A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In2O3/Al2O3 Catalysts for CO2 Hydrogenation

Matthew E. Potter; Sofia Mediavilla Madrigal; Emma Campbell; Lisa J. Allen; Urvashi Vyas; Stephen Parry; Adrián García-Zaragova; Luis M. Martínez-Prieto; Pascual Oña-Burgos; Mads Lützen; Christian D. Damsgaard; Enrique Rodríguez-Castellón; Nicola Schiaroli; Giuseppe Fornasari; Patricia Benito; Andrew M. Beale

doi:10.1002/anie.202312645

A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In₂O₃/Al₂O₃ Catalysts for CO₂ Hydrogenation

Matthew E. Potter, Sofia Mediavilla Madrigal, Emma Campbell, Lisa J. Allen, Urvashi Vyas, Stephen Parry, Adrián García-Zaragova, Luis M. Martínez-Prieto, Pascual Oña-Burgos, Mads Lützen, Christian D. Damsgaard, Enrique Rodríguez-Castellón, Nicola Schiaroli, Giuseppe Fornasari, Patricia Benito, Andrew M. Beale

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

2 Citations (SciVal)

Abstract

CO₂ hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In₂O₃ (Palldium on Indium Oxide) catalysts show high CO₂ conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In₂O₃ species dispersed on Al₂O₃ can match the performance of pure Pd/In₂O₃ systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.

Original language	English
Article number	e202312645
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	45
DOIs	https://doi.org/10.1002/anie.202312645
Publication status	Published - 6 Nov 2023

Funding

UK Catalysis Hub is kindly thanked for resources and support provided via the membership of the UK Catalysis Hub Consortium and funded by current EPSRC grants: EP/R026939/1 and EP/R026815/1. We thank Diamond Light Source for provision of beam time and support facilities at the beamline B18, under proposal SP30647. We also acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities and we would like to thank Dragos Stoian, Kenneth Marshall, Wouter van Beek and Naomi Lawes for assistance and support in using beamline BM31. This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 101022507. This work was supported by a research grant (9455) from VILLUM FONDEN. ERC and PBM wish to thanks the Spanish Ministry of Science and Innovation, for projects PID2021‐126235OB‐C32 and TED2021‐130756B‐C31 funded by MCIN/AEIMCIN/AEI/10.13039/501100011033 and FEDER funds, and by “ERDF A way of making Europe, repectively”. We thank Elena Rodríguez Aguado for performing XPS measurements. UK Catalysis Hub is kindly thanked for resources and support provided via the membership of the UK Catalysis Hub Consortium and funded by current EPSRC grants: EP/R026939/1 and EP/R026815/1. We thank Diamond Light Source for provision of beam time and support facilities at the beamline B18, under proposal SP30647. We also acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities and we would like to thank Dragos Stoian, Kenneth Marshall, Wouter van Beek and Naomi Lawes for assistance and support in using beamline BM31. This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 101022507. This work was supported by a research grant (9455) from VILLUM FONDEN. ERC and PBM wish to thanks the Spanish Ministry of Science and Innovation, for projects PID2021-126235OB-C32 and TED2021-130756B-C31 funded by MCIN/AEIMCIN/AEI/10.13039/501100011033 and FEDER funds, and by “ERDF A way of making Europe, repectively”. We thank Elena Rodríguez Aguado for performing XPS measurements.

Funders	Funder number
AEIMCIN
Villum Fonden
Engineering and Physical Sciences Research Council	SP30647, EP/R026815/1, EP/R026939/1
European Synchrotron Radiation Facility
Ministerio de Ciencia e Innovacion	TED2021‐130756B‐C31, PID2021‐126235OB‐C32
Horizon 2020	9455, 101022507
European Regional Development Fund
Agencia Estatal de Investigación

Keywords

Catalysis
CO Utilization
EXAFS
Operando
Spectroscopy

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.202312645Licence: CC BY

Cite this

Potter, M. E., Mediavilla Madrigal, S., Campbell, E., Allen, L. J., Vyas, U., Parry, S., García-Zaragova, A., Martínez-Prieto, L. M., Oña-Burgos, P., Lützen, M., Damsgaard, C. D., Rodríguez-Castellón, E., Schiaroli, N., Fornasari, G., Benito, P., & Beale, A. M. (2023). A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In₂O₃/Al₂O₃ Catalysts for CO₂ Hydrogenation. Angewandte Chemie - International Edition, 62(45), Article e202312645. https://doi.org/10.1002/anie.202312645

A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In₂O₃/Al₂O₃ Catalysts for CO₂ Hydrogenation. / Potter, Matthew E.; Mediavilla Madrigal, Sofia; Campbell, Emma et al.
In: Angewandte Chemie - International Edition, Vol. 62, No. 45, e202312645, 06.11.2023.

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

Potter, ME, Mediavilla Madrigal, S, Campbell, E, Allen, LJ, Vyas, U, Parry, S, García-Zaragova, A, Martínez-Prieto, LM, Oña-Burgos, P, Lützen, M, Damsgaard, CD, Rodríguez-Castellón, E, Schiaroli, N, Fornasari, G, Benito, P & Beale, AM 2023, 'A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In₂O₃/Al₂O₃ Catalysts for CO₂ Hydrogenation', Angewandte Chemie - International Edition, vol. 62, no. 45, e202312645. https://doi.org/10.1002/anie.202312645

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abstract = "CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In2O3 species dispersed on Al2O3 can match the performance of pure Pd/In2O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.",

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