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Endothermic reaction at room temperature enabled by deep-ultraviolet plasmons


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.


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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




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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The authors declare no competing interests.

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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).

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