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      New advances in using Raman spectroscopy for the characterization of catalysts and catalytic reactions

      1 , 2 , 3 , 4
      Chemical Society Reviews
      Royal Society of Chemistry (RSC)

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          Abstract

          Besides new methods this review highlights developments in signal enhancement, the types of information available from Raman spectra and their theoretical description, the application to working catalysts ( operando), as well as future directions.

          Abstract

          Gaining insight into the mode of operation of heterogeneous catalysts is of great scientific and economic interest. Raman spectroscopy has proven its potential as a powerful vibrational spectroscopic technique for a fundamental and molecular-level characterization of catalysts and catalytic reactions. Raman spectra provide important insight into reaction mechanisms by revealing specific information on the catalysts’ (defect) structure in the bulk and at the surface, as well as the presence of adsorbates and reaction intermediates. Modern Raman instrumentation based on single-stage spectrometers allows high throughput and versatility in design of in situ/operando cells to study working catalysts. This review highlights major advances in the use of Raman spectroscopy for the characterization of heterogeneous catalysts made during the past decade, including the development of new methods and potential directions of research for applying Raman spectroscopy to working catalysts. The main focus will be on gas–solid catalytic reactions, but (photo)catalytic reactions in the liquid phase will be touched on if it appears appropriate. The discussion begins with the main instrumentation now available for applying vibrational Raman spectroscopy to catalysis research, including in situ/operando cells for studying gas–solid catalytic processes. The focus then moves to the different types of information available from Raman spectra in the bulk and on the surface of solid catalysts, including adsorbates and surface depositions, as well as the use of theoretical calculations to facilitate band assignments and to describe (resonance) Raman effects. This is followed by a presentation of major developments in enhancing the Raman signal of heterogeneous catalysts by use of UV resonance Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS), and shell-isolated nanoparticle surface-enhanced Raman spectroscopy (SHINERS). The application of time-resolved Raman studies to structural and kinetic characterization is then discussed. Finally, recent developments in spatially resolved Raman analysis of catalysts and catalytic processes are presented, including the use of coherent anti-Stokes Raman spectroscopy (CARS) and tip-enhanced Raman spectroscopy (TERS). The review concludes with an outlook on potential future developments and applications of Raman spectroscopy in heterogeneous catalysis.

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          Raman spectroscopy as a versatile tool for studying the properties of graphene

          Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
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            Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals.

            When used as a photocatalyst, titanium dioxide (TiO(2)) absorbs only ultraviolet light, and several approaches, including the use of dopants such as nitrogen, have been taken to narrow the band gap of TiO(2). We demonstrated a conceptually different approach to enhancing solar absorption by introducing disorder in the surface layers of nanophase TiO(2) through hydrogenation. We showed that disorder-engineered TiO(2) nanocrystals exhibit substantial solar-driven photocatalytic activities, including the photo-oxidation of organic molecules in water and the production of hydrogen with the use of a sacrificial reagent.
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              Present and Future of Surface-Enhanced Raman Scattering

              The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.
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                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                CSRVBR
                Chemical Society Reviews
                Chem. Soc. Rev.
                Royal Society of Chemistry (RSC)
                0306-0012
                1460-4744
                March 15 2021
                2021
                : 50
                : 5
                : 3519-3564
                Affiliations
                [1 ]Eduard-Zintl-Institut für Anorganische und Physikalische Chemie
                [2 ]Technische Universität Darmstadt
                [3 ]Darmstadt
                [4 ]Germany
                Article
                10.1039/D0CS01059F
                33501926
                e645bdb1-b1d7-4d42-93d1-581819cf5bf9
                © 2021

                http://rsc.li/journals-terms-of-use

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