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  • Primer
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Plasmon-mediated chemical reactions

Abstract

Plasmon-mediated chemical reactions (PMCRs) are processes that make use of nanostructure-based surface plasmons as mediators to redistribute and convert photon energy in various time, space and energy scales, thereby driving chemical reactions by localizing photon, electronic and/or thermal energies. PMCRs can enhance the efficiency of an array of reactions, with potential advantages and unique features over thermochemistry, electrochemistry, photochemistry and photocatalysis. This Primer aims to give a general overview of the key points regarding PMCRs. Following the introduction of the main fundamental mechanism of plasmonic effects including enhanced electromagnetic near field, excited carriers and local heating on chemical reactions, the primary consideration and techniques for designing and constructing plasmonic catalysts are outlined. The typical methods used to characterize plasmonic catalysts and their properties are presented, as well as a discussion of PMCR mechanisms. Recent advances in PMCR application are also reviewed with some typical examples. Finally, the reproducibility and key optimization factors are emphasized, followed by a summary of future challenges and opportunities for the field.

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Fig. 1: PMCRs and their main mechanism.
Fig. 2: Workflow of PMCRs.
Fig. 3: Schematics of the simulations of plasmonic effect.
Fig. 4: Schematics of the characterization and catalytic test of the plasmonic catalysts.
Fig. 5: Typical experimental results analysis for the determination of catalytic performance and mechanism.
Fig. 6: Typical theoretical calculation process of plasmon-mediated chemical reactions.
Fig. 7: Applications of PMCRs.

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Acknowledgements

This work was supported by the Ministry of Science and Technology of China (2015CB932300) and the National Natural Science Foundation of China (21727807, 21533006, 22032004, 91427304, 22002036 and 22272140). C.Z. thanks the Alexander von Humboldt Foundation (AvH) for support with an AvH postdoctoral research grant. The authors thank B. Roldan (Fritz-Haber Institute of the Max-Planck Society) for helpful discussions.

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Contributions

Introduction (C.Z., S.H., Z.-Q.T.); Experimentation (S.H., J.Y., C.Z.); Results (C.Z., X.-G.Z. D.-Y.W.); Applications (C.Z., Z.-Q.T.); Reproducibility and data deposition (C.Z.); Limitations and optimizations (C.Z., Z.-Q.T.); Outlook (all authors); Overview of the Primer (Z.-Q.T., C.Z.).

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Correspondence to Chao Zhan or Zhong-Qun Tian.

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Glossary

Direct charge transfer

The decay of a surface plasmon results in the direct excitation of an electron/hole into an unoccupied adsorbate orbital/semiconductor band with matching energy and leaves the hole/electron in the plasmonic nanostructure.

Fermi–Dirac distribution

The distribution of particles over energy states in systems consisting of many identical particles that obey the Pauli exclusion principle.

Hot carriers

Carriers including electrons or holes not in thermal equilibrium with the atoms in a material are frequently referred to as hot carriers.

Indirect charge transfer

Excited carriers are formed in the plasmonic nanostructure with a roughly flat energy distribution and, subsequently, transfer to adsorbed molecules/semiconductor forming the charged state.

Landau damping

A process occurring because of the energy exchange between an electromagnetic wave and particles in the plasma, which can interact strongly with the wave. In a surface plasmon system, the Landau damping process results in direct transition between two states near the Fermi surface, assisted by the surface plasmon momentum, and creating a hot hole and a hot electron.

Lossy media

In optics, the media are not transparent to the incident light waves and result in absorptions. The dissipation of a medium is usually described by the imaginary part of its dielectric permittivity.

Periodic boundary condition

A term often used in computer simulations and mathematical models, for which a unit cell is chosen to approximate a large (infinite) system.

Photothermal effect

The conversion of photon energy to thermal energy.

Surface plasmon resonance

(SPR). The resonant collective oscillation of conduction electrons in nanostructures stimulated by incident light.

Turnover frequency

The derivative of the number of turnovers with respect to the time per active site.

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Zhan, C., Yi, J., Hu, S. et al. Plasmon-mediated chemical reactions. Nat Rev Methods Primers 3, 12 (2023). https://doi.org/10.1038/s43586-023-00195-1

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