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Volume 188, 2016
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A unified view on heterogeneous and homogeneous catalysts through a combination of spectroscopy and quantum chemistry

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Identifying catalytically active structures or intermediates in homogeneous and heterogeneous catalysis is a formidable challenge. However, obtaining experimentally verified insight into the active species in heterogeneous catalysis is a tremendously challenging problem. Many highly advanced spectroscopic and microscopic methods have been developed to probe surfaces. In this discussion we employ a combination of spectroscopic methods to study two closely related systems from the heterogeneous (the silica-supported vanadium oxide VOx/SBA-15) and homogeneous (the complex K[VO(O2)Hheida]) domains. Spectroscopic measurements were conducted strictly in parallel for both systems and consisted of oxygen K-edge and vanadium L-edge X-ray absorption measurements in conjunction with resonance Raman spectroscopy. It is shown that the full information content of the spectra can be developed through advanced quantum chemical calculations that directly address the sought after structure–spectra relationships. To this end we employ the recently developed restricted open shell configuration interaction theory together with the time-dependent theory of electronic spectroscopy to calculate XAS and rR spectra respectively. The results of the study demonstrate that: (a) a combination of several spectroscopic techniques is of paramount importance in identifying signature structural motifs and (b) quantum chemistry is an extremely powerful guide in cross connecting theory and experiment as well as the homogeneous and heterogeneous catalysis fields. It is emphasized that the calculation of spectroscopic observables provides an excellent way for the critical experimental validation of theoretical results.

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The article was received on 25 Nov 2015, accepted on 04 Jan 2016 and first published on 04 Jan 2016

Article type: Paper
DOI: 10.1039/C5FD00193E
Citation: Faraday Discuss., 2016,188, 181-197
  • Open access: Creative Commons BY license
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    A unified view on heterogeneous and homogeneous catalysts through a combination of spectroscopy and quantum chemistry

    D. Maganas, A. Trunschke, R. Schlögl and F. Neese, Faraday Discuss., 2016, 188, 181
    DOI: 10.1039/C5FD00193E

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