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      Estimation of the molecular vibration of gases using electron microscopy

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          Abstract

          Reactions in gaseous phases and at gas/solid interfaces are widely used in industry. Understanding of the reaction mechanism, namely where, when, and how these gaseous reactions proceed, is crucial for the development of further efficient reaction systems. To achieve such an understanding, it is indispensable to grasp the dynamic behavior of the gaseous molecules at the active site of the chemical reaction. However, estimation of the dynamic behavior of gaseous molecules in specific nanometer-scale regions is always accompanied by great difficulties. Here, we propose a method for the identification of the dynamic behavior of gaseous molecules using an electron spectroscopy observed with a transmission electron microscope in combination with theoretical calculations. We found that our method can successfully identify the dynamic behavior of some gaseous molecules, such as O 2 and CH 4, and the sensitivity of the method is affected by the rigidity of the molecule. The method has potential to measure the local temperature of gaseous molecules as well. The knowledge obtained from this technique is fundamental for further high resolution studies of gaseous reactions using electron microscopy.

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          Vibrational spectroscopy in the electron microscope.

          Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample--that is, for 'aloof' spectroscopy that largely avoids radiation damage.
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            In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation.

            We present atomic-scale, video-rate environmental transmission electron microscopy and in situ time-resolved X-ray photoelectron spectroscopy of surface-bound catalytic chemical vapor deposition of single-walled carbon nanotubes and nanofibers. We observe that transition metal catalyst nanoparticles on SiOx support show crystalline lattice fringe contrast and high deformability before and during nanotube formation. A single-walled carbon nanotube nucleates by lift-off of a carbon cap. Cap stabilization and nanotube growth involve the dynamic reshaping of the catalyst nanocrystal itself. For a carbon nanofiber, the graphene layer stacking is determined by the successive elongation and contraction of the catalyst nanoparticle at its tip.
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              Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions.

              Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.
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                Author and article information

                Contributors
                teru@iis.u-tokyo.ac.jp
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                12 December 2017
                12 December 2017
                2017
                : 7
                : 16434
                Affiliations
                [1 ]ISNI 0000 0001 2151 536X, GRID grid.26999.3d, Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, ; Tokyo, 153-8505 Japan
                [2 ]Hitachi High-Technologies Corporation, 24-14, Nishi-shimbashi 1-chome, Minato-ku, Tokyo, 105-8717 Japan
                Article
                16423
                10.1038/s41598-017-16423-0
                5727207
                1434efdf-027f-45b4-95a0-43b8171781f8
                © The Author(s) 2017

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 10 July 2017
                : 9 November 2017
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