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Operando monitoring of temperature and active species at the single catalyst particle level

Abstract

The development of improved catalysts requires insights into the relationship between catalytic activity and catalyst structure, including the underlying reaction mechanism. Here, we demonstrate a unique set of catalyst extrudate sensors that allow for the simultaneous detection of local temperature by luminescence thermometry, and of surface species by shell-isolated nanoparticle-enhanced Raman spectroscopy. This sensing approach was applied to the characterization of direct conversion of syngas into hydrocarbons and C2+ oxygenates over supported Rh and RhFe catalysts. Luminescence thermometry demonstrated a mismatch between the set temperature and the local catalyst temperature, with variations up to 40 °C. Furthermore, by investigating the surface species on varying extrudate and catalyst compositions, we identified tilted carbonyl species on the Rh/SiO2 interface that are probable precursors for the hydrogen-assisted CO dissociation. The implementation of extrudate catalyst sensors as a characterization tool provides a unique approach towards the further understanding of the relevant parameters in catalysis.

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Fig. 1: Schematic illustration of a catalyst extrudate sensor for operando spectroscopy research.
Fig. 2: Electron microscopy images of the nanoparticle sensors and catalysts.
Fig. 3: Temperature-dependent luminescence of NaYF4:Er3+,Yb3+.
Fig. 4: Combined operando luminescence thermometry with SHINERS and online MS.
Fig. 5: Rh-catalysed CO hydrogenation pathways.
Fig. 6: Catalyst–support interface probed with SHINERS during CO hydrogenation at 250 °C.
Fig. 7: Altering product selectivity of Rh catalysts by Fe alloying for CO hydrogenation at 250 °C.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the Netherlands Center for Multiscale Catalytic Energy Conversion, an Netherlands Organization for Scientific Research Gravitation programme funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We thank the Netherlands Organization for Scientific Research and Shell Global Solutions in the framework of the Chemical Innovation Partnership Project for financial support. We gratefully acknowledge A. Meijerink (Utrecht University, UU) for his valuable input and discussions. We thank N. Krans (UU) for her contributions to the TEM-EDX measurements, I. ten Have (UU) for her contributions to the SEM measurements and S. van Vreeswijk (UU) and R. Oord (UU) for their help with the GC measurements.

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The manuscript was written with contributions of all authors. All authors have given approval to the final version of the manuscript. T.H., R.G.G. and B.M.W. conceived and designed the experiments. NaYF4@SiO2 NPs were prepared by R.G.G. and were used by G.T.W. to form extrudates. T.H prepared and deposited Au@SiO2 and Au@TiO2 SHINs with Rh on the extrudates. The operando experiments were performed by T.H. and R.G.G.

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Correspondence to Bert M. Weckhuysen.

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Hartman, T., Geitenbeek, R.G., Whiting, G.T. et al. Operando monitoring of temperature and active species at the single catalyst particle level. Nat Catal 2, 986–996 (2019). https://doi.org/10.1038/s41929-019-0352-1

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