Approaches to Exploring Spatio-Temporal Surface Dynamics in Nanoparticles with In Situ Transmission Electron Microscopy.

Many nanoparticles in fields such as heterogeneous catalysis undergo surface structural fluctuations during chemical reactions, which may control functionality. These dynamic structural changes may be ideally investigated with time-resolved in situ electron microscopy. We have explored approaches for extracting quantitative information from large time-resolved image data sets with a low signal to noise recorded with a direct electron detector on an aberration-corrected transmission electron microscope. We focus on quantitatively characterizing beam-induced dynamic structural rearrangements taking place on the surface of CeO2 (ceria). A 2D Gaussian fitting procedure is employed to determine the position and occupancy of each atomic column in the nanoparticle with a temporal resolution of 2.5 ms and a spatial precision of 0.25 Å. Local rapid lattice expansions/contractions and atomic migration were revealed to occur on the (100) surface, whereas (111) surfaces were relatively stable throughout the experiment. The application of this methodology to other materials will provide new insights into the behavior of nanoparticle surface reconstructions that were previously inaccessible using other methods, which will have important consequences for the understanding of dynamic structure-property relationships.

Advanced and In Situ Analytical Methods for Solar Fuel Materials.

In situ and operando techniques can play important roles in the development of better performing photoelectrodes, photocatalysts, and electrocatalysts by helping to elucidate crucial intermediates and mechanistic steps. The development of high throughput screening methods has also accelerated the evaluation of relevant photoelectrochemical and electrochemical properties for new solar fuel materials. In this chapter, several in situ and high throughput characterization tools are discussed in detail along with their impact on our understanding of solar fuel materials.

Analysis of catalytic gas products using electron energy-loss spectroscopy and residual gas analysis for operando transmission electron microscopy.

Operando transmission electron microscopy (TEM) of catalytic reactions requires that the gas composition inside the TEM be known during the in situ reaction. Two techniques for measuring gas composition inside the environmental TEM are described and compared here. First, electron energy-loss spectroscopy, both in the low-loss and core-loss regions of the spectrum was utilized. The data were quantified using a linear combination of reference spectra from individual gasses to fit a mixture spectrum. Mass spectrometry using a residual gas analyzer was also used to quantify the gas inside the environmental cell. Both electron energy-loss spectroscopy and residual gas analysis were applied simultaneously to a known 50/50 mixture of CO and CO2, so the results from the two techniques could be compared and evaluated. An operando TEM experiment was performed using a Ru catalyst supported on silica spheres and loaded into the TEM on a specially developed porous pellet TEM sample. Both techniques were used to monitor the conversion of CO to CO2 over the catalyst, while simultaneous atomic resolution imaging of the catalyst was performed.

Atomic level in situ observation of surface amorphization in anatase nanocrystals during light irradiation in water vapor.

An in situ atomic level investigation of the surface structure of anatase nanocrystals has been conducted under conditions relevant to gas phase photocatalytic splitting of water. The experiments were carried out in a modified environmental transmission electron microscope fitted with a high intensity broadband light source with an illumination intensity of 1430 mW/cm(2) close to 10 suns. When the titania is exposed to light and water vapor, the initially crystalline surface converts to an amorphous phase one to two monolayers thick. Spectroscopic analyses show that the amorphous layer contains titanium in a +3 oxidation state. The amorphous layer is stable and does not increase in thickness with time and is heavily hydroxylated. This disorder layer will be present on the anatase surface under reaction conditions relevant to photocatalytic splitting of water.

System for in situ UV-visible illumination of environmental transmission electron microscopy samples.

A system for illuminating a sample in situ with visible and ultraviolet light inside a transmission electron microscope was devised to study photocatalysts. There are many mechanical and optical factors that must be considered when designing and building such a system. Some of the restrictions posed by the electron microscope column are significant, and care must be taken not to degrade the microscope's electron-optical performance or to unduly restrict the other capabilities of the microscope. We discuss the nature of the design considerations, as well as the practical implementation and characterization of a solution. The system that has been added to an environmental transmission electron microscope includes a high brightness broadband light source with optical filters, a fiber to guide the light to the sample, and a mechanism for precisely aligning the fiber tip.

Chemical kinetics for operando electron microscopy of catalysts: 3D modeling of gas and temperature distributions during catalytic reactions.

In situ environmental transmission electron microscopy (ETEM) is a powerful tool for observing structural modifications taking place in heterogeneous catalysts under reaction conditions. However, to strengthen the link between catalyst structure and functionality, an operando measurement must be performed in which reaction kinetics and catalyst structure are simultaneously determined. To determine chemical kinetics for gas-phase catalysis, it is necessary to develop a reliable chemical engineering model to describe catalysis as well as heat and mass transport processes within the ETEM cell. Here, we establish a finite element model to determine the gas and temperature profiles during catalysis in an open-cell operando ETEM experiment. The model is applied to a SiO2-supported Ru catalyst performing CO oxidation. Good agreement is achieved between simulated compositions and those measured experimentally across a temperature range of 25 - 350 °C. In general, for lower conversions, the simulations show that the temperature and gas are relatively homogeneous within the hot zone of the TEM holder where the catalyst is located. The uniformity of gas and temperature indicates that the ETEM reactor system behavior approximates that of a continuously stirred tank reactor (CSTR). The large degree of gas-phase uniformity also allows one to estimate the catalytic conversion of reactants in the cell to within 10% using electron energy-loss spectroscopy. Moreover, the findings indicate that for reactant conversions below 35%, one can reliably evaluate the steady-state reaction rate of catalyst nanoparticles that are imaged on the TEM grid.

Novel sample preparation for operando TEM of catalysts.

A new TEM sample preparation method is developed to facilitate operando TEM of gas phase catalysis. A porous Pyrex-fiber pellet TEM sample was produced, allowing a comparatively large amount of catalyst to be loaded into a standard Gatan furnace-type tantalum heating holder. The increased amount of catalyst present inside the environmental TEM allows quantitative determination of the gas phase products of a catalytic reaction performed in-situ at elevated temperatures. The product gas concentration was monitored using both electron energy loss spectroscopy (EELS) and residual gas analysis (RGA). Imaging of catalyst particles dispersed over the pellet at atomic resolution is challenging, due to charging of the insulating glass fibers. To overcome this limitation, a metal grid is placed into the holder in addition to the pellet, allowing catalyst particles dispersed over the grid to be imaged, while particles in the pellet, which are assumed to experience identical conditions, contribute to the overall catalytic conversion inside the environmental TEM cell. The gas within the cell is determined to be well-mixed, making this assumption reasonable.