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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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.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Figs. 1–13, Table 1 and description of data analysis methods.
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