Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts

Abstract

Syngas, an extremely important chemical feedstock composed of carbon monoxide and hydrogen, can be generated through methane (CH4) dry reforming with CO2. However, traditional thermocatalytic processes require high temperatures and suffer from coke-induced instability. Here, we report a plasmonic photocatalyst consisting of a Cu nanoparticle ‘antenna’ with single-Ru atomic ‘reactor’ sites on the nanoparticle surface, ideal for low-temperature, light-driven methane dry reforming. This catalyst provides high light energy efficiency when illuminated at room temperature. In contrast to thermocatalysis, long-term stability (50 h) and high selectivity (>99%) were achieved in photocatalysis. We propose that light-excited hot carriers, together with single-atom active sites, cause the observed performance. Quantum mechanical modelling suggests that single-atom doping of Ru on the Cu(111) surface, coupled with excited-state activation, results in a substantial reduction in the barrier for CH4 activation. This photocatalyst design could be relevant for future energy-efficient industrial processes.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Effect of ruthenium concentration on the photocatalytic behaviour of Cu–Ru surface alloys.
Fig. 2: Characterization of surface structure of Cu–Ru photocatalysts.
Fig. 3: Photo- and thermocatalytic characterization of the Cu19.8Ru0.2 catalyst for methane dry reforming.
Fig. 4: Schematics of enhanced selectivity and stability in photocatalysis via the DIET mechanism.
Fig. 5: Calculated ground- and excited-state energy curves along the MEP for CH4 and CH dehydrogenation.
Fig. 6: Photocatalytic energy efficiency and methane conversion of Cu19.8Ru0.2.

Data availability

All atomic structures used in the quantum mechanical simulations are provided as Supplementary Data 16. Source data for Figs. 3 and 6 are provided with the paper. Additional datasets generated and/or analysed during the current study that are not included in this published article (and its Supplementary information files) are available from the corresponding author on reasonable request.

Code availability

The modified VASP 5.3.3 code subroutines with embedding implementation and associated Python scripts, and the standalone embedding integral generator code used to transform the embedding potential from Cartesian grid to atomic orbital (GTO) bases, are available via GitHub: https://github.com/EACcodes/VASPEmbedding and https://github.com/EACcodes/EmbeddingIntegralGenerator, respectively, both under the Mozilla Public License 2.0.

References

  1. 1.

    Rostrup-Nielsen, J. & Christiansen, L. J. Concepts in Syngas Manufacture Ch. 2 (Imperial College Press, 2011).

  2. 2.

    Mhadeshwar, A. B. & Vlachos, D. G. A catalytic reaction mechanism for methane partial oxidation at short contact times, reforming, and combustion, and for oxygenate decomposition and oxidation on platinum. Ind. Eng. Chem. Res. 46, 5310–5324 (2007).

    Article  Google Scholar 

  3. 3.

    Hickman, D. A. & Schmidt, L. D. Production of syngas by direct catalytic oxidation of methane. Science 259, 343–346 (1993).

    Article  Google Scholar 

  4. 4.

    Aramouni, N. A. K., Touma, J. G., Tarboush, B. A., Zeaiter, J. & Ahmad, M. N. Catalyst design for dry reforming of methane: analysis review. Renew. Sust. Energy Rev. 82, 2570–2585 (2018).

    Article  Google Scholar 

  5. 5.

    Van Hook, J. P. Methane-steam reforming. Cat. Rev. 21, 1–51 (1980).

    Article  Google Scholar 

  6. 6.

    Lavoie, J.-M. Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation. Front. Chem. 2, 81 (2014).

    Article  Google Scholar 

  7. 7.

    Arora, S. & Prasad, R. An overview on dry reforming of methane: strategies to reduce carbonaceous deactivation of catalysts. RSC Adv. 6, 108668–108688 (2016).

    Article  Google Scholar 

  8. 8.

    Pakhare, D. & Spivey, J. A review of dry (CO2) reforming of methane over noble metal catalysts. Chem. Soc. Rev. 43, 7813–7837 (2014).

    Article  Google Scholar 

  9. 9.

    Zhang, Y. et al. Surface-plasmon-driven hot electron photochemistry. Chem. Rev. 118, 2927–2954 (2018).

    Article  Google Scholar 

  10. 10.

    Mukherjee, S. et al. Hot electrons do the impossible: plasmon-induced dissociation of H2 on Au. Nano Lett. 13, 240–247 (2013).

    Article  Google Scholar 

  11. 11.

    Mukherjee, S. et al. Hot-electron-induced dissociation of H2 on gold nanoparticles supported on SiO2. J. Am. Chem. Soc. 136, 64–67 (2014).

    Article  Google Scholar 

  12. 12.

    Christopher, P., Xin, H. & Linic, S. Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. Nat. Chem. 3, 467–472 (2011).

    Article  Google Scholar 

  13. 13.

    Marimuthu, A., Zhang, J. & Linic, S. Tuning selectivity in propylene epoxidation by plasmon mediated photo-switching of Cu oxidation state. Science 339, 1590–1593 (2013).

    Article  Google Scholar 

  14. 14.

    Zhou, L. et al. Aluminum nanocrystals as a plasmonic photocatalyst for hydrogen dissociation. Nano Lett. 16, 1478–1484 (2016).

    Article  Google Scholar 

  15. 15.

    Hou, W. B. et al. Photocatalytic conversion of CO2 to hydrocarbon fuels via plasmon-enhanced absorption and metallic interband transitions. ACS Catal. 1, 929–936 (2011).

    Article  Google Scholar 

  16. 16.

    Swearer, D. F. et al. Heterometallic antenna−reactor complexes for photocatalysis. Proc. Natl Acad. Sci. USA 113, 8916–8920 (2016).

    Article  Google Scholar 

  17. 17.

    Zhang, C. et al. Al–Pd nanodisk heterodimers as antenna–reactor photocatalysts. Nano Lett. 16, 6677–6682 (2016).

    Article  Google Scholar 

  18. 18.

    Robatjazi, H. et al. Plasmon-induced selective carbon dioxide conversion on earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles. Nat. Commun. 8, 27 (2017).

    Article  Google Scholar 

  19. 19.

    Aslam, U., Chavez, S. & Linic, S. Controlling energy flow in multimetallic nanostructures for plasmonic catalysis. Nat. Nanotechnol. 12, 1000–1005 (2017).

    Article  Google Scholar 

  20. 20.

    Martirez, J. M. P. & Carter, E. A. Excited-state N2 dissociation pathway on Fe-functionalized Au. J. Am. Chem. Soc. 139, 4390–4398 (2017).

    Article  Google Scholar 

  21. 21.

    Martirez, J. M. P. & Carter, E. A. Prediction of a low-temperature N2 dissociation catalyst exploiting near-IR-to-visible light nanoplasmonics. Sci. Adv. 3, eaao4710 (2017).

    Article  Google Scholar 

  22. 22.

    Liu, H. et al. Design of PdAu alloy plasmonic nanoparticles for improved catalytic performance in CO2 reduction with visible light irradiation. Nano Energy 26, 398–404 (2016).

    Article  Google Scholar 

  23. 23.

    Song, H. et al. Light-enhanced carbon dioxide activation and conversion by effective plasmonic coupling effect of Pt and Au nanoparticles. ACS Appl. Mater. Interfaces 10, 408–416 (2018).

    Article  Google Scholar 

  24. 24.

    Marcinkowski, M. D. et al. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. Nat. Chem. 10, 325–332 (2018).

    Article  Google Scholar 

  25. 25.

    Zhou, L. et al. Quantifying hot carrier and thermal contributions in plasmonic photocatalysis. Science 362, 69–72 (2018).

    Article  Google Scholar 

  26. 26.

    Behrens, M. Coprecipitation: an excellent tool for the synthesis of supported metal catalysts – from the understanding of the well known recipes to new materials. Catal. Today 246, 46–54 (2015).

    Article  Google Scholar 

  27. 27.

    Abrikosov, I. A., Olovsson, W. & Johansson, B. Valence-band hybridization and core level shifts in random Ag-Pd alloys. Phys. Rev. Lett. 87, 176403 (2001).

    Article  Google Scholar 

  28. 28.

    Darugar, Q., Qian, W., El-Sayed, M. A. & Pileni, M.-P. Size-dependent ultrafast electronic energy relaxation and enhanced fluorescence of copper nanoparticles. J. Phys. Chem. B 110, 143–149 (2006).

    Article  Google Scholar 

  29. 29.

    Guangyi, J. et al. Remarkably enhanced surface plasmon resonance absorption of Cu nanoparticles in SiO2 by post Zn ion implantation. Europhy. Lett. 101, 57005 (2013).

    Article  Google Scholar 

  30. 30.

    Daza, Y. A. & Kuhn, J. N. CO2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO2 conversion to liquid fuels. RSC Adv. 6, 49675–49691 (2016).

    Article  Google Scholar 

  31. 31.

    Hadjiivanov, K. I. & Vayssilov, G. N. in Advances in Catalysis Vol. 47 307–511 (Academic Press, 2002).

  32. 32.

    DeRita, L. et al. Structural evolution of atomically dispersed Pt catalysts dictates reactivity. Nat. Mater. 18, 746–751 (2019).

    Article  Google Scholar 

  33. 33.

    Luntz, A. C., Persson, M., Wagner, S., Frischkorn, C. & Wolf, M. Femtosecond laser induced associative desorption of H2 from Ru(0001): comparison of ‘first principles’ theory with experiment. J. Chem. Phys. 124, 244702 (2006).

    Article  Google Scholar 

  34. 34.

    Spata, V. A. & Carter, E. A. Mechanistic insights into photocatalyzed hydrogen desorption from palladium surfaces assisted by localized surface plasmon resonances. ACS Nano 12, 3512–3522 (2018).

    Article  Google Scholar 

  35. 35.

    Zhang, W. H., Wu, P., Li, Z. Y. & Yang, J. L. First-principles thermodynamics of graphene growth on Cu surfaces. J. Phys. Chem. C 115, 17782–17787 (2011).

    Article  Google Scholar 

  36. 36.

    Gajewski, G. & Pao, C. W. Ab initio calculations of the reaction pathways for methane decomposition over the Cu (111) surface. J. Chem. Phys. 135, 064707 (2011).

    Article  Google Scholar 

  37. 37.

    Wang, X. L., Yuan, Q. H., Li, J. & Ding, F. The transition metal surface dependent methane decomposition in graphene chemical vapor deposition growth. Nanoscale 9, 11584–11589 (2017).

    Article  Google Scholar 

  38. 38.

    Angeli, C., Cimiraglia, R., Evangelisti, S., Leininger, T. & Malrieu, J. P. Introduction of n-electron valence states for multireference perturbation theory. J. Chem. Phys. 114, 10252–10264 (2001).

    Article  Google Scholar 

  39. 39.

    Yu, K., Krauter, C. M., Dieterich, J. M. & Carter, E. A. in Fragmentation: Toward Accurate Calculations on Complex Molecular Systems (ed. Gordon, M. S.) Ch. 2 (John Wiley & Sons, 2017).

  40. 40.

    Huang, C., Pavone, M. & Carter, E. A. Quantum mechanical embedding theory based on a unique embedding potential. J. Chem. Phys. 134, 154110 (2011).

    Article  Google Scholar 

  41. 41.

    Libisch, F., Huang, C. & Carter, E. A. Embedded correlated wavefunction schemes: theory and applications. Acc. Chem. Res. 47, 2768–2775 (2014).

    Article  Google Scholar 

  42. 42.

    Lundberg, M. & Siegbahn, P. E. M. Quantifying the effects of the self-interaction error in DFT: when do the delocalized states appear? J. Chem. Phys. 122, 224103 (2005).

    Article  Google Scholar 

  43. 43.

    Cohen, A. J., Mori-Sanchez, P. & Yang, W. T. Insights into current limitations of density functional theory. Science 321, 792–794 (2008).

    Article  Google Scholar 

  44. 44.

    Simakov, D. S. A., Wright, M. M., Ahmed, S., Mokheimer, E. M. A. & Roman-Leshkov, Y. Solar thermal catalytic reforming of natural gas: a review on chemistry, catalysis and system design. Catal. Sci. Technol. 5, 1991–2016 (2015).

    Article  Google Scholar 

  45. 45.

    Said, S. A. M., Waseeuddin, M. & Simakov, D. S. A. A review on solar reforming systems. Renew. Sust. Energy Rev. 59, 149–159 (2016).

    Article  Google Scholar 

  46. 46.

    Yu, S. & Jain, P. K. Plasmonic photosynthesis of C1–C3 hydrocarbons from carbon dioxide assisted by an ionic liquid. Nat. Commun. 10, 2022 (2019).

    Article  Google Scholar 

  47. 47.

    Dhiman, M. et al. Plasmonic colloidosomes of black gold for solar energy harvesting and hotspots directed catalysis for CO2 to fuel conversion. Chem. Sci. 10, 6594–6603 (2019).

    Article  Google Scholar 

  48. 48.

    Kale, M. J. & Christopher, P. Utilizing quantitative in situ FTIR spectroscopy to identify well-coordinated Pt atoms as the active site for CO oxidation on Al2O3-supported Pt catalysts. ACS Catal. 6, 5599–5609 (2016).

    Article  Google Scholar 

  49. 49.

    Matsubu, J. C. et al. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2016).

    Article  Google Scholar 

  50. 50.

    Johnson, P. B. & Christy, R. W. Optical constants of the noble metals. Phys. Rev. B 6, 4370–4379 (1972).

    Article  Google Scholar 

  51. 51.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  52. 52.

    Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  Google Scholar 

  53. 53.

    Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).

    Article  Google Scholar 

  54. 54.

    Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  55. 55.

    Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  56. 56.

    Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    MathSciNet  Article  Google Scholar 

  57. 57.

    Methfessel, M. & Paxton, A. T. High-precision sampling for Brillouin-zone integration in metals. Phys. Rev. B 40, 3616–3621 (1989).

    Article  Google Scholar 

  58. 58.

    Makov, G. & Payne, M. C. Periodic boundary conditions in ab-initio calculations. Phys. Rev. B 51, 4014–4022 (1995).

    Article  Google Scholar 

  59. 59.

    Neugebauer, J. & Scheffler, M. Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111). Phys. Rev. B 46, 16067–16080 (1992).

    Article  Google Scholar 

  60. 60.

    Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    Article  Google Scholar 

  61. 61.

    Yu, K., Libisch, F. & Carter, E. A. Implementation of density functional embedding theory within the projector-augmented-wave method and applications to semiconductor defect states. J. Chem. Phys. 143, 102806 (2015).

    Article  Google Scholar 

  62. 62.

    Werner, H.-J., Knowles, P. J., Knizia, G., Manby, F. R. & Schütz, M. Molpro: a general-purpose quantum chemistry program package. WIREs Comput. Mol. Sci. 2, 242–253 (2012).

    Article  Google Scholar 

  63. 63.

    Peterson, K. A. & Puzzarini, C. Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements. Theor. Chem. Acc. 114, 283–296 (2005).

    Article  Google Scholar 

  64. 64.

    Peterson, K. A., Figgen, D., Dolg, M. & Stoll, H. Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y–Pd. J. Chem. Phys. 126, 124101 (2007).

    Article  Google Scholar 

  65. 65.

    Figgen, D., Rauhut, G., Dolg, M. & Stoll, H. Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data. Chem. Phys. 311, 227–244 (2005).

    Article  Google Scholar 

  66. 66.

    Bergner, A., Dolg, M., Küchle, W., Stoll, H. & Preuß, H. Ab initio energy-adjusted pseudopotentials for elements of groups 13–17. Mol. Phys. 80, 1431–1441 (1993).

    Article  Google Scholar 

  67. 67.

    Dunning, T. H. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J. Chem. Phys. 90, 1007–1023 (1989).

    Article  Google Scholar 

  68. 68.

    Woon, D. E. & Dunning, T. H. Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon. J. Chem. Phys. 103, 4572–4585 (1995).

    Article  Google Scholar 

  69. 69.

    Roos, B. O. The complete active space SCF method in a Fock-matrix-based super-CI formulation. Int. J. Quantum Chem. 17, 175–189 (1980).

    Article  Google Scholar 

  70. 70.

    Siegbahn, P. E. M., Almlof, J., Heiberg, A. & Roos, B. O. The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule. J. Chem. Phys. 74, 2384–2396 (1981).

    Article  Google Scholar 

Download references

Acknowledgements

This article is based on work supported by the Robert A. Welch foundation under grants C-1220 (N.J.H.) and C-1222 (P.N.) and by the Air Force Office of Scientific Research (AFOSR) via the Department of Defense Multidisciplinary University Research Initiative under AFOSR award no. FA9550-15-1-0022. E.A.C. thanks the High Performance Computing Modernization Program (HPCMP) of the US Department of Defense and Princeton University’s Terascale Infrastructure for Groundbreaking Research in Engineering and Science (TIGRESS) for providing the computational resources. We thank B. Seemala for his assistance in CO-DRIFTS experiments.

Author information

Affiliations

Authors

Contributions

L.Z. and N.J.H. initiated the project. L.Z. developed the photocatalysts, performed the characterizations (XRD, XPS, UV–visible diffuse reflectance, HR-TEM) and the photocatalysis studies and analysed the data. J.M.P.M. carried out all the quantum mechanical calculations. J.F. performed the CO-DRIFTS measurement. C.Z. helped with the photocatalysis studies and data analysis. D.F.S. performed the HAADF–STEM. S.T. performed the Raman measurements. H.R. helped to interpret the results. M.L. performed the electromagnetic calculations. L.D. performed the TGA experiment. L.H. performed the ICP–MS. E.A.C., P.N. and N.J.H. supervised the research. L.Z., J.M.P.M., J.F., C.Z., D.F.S., P.C., E.A.C., P.N. and N.J.H. contributed to the interpretation of the data and preparation of the manuscript.

Corresponding authors

Correspondence to Emily A. Carter or Peter Nordlander or Naomi J. Halas.

Ethics declarations

Competing interests

An international patent application for the antenna-reactor concept under the Patent Cooperation Treaty is pending (15977843). N.J.H. and P.N. are cofounders of a company that is in the process of commercializing an alternative technology, photocatalytic steam methane reforming.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Methods 1 and 2, Notes 1–9, Figs. 1–42, Tables 1–11 and refs. 1–31.

Supplementary Data 1

A summary of the structures used in the quantum mechanical simulations, and identifies in which figures these structures appear.

Supplementary Data 2

Atomic coordinates, in VASP format, for the surface reaction simulations involving the (3 × 3) pure Cu(111) slab.

Supplementary Data 3

Atomic coordinates, in VASP format, for the surface reaction simulations involving the (3 × 3) Ru-doped Cu(111) slab.

Supplementary Data 4

Atomic coordinates, in VASP format, for the surface reaction simulations involving the (√(21) × √(21)) pure and Ru-doped Cu(111) slab.

Supplementary Data 5

Atomic coordinates, in xyz format, for the embedded-cluster simulations involving the Cu10 cluster.

Supplementary Data 6

Atomic coordinates, in xyz format, for the embedded-cluster simulations involving the Cu10Ru cluster.

Supplementary Video 1

DFT+D3 minimum energy path for the first CH activation on Cu(111).

Supplementary Video 2

DFT+D3 minimum energy path for the fourth CH activation on Cu(111).

Supplementary Video 3

DFT+D3 minimum energy path for the first CH activation on Ru-doped Cu(111).

Supplementary Video 4

DFT+D3 minimum energy path for the fourth CH activation on Ru-doped Cu(111).

Supplementary Video 5

DFT+D3 minimum energy path for the second CH activation on Ru-doped Cu(111).

Supplementary Video 6

DFT+D3 minimum energy path for the third CH activation on Ru-doped Cu(111).

Source data

Source Data Fig. 3

Statistical source data for Fig. 3b and c.

Source Data Fig. 6

Statistical source data for Fig. 6a and b.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhou, L., Martirez, J.M.P., Finzel, J. et al. Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts. Nat Energy 5, 61–70 (2020). https://doi.org/10.1038/s41560-019-0517-9

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing