Abstract
In photocatalysis, a set of elemental steps are involved together at different timescales to govern the overall efficiency of the process. These steps are divided as follow: (1) photon absorption and excitation (in femtoseconds), (2) charge separation (femto- to picoseconds), (3) charge carrier diffusion/transport (nano- to microseconds), and (4 and 5) reactant activation/conversion and mass transfer (micro- to milliseconds). The identification and quantification of these steps, using the appropriate tool/technique, can provide the guidelines to emphasize the most influential key parameter that improve the overall efficiency and to develop the “photocatalyst by design” concept. In this review, the identification/quantification of reactant activation/conversion and mass transfer (steps 4 and 5) is discussed in details using the in situ/operando techniques, especially the infrared (IR), Raman, and X-ray absorption spectroscopy (XAS). The use of these techniques in photocatalysis was highlighted by the most recent and conclusive case studies which allow a better characterization of the active site and reveal the reaction pathways in order to establish a structure–performance relationship. In each case study, the reaction conditions and the reactor design for photocatalysis (pressure, temperature, concentration, etc.) were thoroughly discussed. In the last part, some examples in the use of time-resolved techniques (time-resolved FTIR, photoluminescence, and transient absorption) are also presented as an author’s guideline to study the elemental steps in photocatalysis at shorter timescale (ps, ns, and µs).
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Acknowledgements
Mohamad El-Roz and Houeida Issa Hamoud acknowledge the Normandy Region (H2CO2 Project) for the financial support. Lukasz Wolski gratefully acknowledges the Foundation for Polish Science (FNP) (decision no. START 95.2021) and the Polish Minister of Education and Science (decision no. SMN/16/0997/2020) for the financial support. Ilia Pankin acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (State assignment in the field of scientific activity, № 0852-2020-0019).
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This article is part of the Topical Collection “Solar-driven catalysis”; edited by Nicolas Keller, Fernando Fresno, Agnieszka Ruppert and Patricia Garcia-Munoz.
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Issa Hamoud, H., Wolski, L., Pankin, I. et al. In situ and Operando Spectroscopies in Photocatalysis: Powerful Techniques for a Better Understanding of the Performance and the Reaction Mechanism. Top Curr Chem (Z) 380, 37 (2022). https://doi.org/10.1007/s41061-022-00387-5
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DOI: https://doi.org/10.1007/s41061-022-00387-5