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Endothermic reaction at room temperature enabled by deep-ultraviolet plasmons

Abstract

Metallic nanoparticles have been used to harvest energy from a light source and transfer it to adsorbed gas molecules, which results in a reduced chemical reaction temperature. However, most reported reactions, such as ethylene epoxidation, ammonia decomposition and H–D bond formation are exothermic, and only H–D bond formation has been achieved at room temperature. These reactions require low activation energies (<2 eV), which are readily attained using visible-frequency localized surface plasmons (from ~1.75 eV to ~3.1 eV). Here, we show that endothermic reactions that require higher activation energy (>3.1 eV) can be initiated at room temperature by using localized surface plasmons in the deep-UV range. As an example, by leveraging simultaneous excitation of multiple localized surface plasmon modes of Al nanoparticles by using high-energy electrons, we initiate the reduction of CO2 to CO by carbon at room temperature. We employ an environmental transmission electron microscope to excite and characterize Al localized surface plasmon resonances, and simultaneously measure the spatial distribution of carbon gasification near the nanoparticles in a CO2 environment. This approach opens a path towards exploring other industrially relevant chemical processes that are initiated by plasmonic fields at room temperature.

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Fig. 1: Electric field distribution of electron-beam-excited LSP resonance.
Fig. 2: Carbon etching with the aloof electron beam.
Fig. 3: Carbon etching as a function of nanoparticle number and electron flux.
Fig. 4: Correlation between the reaction rate distribution and the electric field distribution of the LSP resonance.
Fig. 5: Measurement of graphite etching in control experiments.
Fig. 6: Detection of CO as reverse Boudouard reaction product by using GCMS.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

References

  1. 1.

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

    CAS  Article  Google Scholar 

  2. 2.

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

    CAS  Article  Google Scholar 

  3. 3.

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

    CAS  Article  Google Scholar 

  4. 4.

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

    CAS  Article  Google Scholar 

  5. 5.

    Hartland, G. V., Besteiro, L. V., Johns, P. & Govorov, A. O. What’s so hot about electrons in metal nanoparticles? ACS Energy Lett. 2, 1641–1653 (2017).

    CAS  Article  Google Scholar 

  6. 6.

    Christopher, P., Xin, H., Marimuthu, A. & Linic, S. Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures. Nat. Mater. 11, 1044–1050 (2012).

    CAS  Article  Google Scholar 

  7. 7.

    Yang, J., Guo, Y., Lu, W., Jiang, R. & Wang, J. Emerging applications of plasmons in driving CO2 reduction and N2 fixation. Adv. Mater. 30, 1802227 (2018).

    Article  Google Scholar 

  8. 8.

    Wang, P. et al. Ag@AgCl: a highly efficient and stable photocatalyst active under visible light. Angew. Chem. Int. Ed. 47, 7931–7933 (2008).

    CAS  Article  Google Scholar 

  9. 9.

    Christopher, P., Ingram, D. B. & Linic, S. Enhancing photochemical activity of semiconductor nanoparticles with optically active Ag nanostructures: photochemistry mediated by Ag surface plasmons. J. Phys. Chem. C 114, 9173–9177 (2010).

    CAS  Article  Google Scholar 

  10. 10.

    Ingram, D. B. & Linic, S. Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface. J. Am. Chem. Soc. 133, 5202–5205 (2011).

    CAS  Article  Google Scholar 

  11. 11.

    Zheng, Z. et al. Facile in situ synthesis of visible-light plasmonic photocatalysts M@TiO2 (M = Au, Pt, Ag) and evaluation of their photocatalytic oxidation of benzene to phenol. J. Mater. Chem. 21, 9079–9087 (2011).

    CAS  Article  Google Scholar 

  12. 12.

    Mubeen, S. et al. An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. Nat. Nanotechnol. 8, 247–251 (2013).

    CAS  Article  Google Scholar 

  13. 13.

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

    CAS  Article  Google Scholar 

  14. 14.

    Kale, M. J., Avanesian, T. & Christopher, P. Direct photocatalysis by plasmonic nanostructures. ACS Catal. 4, 116–128 (2014).

    CAS  Article  Google Scholar 

  15. 15.

    Zhang, X., Chen, Y. L., Liu, R.-S. & Tsai, D. P. Plasmonic photocatalysis. Rep. Prog. Phys. 76, 046401 (2013).

    Article  Google Scholar 

  16. 16.

    Yang, W.-C. D. et al. Site-selective CO disproportionation mediated by localized surface plasmon resonance excited by electron beam. Nat. Mater. 18, 614–619 (2019).

    CAS  Article  Google Scholar 

  17. 17.

    Hunt, J. et al. Microwave-specific enhancement of the carbon–carbon dioxide (Boudouard) reaction. J. Phys. Chem. C 117, 26871–26880 (2013).

    CAS  Article  Google Scholar 

  18. 18.

    Marchon, B., Tysoe, W. T., Carrazza, J., Heinemann, H. & Somorjai, G. A. Reactive and kinetic properties of carbon monoxide and carbon dioxide on a graphite surface. J. Phys. Chem. 92, 5744–5749 (1988).

    CAS  Article  Google Scholar 

  19. 19.

    Strange, J. F. & Walker, P. L.Jr. Carbon–carbon dioxide reaction: Langmuir–Hinshelwood kinetics at intermediate pressures. Carbon 14, 345–350 (1976).

    CAS  Article  Google Scholar 

  20. 20.

    Batson, P. E. A new surface plasmon resonance in clusters of small aluminum spheres. Ultramicroscopy 9, 277–282 (1982).

    CAS  Article  Google Scholar 

  21. 21.

    McClain, M. J. et al. Aluminum nanocrystals. Nano Lett. 15, 2751–2755 (2015).

    CAS  Article  Google Scholar 

  22. 22.

    Fujimoto, F. & Komaki, K.-I. Plasma oscillations excited by a fast electron in metallic particle. J. Phys. Soc. Jpn. 25, 1679–1687 (1968).

    Article  Google Scholar 

  23. 23.

    Hohenester, U. Simulating electron energy loss spectroscopy with the MNPBEM toolbox. Comput. Phys. Commun. 185, 1177–1187 (2014).

    CAS  Article  Google Scholar 

  24. 24.

    Hohenester, U., Ditlbacher, H. & Krenn, J. R. Electron-energy-loss spectra of plasmonic nanoparticles. Phys. Rev. Lett. 103, 106801 (2009).

    Article  Google Scholar 

  25. 25.

    Busch, K., König, M. & Niegemann, J. Discontinuous Galerkin methods in nanophotonics. Laser Photonics Rev. 5, 773–809 (2011).

    Article  Google Scholar 

  26. 26.

    Seemala, B. et al. Plasmon-mediated catalytic O2 dissociation on Ag nanostructures: hot electrons or near fields? ACS Energy Lett. 4, 1803–1809 (2019).

    CAS  Article  Google Scholar 

  27. 27.

    Nordlander, P., Oubre, C., Prodan, E., Li, K. & Stockman, M. I. Plasmon Hybridization in nanoparticle dimers. Nano Lett. 4, 899–903 (2004).

    CAS  Article  Google Scholar 

  28. 28.

    Egerton, R. F., Li, P. & Malac, M. Radiation damage in the TEM and SEM. Micron 35, 399–409 (2004).

    CAS  Article  Google Scholar 

  29. 29.

    Hohenester, U. & Trügler, A. MNPBEM – a Matlab toolbox for the simulation of plasmonic nanoparticles. Comput. Phys. Commun. 183, 370–381 (2012).

    CAS  Article  Google Scholar 

  30. 30.

    Sharma, R. An environmental transmission electron microscope for in situ synthesis and characterization of nanomaterials. J. Mater. Res. 20, 1695–1707 (2005).

    CAS  Article  Google Scholar 

  31. 31.

    Mecklenburg, M. et al. Nanoscale temperature mapping in operating microelectronic devices. Science 347, 629–632 (2015).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

We gratefully thank D. Sil (National Institute of Standards and Technology, now at IBM) for useful discussions. C.W., W.-C.D.Y., A.B. and A.A. acknowledge support under the cooperative research agreement between the University of Maryland and the Physical Measurement Laboratory of the National Institute of Standards and Technology (award no. 70NANB14H209), through the University of Maryland.

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C.W., W.-C.D.Y., and R.S. conceived and designed the research. C.W. prepared the samples, conducted in situ measurements by ESTEM and processed the data. W.-C.D.Y. and A.B. carried out electromagnetic boundary element method calculations. A.A. contributed to designing the models for simulation. D.R. and A.A. contributed to the design of the experiments and the analysis of the results. R.M. and D.R. designed and helped in conducting the GCMS experiments. All authors contributed to writing the manuscript.

Corresponding authors

Correspondence to Wei-Chang D. Yang or Renu Sharma.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–13, Table 1 and description of data analysis methods.

Supplementary Video 1

Movie showing etching of graphite near the surface of an Al nanoparticle in a CO2 environment with a pressure of ~50 Pa, illuminated with an electron flux of ~9.1 × 10−6 nA nm−2. The movie plays at 120 times normal speed. Note the formation of pillar-shaped graphite structures due to the uneven etching rate resulting from spatial distribution of electric field around the nanoparticle. The scale bar is 25 nm.

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Wang, C., Yang, WC.D., Raciti, D. et al. Endothermic reaction at room temperature enabled by deep-ultraviolet plasmons. Nat. Mater. 20, 346–352 (2021). https://doi.org/10.1038/s41563-020-00851-x

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