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.
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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.
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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).
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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
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