Operando time-gated Raman spectroscopy of solid catalysts

Robin Vogel; P. Tim Prins; Freddy T. Rabouw; Bert M. Weckhuysen

doi:10.1039/d3cy00967j

Operando time-gated Raman spectroscopy of solid catalysts

Robin Vogel, P. Tim Prins, Freddy T. Rabouw, Bert M. Weckhuysen^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Operando Raman spectroscopy is a powerful analytical tool to provide new insights in the working and deactivation principles of solid catalysts. Intense fluorescence can obscure Raman spectra to the extent that they become uninterpretable. Time-gated Raman spectroscopy, based on pulsed excitation and time-gated detection, suppresses background fluorescence based on its slower time dynamics compared to Raman scattering. In this work, we demonstrate and quantify the benefit of time gating for operando Raman spectroscopy, using the propane dehydrogenation reaction over Pt-Sn-based catalyst materials as a case study. Experimental time-gated Raman spectroscopy data are fitted to a time-trace model that is used to optimize time gating for the maximum signal-to-background-noise ratio. Time-gated Raman spectra of a spent propane dehydrogenation catalyst material show lower background fluorescence compared to the time-integrated Raman spectra counterparts. Simultaneous operando time-gated and time-integrated Raman spectroscopy experiments demonstrate the benefit of time gating to obtain more distinct Raman features, especially in the early coking stages where spectra are dominated by background fluorescence.

Original language	English
Pages (from-to)	6366–6376
Number of pages	11
Journal	Catalysis Science and Technology
Volume	13
Issue number	22
Early online date	Sept 2023
DOIs	https://doi.org/10.1039/d3cy00967j
Publication status	Published - 21 Nov 2023

Bibliographical note

Publisher Copyright:
© 2023 The Royal Society of Chemistry

Funding

BMW acknowledges financial support for this project from the TKI (Top Consortia for Knowledge and Innovation) for Chemistry and BASF, as well as the Netherlands Organization for Scientific Research (NWO) in the frame of the Gravitation program Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC). Thimo Jacobs (Utrecht University, UU) is acknowledged for his help with the confocal Raman microscopy measurements. Dr. Stefan Kotrel (BASF) is acknowledged for his useful advice and stimulating discussions.

Funders	Funder number
MCEC
Netherlands Center for Multiscale Catalytic Energy Conversion
BASF
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Topconsortium voor Kennis en Innovatie

Keywords

In-situ
Fluorescence
Dehydrogenation
Stability
Sers

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d3cy00967jFinal published version, 2.88 MBLicence: CC BY

Cite this

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AU - Rabouw, Freddy T.

AU - Weckhuysen, Bert M.

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Y1 - 2023/11/21

N2 - Operando Raman spectroscopy is a powerful analytical tool to provide new insights in the working and deactivation principles of solid catalysts. Intense fluorescence can obscure Raman spectra to the extent that they become uninterpretable. Time-gated Raman spectroscopy, based on pulsed excitation and time-gated detection, suppresses background fluorescence based on its slower time dynamics compared to Raman scattering. In this work, we demonstrate and quantify the benefit of time gating for operando Raman spectroscopy, using the propane dehydrogenation reaction over Pt-Sn-based catalyst materials as a case study. Experimental time-gated Raman spectroscopy data are fitted to a time-trace model that is used to optimize time gating for the maximum signal-to-background-noise ratio. Time-gated Raman spectra of a spent propane dehydrogenation catalyst material show lower background fluorescence compared to the time-integrated Raman spectra counterparts. Simultaneous operando time-gated and time-integrated Raman spectroscopy experiments demonstrate the benefit of time gating to obtain more distinct Raman features, especially in the early coking stages where spectra are dominated by background fluorescence.

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KW - In-situ

KW - Fluorescence

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KW - Stability

KW - Sers

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Operando time-gated Raman spectroscopy of solid catalysts

Abstract

Bibliographical note

Funding

Keywords

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