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Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane

Nature Materials volume 22, pages 762–768 (2023)Cite this article

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Abstract

The generation of methane fuel using surplus renewable energy with CO2 as the carbon source enables both the decarbonization and substitution of fossil fuel feedstocks. However, high temperatures are usually required for the efficient activation of CO2. Here we present a solid catalyst synthesized using a mild, green hydrothermal synthesis that involves interstitial carbon doped into ruthenium oxide, which enables the stabilization of Ru cations in a low oxidation state and a ruthenium oxycarbonate phase to form. The catalyst shows an activity and selectivity for the conversion of CO2 into methane at lower temperatures than those of conventional catalysts, with an excellent long-term stability. Furthermore, this catalyst is able to operate under intermittent power supply conditions, which couples very well with electricity production systems based on renewable energies. The structure of the catalyst and the nature of the ruthenium species were acutely characterized by combining advanced imaging and spectroscopic tools at the macro and atomic scales, which highlighted the low-oxidation-state Ru sites (Run+, 0 < n < 4) as responsible for the high catalytic activity. This catalyst suggests alternative perspectives for materials design using interstitial dopants.

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Fig. 1: HREM and STEM–EELS analysis of the as-prepared sample.
Fig. 2: SXRD pattern and structure refinement of the as-prepared sample compared to that of RuO2.
Fig. 3: Characterization of the nature of the Ru sites in the as-prepared sample.
Fig. 4: Catalytic performance of the as-prepared sample in the CO2 hydrogenation to yield methane.
Fig. 5: Catalytic performance and structural characterization of pure RuO2 catalysts.
Fig. 6: Methane production over a fresh (zone 1), deactivated (zone 2) and regenerated (zone 4) sample.

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Data availability

The authors declare that the main data supporting the findings of this study are available within the article and its Supplementary Information files. Crystallographic data for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2248295. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Ru and RuO2 structures for analysis were taken from ICSD entries 44615 and 15071, respectively. Extra data are available from the corresponding author upon request.

References

  1. Gary Grim, R. et al. Transforming the carbon economy: challenges and opportunities in the convergence of low-cost electricity and reductive CO2 utilization. Energy Environ. Sci. 13, 472–494 (2020).

    Article  Google Scholar 

  2. Ghaib, K. & Ben-Fares, F. Z. Power-to-methane: a state-of-the-art review. Renew. Sust. Energy Rev. 81, 433–446 (2018).

    Article  CAS  Google Scholar 

  3. Eveloy, V. & Gebreegziabher, T. A review of projected power-to-gas deployment scenarios. Energies 11, 1824 (2018).

    Article  Google Scholar 

  4. Cored, J. et al. Hydrothermal synthesis of ruthenium nanoparticles with a metallic core and a ruthenium carbide shell for low-temperature activation of CO2 to methane. J. Am. Chem. Soc. 141, 19304 (2019).

    Article  CAS  Google Scholar 

  5. Yan, C. et al. Local built-in electric field enabled in carbon-doped Co3O4 nanocrystals for superior lithium-ion storage. Adv. Funct. Mater. 28, 1705951 (2018).

    Article  Google Scholar 

  6. Ruan, F. et al. Enhanced activity for aerobic oxidative of alcohols over manganese oxides stimulated with interstitial nitrogen doping. Green. Synth. Catal. 2, 38–44 (2021).

    Article  Google Scholar 

  7. Aroyo, M. I. et al. Crystallography online: Bilbao Crystallographic Server. Bulg. Chem. Commun. 43, 183–197 (2011).

    CAS  Google Scholar 

  8. Rutt, H. N. & Nicola, J. H. Raman spectra of carbonates of calcite structure. J. Phys. C 7, 4522–4528 (1974).

    Article  CAS  Google Scholar 

  9. Buzgar, N. & Apopei, A. I. The Raman study of certain carbonates. Geologie 55, 97–112 (2009).

    Google Scholar 

  10. Planas, N. et al. Electronic structure of oxidized complexes derived from cis-[Ru-II(bpy) 2(H2 O)2]2+ and its photoisomerization mechanism. Inorg. Chem. 50, 11134–11142 (2011).

    Article  CAS  Google Scholar 

  11. Zhao, Z. et al. Effect of rutile content on the catalytic performance of Ru/TiO2 catalyst for low-temperature CO2 methanation. ACS Sustain. Chem. Eng. 9, 14288–14296 (2021).

    Article  CAS  Google Scholar 

  12. Lippi, R. et al. Highly active catalyst for CO2 methanation derived from a metal organic framework template. J. Mater. Chem. A 5, 12990–12997 (2017).

    Article  CAS  Google Scholar 

  13. Li, X. et al. Controlling CO2 hydrogenation selectivity by metal-supported electron transfer. Angew. Chem. Int. Ed. 59, 19983–19989 (2020).

    Article  CAS  Google Scholar 

  14. Renda, S., Ricca, A. & Palma, V. Precursor salts influence in ruthenium catalysts for CO2 hydrogenation to methane. Appl. Energy 279, 115767 (2020).

    Article  CAS  Google Scholar 

  15. Liao, W. et al. Tuning activity and selectivity of CO2 hydrogenation via metal–oxide interfaces over ZnO-supported metal catalysts. J. Catal. 407, 126–140 (2022).

    Article  CAS  Google Scholar 

  16. Niu, Y. et al. Manipulating interstitial carbon atoms in the nickel octahedral site for highly efficient hydrogenation of alkyne. Nat. Commun. 11, 3324 (2020).

    Article  CAS  Google Scholar 

  17. Tanuma, S., Powell, C. J. & Penn, D. R. Calculations of electron inelastic mean free paths. V. Data for 14 organic compounds over the 50–2000 eV range. Surf. Interf. Anal. 21, 165–176 (1994).

    Article  CAS  Google Scholar 

  18. Shinotsuka, H., Tanuma, S., Powell, C. J. & Penn, D. R. Calculations of electron inelastic mean free paths. X. Data for 41 elemental solids over the 50 eV to 200 keV range with the relativistic full Penn algorithm. Surf. Interf. Anal. 47, 871–888 (2015).

    Article  CAS  Google Scholar 

  19. Morgan, D. J. Resolving ruthenium: XPS studies of common ruthenium materials. Surf. Interf. Anal. 47, 1072–1079 (2015).

    Article  CAS  Google Scholar 

  20. Yeh, J. J. & Lindau, I. Atomic subshell photoionization cross-sections and asymmetry parameters: 1 ≤ Z ≤ 103. Atomic Data Nucl. Data Tables 32, 1–155 (1985).

    Article  CAS  Google Scholar 

  21. Simonelli, L. et al. CLÆSS: The hard X-ray absorption beamline of the ALBA CELLS synchrotron. Cogent Phys. 3, 1231987 (2016).

    Article  Google Scholar 

  22. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Article  CAS  Google Scholar 

  23. Newville, M. EXAFS analysis using FEFF and FEFFIT. J. Synchrotron Radiat. 8, 96–100 (2001).

    Article  CAS  Google Scholar 

  24. Rehr, J. J. & Albers, R. C. Theoretical approaches to X-ray absorption fine structure. Rev. Mod. Phys. 72, 621–654 (2000).

    Article  CAS  Google Scholar 

  25. Robinson, D. K. & Bevington, P. R. Sample Programs for Data Reduction and Error Analysis for the Physical Sciences (McGraw-Hill, 1992).

  26. Newville, M. Larch: an analysis package for XAFS and related spectroscopies. J. Phys. Conf. Ser. 430, 012007 (2013).

    Article  CAS  Google Scholar 

  27. Faut, F. et al. The crystallography stations at the Alba synchrotron. Eur. Phys. J. 130, 160–173 (2015).

    Google Scholar 

  28. Favre-Nicolin, V. & Cerny, R. FOX, ‘free objects for crystallography’: a modular approach to ab initio structure determination from powder diffraction. J. Appl. Cryst. 35, 734–743 (2002).

    Article  CAS  Google Scholar 

  29. Toby, B. & von Dreele, R. B. GSAS-II: the genesis of a modern open-source all purpose crystallography software package. J. Appl. Crystallogr. 46, 544–549 (2013).

    Article  CAS  Google Scholar 

  30. Roy, P., Rouzières, M., Qi, Z. & Chubar, O. The AILES Infrared Beamline on the third generation Synchrotron Radiation Facility SOLEIL. Infrared Phys. Technol. 49, 139–146 (2006).

    Article  CAS  Google Scholar 

  31. Faye, M. et al. Improved mid infrared detector for high spectral or spatial resolution and synchrotron radiation use. Rev. Sci. Instrum. 87, 063119 (2016).

    Article  Google Scholar 

Download references

Acknowledgements

We thank the support of C. Cerdá and M. D. Soriano in the catalyst preparation and testing. This research was funded by the Ministerio de Ciencia, Innovación y Universidades (grant nos. PID2021-1262350B-C31, PID2020-113006-RB-I00, PID2019-110018GA-I00 and MCIN/AEI/10.13039/501100011033), Generalitat Valenciana (grant no. CIAICO/2021/2138), the Department of Economy, Knowledge, Business and the University of the Regional Government of Andalusia (project reference FEDER-UCA18-107139). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from the European Union Next Generation (EU PRTR-C17.11) and by Generalitad Valenciana (ref. MFA/2022/016). C.T.-S. acknowledges the Polytechnical University of Valencia for the economic support through an FPI scholarship associated with the PAID programme ‘Programa de Ayudas de Investigación y Desarrollo’. XAS, XPS and XRD experiments were performed at the ALBA Synchrotron with the collaboration of ALBA staff. Infrared experiments were performed at the SOLEIL Synchrotron with the collaboration of SOLEIL staff.

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Authors and Affiliations

  1. Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Valencia, Spain

    Carmen Tébar-Soler, Patricia Concepción & Avelino Corma

  2. CELLS—ALBA Synchrotron Radiation Facility, Cerdanyola del Vallès, Spain

    Vlad Martin-Diaconescu, Laura Simonelli, Alexander Missyul, Virginia Perez-Dieste & Ignacio J. Villar-García

  3. Synchrotron SOLEIL, AILES Beamline, L’Orme des Merisiers, Saint Aubin, France

    Jean-Blaise Brubach & Pascale Roy

  4. Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad Ciencias, Universidad de Cádiz, Cádiz, Spain

    Miguel Lopez Haro & Jose Juan Calvino

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  1. Carmen Tébar-Soler
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Contributions

P.C. and A.C. planned the study and obtained the financial support. C.T.-S. did the synthesis and catalytic studies assisted by P.C. and A.C. V.M.-D. and L.S. performed the X-ray adsorption studies. A.M. did the SXRD analysis. I.V.-G. and V.P.-D. gave support in the synchrotron XPS analysis. C.T.-S. and J.-B.B. performed the synchrotron infrared studies assisted by R.P. M.L.H. and J.J.C. did the microscopy work. P.C., A.C. and C.T.-S. wrote the paper with the input from all the authors. All the authors contributed to discussing the results.

Corresponding authors

Correspondence to Patricia Concepción or Avelino Corma.

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Nature Materials thanks Bruce Gates and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–42, Tables 1–15 and references 32–70.

Supplementary Data

Structure refinement of the fresh RuO2C0.41 catalyst.

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Tébar-Soler, C., Martin-Diaconescu, V., Simonelli, L. et al. Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane. Nat. Mater. 22, 762–768 (2023). https://doi.org/10.1038/s41563-023-01540-1

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