid surfaces at elevated temperatures and play a critical role in the production of energy, healthcare, pollution control, industrial products, and food. These catalytic reactions take place at the atomic level, with active structures forming under reaction conditions. A fundamental understanding of catalysis at the single atom resolution is therefore a major advance in a rational framework upon which future catalytic processes can be built.

Influence of gas environment and heating on atomic structures of platinum nanoparticle catalysts for proton-exchange membrane fuel cells.

Atomic-scale relaxations of platinum nanoparticles (Pt NPs) for fuel-cell catalysts are evaluated by spherical-aberration corrected environmental transmission electron microscopy (ETEM) under reference high-vacuum and N atmospheres, and then under reactive H, CO and O atmospheres, combined with ex situ durability test using an electrochemical half-cell. In high-vacuum, increasing roughness due to continuous relaxation of surface-adsorbed Pt atoms is quantified in real-space. Under H and N atmospheres at a critical partial pressure of 1 × 10 Pa the stability of the surface facets is for the first time found to be improved.

Visualizing the Cu/Cu2(O) Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy.

Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.

Strain Field in Ultrasmall Gold Nanoparticles Supported on Cerium-Based Mixed Oxides. Key Influence of the Support Redox State.

Using a method that combines experimental and simulated Aberration-Corrected High Resolution Electron Microscopy images with digital image processing and structure modeling, strain distribution maps within gold nanoparticles relevant to real powder type catalysts, i.e., smaller than 3 nm, and supported on a ceria-based mixed oxide have been determined.

Dynamic wet-ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere.

The gas injection line of the latest spherical aberration-corrected environmental transmission electron microscope has been modified for achieving real-time/atomic-scale observations in moisturised gas atmospheres for the first time. The newly developed Wet-TEM system is applied to platinum carbon electrode catalysts to investigate the effect of water molecules on the platinum/carbon interface during deactivation processes such as sintering and corrosion. Dynamic in situ movies obtained in dry and 24% moisturised nitrogen environments visualize the rapid rotation, migration and agglomeration of platinum nanoparticles due to the physical adsorption of water and the hydroxylation of the carbon surface.

Imaging nanostructural modifications induced by electronic metal-support interaction effects at Au||cerium-based oxide nanointerfaces.

A variety of advanced (scanning) transmission electron microscopy experiments, carried out in aberration-corrected equipment, provide direct evidence about subtle structural changes taking place at nanometer-sized Au||ceria oxide interfaces, which agrees with the occurrence of charge transfer effects between the reduced support and supported gold nanoparticles suggested by macroscopic techniques. Tighter binding of the gold nanoparticles onto the ceria oxide support when this is reduced is revealed by the structural analysis. This structural modification is accompanied by parallel deactivation of the CO chemisorption capacity of the gold nanoparticles, which is interpreted in exact quantitative terms as due to deactivation of the gold atoms at the perimeter of the Au||cerium oxide interface.

On the structural origin of the catalytic properties of inherently strained ultrasmall decahedral gold nanoparticles.

A new mechanism for reactivity of multiply twinned gold nanoparticles resulting from their inherently strained structure provides a further explanation of the surprising catalytic activity of small gold nanoparticles. Atomic defect structural studies of surface strains and quantitative analysis of atomic column displacements in the decahedral structure observed by aberration corrected transmission electron microscopy reveal an average expansion of surface nearest neighbor distances of 5.6%, with many strained by more than 10%.

Specific surface area and three-dimensional nanostructure measurements of porous titania photocatalysts by electron tomography and their relation to photocatalytic activity.

Various porous titania photocatalysts are analyzed three-dimensionally in real space by electron tomography. Shapes and three-dimensional (3D) distributions of fine pores and silver (Ag) particles (2 nm in diameter) within the pores are successfully reconstructed from the 3D data. Electron tomography is applied for measuring the specific surface area of the porous structures including open and closed porosity.

Probing structures of nanomaterials using advanced electron microscopy methods, including aberration-corrected electron microscopy at the Angstrom scale.

Structural and compositional studies of nanomaterials of technological importance have been carried out using advanced electron microscopy methods, including aberration-corrected transmission electron microscopy (AC-TEM), AC-high angle annular dark field scanning TEM (AC-HAADF-STEM), AC-energy filtered TEM, electron-stimulated energy dispersive spectroscopy in the AC-(S)TEM and high-resolution TEM (HRTEM) with scanning tunneling microscopy (STM) holder. The AC-EM data reveal improvements in resolution and minimization in image delocalization. A JEOL 2200FS double-AC field emission gun TEM/STEM operating at 200 kV in the Nanocentre at the University of York has been used to image single metal atoms on crystalline supports in catalysts, grain boundaries in nanotwinned metals, and nanostructures of tetrapods.

Advances in atomic resolution in situ environmental transmission electron microscopy and 1A aberration corrected in situ electron microscopy.

Advances in atomic resolution in situ environmental transmission electron microscopy for direct probing of gas-solid reactions, including at very high temperatures (approximately 2000 degrees C) are described. In addition, recent developments of dynamic real time in situ studies at the Angstrom level using a hot stage in an aberration corrected environment are presented. In situ data from Pt/Pd nanoparticles on carbon with the corresponding FFT/optical diffractogram illustrate an achieved resolution of 0.