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.

  • Article
  • Published:

Endothermic reaction at room temperature enabled by deep-ultraviolet plasmons

Nature Materials volume 20, pages 346–352 (2021)Cite this article

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

Data availability

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

References

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  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.

Author information

Authors and Affiliations

  1. Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Canhui Wang, Wei-Chang D. Yang, Alina Bruma, Amit Agrawal & Renu Sharma

  2. Institute for Research in Electronics and Applied Physics, and Maryland NanoCenter, University of Maryland, College Park, MD, USA

    Canhui Wang, Wei-Chang D. Yang, Alina Bruma & Amit Agrawal

  3. Materials Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    David Raciti

  4. DENSsolutions, Delft, the Netherlands

    Ronald Marx

Authors
  1. Canhui Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wei-Chang D. Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. David Raciti
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alina Bruma
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ronald Marx
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Amit Agrawal
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Renu Sharma
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

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.

Ethics declarations

Competing interests

The authors declare no competing interests.

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 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.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-020-00851-x

This article is cited by

Search

Advanced 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