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ナノ構造材料 電子顕微鏡

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          日本顕微鏡学会, 応用物理学会

          Research Center for Energy and Environmental Materials (GREEN)
          Title

          In situ TEM observation by using a specimen holder

          Keywords

          Transmission electron microscopy, In situ observation, Catalyst

          Overview

          The properties of materials are closely linked to their microstructures, making microstructural analysis essential in materials research and development. Transmission electron microscopy (TEM) is a powerful technique that enables the observation and analysis of material structures and behavior at the atomic level. However, because TEM uses an electron beam, specimens must be placed in a vacuum, meaning that observations are made under conditions far removed from the environments in which materials are actually used. This has created a demand for in situ TEM techniques, which allow observation under conditions close to real operating environments. Catalysts, for example, which are attracting attention as a solution to environmental and energy problems, are often used in gas atmospheres at high temperatures. To enable in situ observation of such catalytic materials, our group has developed an in situ observation system based on TEM specimen holders. Because the specimen holder is independent of a microscope itself, it can be flexibly developed and modified to suit the target of observation. Furthermore, recent advances in microfabrication technology have made it possible to integrate multiple components into the holder tip, only a few mm thick, to create a variety of environmental conditions. By combining this system with various TEM observation and analysis techniques, we can observe and measure catalysts from multiple perspectives and capture changes in their microstructure and composition under operating conditions. Through this approach, we aim to elucidate the reaction and degradation mechanisms that hold the key to improving the efficiency, durability, and cost-effectiveness of catalysts.

          Novelty and originality

          ・Differential pumping mechanism integrated into the TEM specimen holder, maintaining a gas atmosphere around the specimen ・Membrane-free design eliminates electron scattering by a membrane, advantageous for electron energy-loss spectroscopy (EELS) and electron holography ・In situ observation and analysis of catalyst structure, composition, chemical bonding states, and valence states

          Details

          image
          To enable in situ TEM observation of gas-phase reaction catalysts, we have developed a gas-heating specimen holder. While many commercially available holders use membranes, our holder creates a gas atmosphere without a membrane by means of differential pumping. With the TEM specimen holder, specimens can be observed while being heated up to 1000 °C in a gas atmosphere of 20 Pa. Furthermore, as there is no electron scattering by a membrane, chemical state analysis and phase measurements performed in the TEM are unaffected by a membrane. This allows us to combine TEM and scanning TEM (STEM) observation and electron diffraction with electron energy-loss spectroscopy (EELS) and electron holography, enabling local analysis not only of changes in the microstructure of catalyst particles but also of their composition, chemical bonding states, valence states, and oxidation/reduction states. Using the developed holder system, we observed the “rooted catalyst” Ni#Y₂O₃, developed at NIMS, in which two phases, a Ni catalyst and a Y₂O₃ support, are intertwined in a string-like structure. We found that, unlike conventional supported Ni catalyst particles, the rooted catalyst remains structurally and chemically stable during the methane conversion reaction, and revealed that this stability is the reason the reaction is sustained over long periods.

          Summary

          We have developed an in situ TEM observation system that enables specimens to be observed while being heated in a gas atmosphere. Although the system was designed for the observation of catalytic materials, it is expected to be applicable to the observation of metallic and ceramic materials as well. Beyond heating in a gas atmosphere, the system can also be extended to electrical property measurements and switching gas species during observation, and we will continue to expand its range of applications.
          この機能は所内限定です。
          この機能は所内限定です。

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