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PreprintCC BYChemRxiv

Oxidative strong metal-support interaction determines selectivity in supported Rh catalysts for CO2 hydrogenation

  • Jake Heinlein1,2
  • Jake Erbez3,4
  • Anastassiya Khan5,6
  • Sabrina M. Gericke7,8
  • Xiaobo Chen7,8
  • Meng Li7,8
  • Greg Barber1,9
  • Zhihengyu Chen5,6
  • Christopher J. Tassone6
  • Robert M. Rioux1,9,10
  • Ashley R. Head7,8
  • Judith Yang7,8,11,12
4 more authors
  • Adam S. Hoffman5,6,13,2
  • Simon R. Bare5,6,13,2
  • Anastassia N. Alexandrova3,4
  • Matteo Cargnello1,2,13,14,15
15 affiliations
  1. 1Department of Chemical Engineering
  2. 2Stanford University
  3. 3Department of Chemistry and Biochemistry
  4. 4University of California
  5. 5Stanford Synchrotron Radiation Lightsource
  6. 6SLAC National Accelerator Laboratory
  7. 7Center for Functional Nanomaterials
  8. 8Brookhaven National Laboratory
  9. 9Pennsylvania State University
  10. 10Department of Chemistry
  11. 11Department of Chemical and Petroleum Engineering, Physics
  12. 12University of Pittsburgh
  13. 13SUNCAT Center for Interface Science and Catalysis
  14. 14CO2 Research Center (CORC
  15. 15Aarhus University
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Abstract

The restructuring of a catalyst’s interface with its support can be tailored via strong metal-support interactions (SMSI) in order to achieve desired product selectivity. SMSI is usually associated with reductive conditions, where a reduced oxide support covers a supported metal phase and alters catalytic activity. Here, pretreatment-dependent SMSI of rhodium nanoparticles supported on rutile titania is shown to control the selectivity profile for CO 2 hydrogenation reactions between methanation and the reverse water-gas shift reaction at 500 °C. Oxidative pretreatments at 400 °C were found to promote methanation with an initial rate of 5.1 mol/mol Rh /s for an O 2 pretreated sample and 5.8 mol/mol Rh /s for an O 2 followed by H 2 pretreated sample, whereas a H 2 pretreatment at 400 °C suppressed the methanation reaction to an initial rate of 0.25 mol/mol Rh /s. Instead of following classical methods of catalyst restructuring, such as sintering and reductive SMSI, the catalyst forms an SMSI overlayer under oxidative conditions, which restructures its active sites to selectively promote the methanation reaction. The effects of the restructuring are long-lived and dominated the catalyst selectivity even after more than 100 hours under reaction conditions. We demonstrate that this oxidative SMSI overlayer grows via a rhodium titanate intermediate and is necessary for creating active sites for methanation, shifting the catalyst’s selectivity away from the RWGS reaction. Theoretical calculations further demonstrate the thermodynamic favorability of TiO 2 overlayer growth under experimentally-relevant oxidative conditions. These results demonstrate that catalyst pretreatment conditions are a facile and effective tool for tuning the catalyst-support interface by allowing for the construction of an oxidative strong metal-support interaction that determines the product selectivity of supported rhodium catalysts.

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Cite

BibTeXRIS
BibTeX
@misc{heinlein2026oxidative,
  title = {{Oxidative strong metal-support interaction determines selectivity in supported Rh catalysts for CO2 hydrogenation}},
  author = {Jake Heinlein and Jake Erbez and Anastassiya Khan and Sabrina M. Gericke and Xiaobo Chen and Meng Li and Greg Barber and Zhihengyu Chen and Christopher J. Tassone and Robert M. Rioux and Ashley R. Head and Judith Yang and Adam S. Hoffman and Simon R. Bare and Anastassia N. Alexandrova and Matteo Cargnello},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15009725/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009725/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Oxidative strong metal-support interaction determines selectivity in supported Rh catalysts for CO2 hydrogenation
AU  - Jake Heinlein
AU  - Jake Erbez
AU  - Anastassiya Khan
AU  - Sabrina M. Gericke
AU  - Xiaobo Chen
AU  - Meng Li
AU  - Greg Barber
AU  - Zhihengyu Chen
AU  - Christopher J. Tassone
AU  - Robert M. Rioux
AU  - Ashley R. Head
AU  - Judith Yang
AU  - Adam S. Hoffman
AU  - Simon R. Bare
AU  - Anastassia N. Alexandrova
AU  - Matteo Cargnello
PY  - 2026
DA  - 2026/10/01
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009725/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009725/v1
AB  - The restructuring of a catalyst’s interface with its support can be tailored via strong metal-support interactions (SMSI) in order to achieve desired product selectivity. SMSI is usually associated with reductive conditions, where a reduced oxide support covers a supported metal phase and alters catalytic activity. Here, pretreatment-dependent SMSI of rhodium nanoparticles supported on rutile titania is shown to control the selectivity profile for CO 2 hydrogenation reactions between methanation and the reverse water-gas shift reaction at 500 °C. Oxidative pretreatments at 400 °C were found to promote methanation with an initial rate of 5.1 mol/mol Rh /s for an O 2 pretreated sample and 5.8 mol/mol Rh /s for an O 2 followed by H 2 pretreated sample, whereas a H 2 pretreatment at 400 °C suppressed the methanation reaction to an initial rate of 0.25 mol/mol Rh /s. Instead of following classical methods of catalyst restructuring, such as sintering and reductive SMSI, the catalyst forms an SMSI overlayer under oxidative conditions, which restructures its active sites to selectively promote the methanation reaction. The effects of the restructuring are long-lived and dominated the catalyst selectivity even after more than 100 hours under reaction conditions. We demonstrate that this oxidative SMSI overlayer grows via a rhodium titanate intermediate and is necessary for creating active sites for methanation, shifting the catalyst’s selectivity away from the RWGS reaction. Theoretical calculations further demonstrate the thermodynamic favorability of TiO 2 overlayer growth under experimentally-relevant oxidative conditions. These results demonstrate that catalyst pretreatment conditions are a facile and effective tool for tuning the catalyst-support interface by allowing for the construction of an oxidative strong metal-support interaction that determines the product selectivity of supported rhodium catalysts.
ER  -