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Techniques in catalysis

Photoionization reveals catalytic mechanisms

Nature Catalysis volume 5, pages 850–851 (2022)Cite this article

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Sensitive and isomer-specific analytical tools detect elusive intermediates and reveal reaction mechanisms. Photoelectron photoion coincidence spectroscopy, introduced in 1966, now serves as a reaction microscope, identifies intermediates, and delineates gaseous and surface-confined processes in heterogeneous catalysis.

Reactive intermediates shed light on the mechanism and the function of the active site in catalysis to aid intelligent catalyst design and process optimization. Catalytic cycles may be inferred based on kinetic studies, isotope labelling experiments, and surface-specific approaches, including nuclear magnetic resonance, infrared, ultraviolet (UV)–visible light, UV–Raman, and X-ray spectroscopies. However, key intermediates driving the process chemistry may be short-lived and only present in low concentrations. They are only detectable under operando and in situ conditions and, because of their reactivity, are usually quenched in conventional sampling. This can be overcome by operando photoelectron photoion coincidence (PEPICO) spectroscopy with molecular beam sampling, which has been shown to be a complementary analytical tool to identify such fleeting species in complex reactive mixtures1.

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Fig. 1: Double imaging PEPICO experiment.

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Authors and Affiliations

  1. NCCR Catalysis, Paul Scherrer Institute, Villigen, Switzerland

    Andras Bodi & Patrick Hemberger

  2. NCCR Catalysis, Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich, Switzerland

    Javier Pérez-Ramírez

Authors
  1. Andras Bodi
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  2. Patrick Hemberger
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  3. Javier Pérez-Ramírez
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Correspondence to Andras Bodi.

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The authors declare no competing interests.

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Bodi, A., Hemberger, P. & Pérez-Ramírez, J. Photoionization reveals catalytic mechanisms. Nat Catal 5, 850–851 (2022). https://doi.org/10.1038/s41929-022-00847-7

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