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


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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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: and, 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.

Author information

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.

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

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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.

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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.

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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).

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