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.
Subscribe to Journal
Get full journal access for 1 year
only $5.17 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All atomic structures used in the quantum mechanical simulations are provided as Supplementary Data 1–6. 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.
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.
Rostrup-Nielsen, J. & Christiansen, L. J. Concepts in Syngas Manufacture Ch. 2 (Imperial College Press, 2011).
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).
Hickman, D. A. & Schmidt, L. D. Production of syngas by direct catalytic oxidation of methane. Science 259, 343–346 (1993).
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).
Van Hook, J. P. Methane-steam reforming. Cat. Rev. 21, 1–51 (1980).
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).
Arora, S. & Prasad, R. An overview on dry reforming of methane: strategies to reduce carbonaceous deactivation of catalysts. RSC Adv. 6, 108668–108688 (2016).
Pakhare, D. & Spivey, J. A review of dry (CO2) reforming of methane over noble metal catalysts. Chem. Soc. Rev. 43, 7813–7837 (2014).
Zhang, Y. et al. Surface-plasmon-driven hot electron photochemistry. Chem. Rev. 118, 2927–2954 (2018).
Mukherjee, S. et al. Hot electrons do the impossible: plasmon-induced dissociation of H2 on Au. Nano Lett. 13, 240–247 (2013).
Mukherjee, S. et al. Hot-electron-induced dissociation of H2 on gold nanoparticles supported on SiO2. J. Am. Chem. Soc. 136, 64–67 (2014).
Christopher, P., Xin, H. & Linic, S. Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. Nat. Chem. 3, 467–472 (2011).
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).
Zhou, L. et al. Aluminum nanocrystals as a plasmonic photocatalyst for hydrogen dissociation. Nano Lett. 16, 1478–1484 (2016).
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).
Swearer, D. F. et al. Heterometallic antenna−reactor complexes for photocatalysis. Proc. Natl Acad. Sci. USA 113, 8916–8920 (2016).
Zhang, C. et al. Al–Pd nanodisk heterodimers as antenna–reactor photocatalysts. Nano Lett. 16, 6677–6682 (2016).
Robatjazi, H. et al. Plasmon-induced selective carbon dioxide conversion on earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles. Nat. Commun. 8, 27 (2017).
Aslam, U., Chavez, S. & Linic, S. Controlling energy flow in multimetallic nanostructures for plasmonic catalysis. Nat. Nanotechnol. 12, 1000–1005 (2017).
Martirez, J. M. P. & Carter, E. A. Excited-state N2 dissociation pathway on Fe-functionalized Au. J. Am. Chem. Soc. 139, 4390–4398 (2017).
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).
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).
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).
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).
Zhou, L. et al. Quantifying hot carrier and thermal contributions in plasmonic photocatalysis. Science 362, 69–72 (2018).
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).
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).
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).
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).
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).
Hadjiivanov, K. I. & Vayssilov, G. N. in Advances in Catalysis Vol. 47 307–511 (Academic Press, 2002).
DeRita, L. et al. Structural evolution of atomically dispersed Pt catalysts dictates reactivity. Nat. Mater. 18, 746–751 (2019).
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).
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).
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).
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).
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).
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).
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).
Huang, C., Pavone, M. & Carter, E. A. Quantum mechanical embedding theory based on a unique embedding potential. J. Chem. Phys. 134, 154110 (2011).
Libisch, F., Huang, C. & Carter, E. A. Embedded correlated wavefunction schemes: theory and applications. Acc. Chem. Res. 47, 2768–2775 (2014).
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).
Cohen, A. J., Mori-Sanchez, P. & Yang, W. T. Insights into current limitations of density functional theory. Science 321, 792–794 (2008).
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).
Said, S. A. M., Waseeuddin, M. & Simakov, D. S. A. A review on solar reforming systems. Renew. Sust. Energy Rev. 59, 149–159 (2016).
Yu, S. & Jain, P. K. Plasmonic photosynthesis of C1–C3 hydrocarbons from carbon dioxide assisted by an ionic liquid. Nat. Commun. 10, 2022 (2019).
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).
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).
Matsubu, J. C. et al. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2016).
Johnson, P. B. & Christy, R. W. Optical constants of the noble metals. Phys. Rev. B 6, 4370–4379 (1972).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
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).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).
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).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Methfessel, M. & Paxton, A. T. High-precision sampling for Brillouin-zone integration in metals. Phys. Rev. B 40, 3616–3621 (1989).
Makov, G. & Payne, M. C. Periodic boundary conditions in ab-initio calculations. Phys. Rev. B 51, 4014–4022 (1995).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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.
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.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Methods 1 and 2, Notes 1–9, Figs. 1–42, Tables 1–11 and refs. 1–31.
A summary of the structures used in the quantum mechanical simulations, and identifies in which figures these structures appear.
Atomic coordinates, in VASP format, for the surface reaction simulations involving the (3 × 3) pure Cu(111) slab.
Atomic coordinates, in VASP format, for the surface reaction simulations involving the (3 × 3) Ru-doped Cu(111) slab.
Atomic coordinates, in VASP format, for the surface reaction simulations involving the (√(21) × √(21)) pure and Ru-doped Cu(111) slab.
Atomic coordinates, in xyz format, for the embedded-cluster simulations involving the Cu10 cluster.
Atomic coordinates, in xyz format, for the embedded-cluster simulations involving the Cu10Ru cluster.
DFT+D3 minimum energy path for the first CH activation on Cu(111).
DFT+D3 minimum energy path for the fourth CH activation on Cu(111).
DFT+D3 minimum energy path for the first CH activation on Ru-doped Cu(111).
DFT+D3 minimum energy path for the fourth CH activation on Ru-doped Cu(111).
DFT+D3 minimum energy path for the second CH activation on Ru-doped Cu(111).
DFT+D3 minimum energy path for the third CH activation on Ru-doped Cu(111).
About this article
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