Plasmonic‐assisted Electrocatalysis for CO₂ Reduction Reaction

Abstract

Integrating plasmonic features as an emerging strategy for enhancing electrocatalysis for the carbon dioxide reduction reaction (CO2RR). The key parameters responsible for the enhanced electrocatalysis performance are the local heating, the hot carriers, and near‐field enhancement induced by localized surface plasmon resonance (LSPR, that is, plasmonic) excitation. This review provides a concise overview of the fundamental mechanism of CO2RR, detailing the generation and decay of plasmonic and the energy transfer dynamics between plasmonic nanostructures and adsorbates. It further involves recent progress in plasmonic‐assisted electrocatalysis for CO2RR, including experimental and theoretical research to decipher plasmonic mechanisms. Finally, it ends with an insightful discussion of the existing challenges and potential future directions in this field.

Influence of molecular structure on the coupling strength to a plasmonic nanoparticle and hot carrier generation

“…Finally, the orientation of the molecules within the plasmonic near-field are important both from the point of view of hybridized KS states and from the coherent energy exchange which can be increased preferentially for specific binding. Hence, this research highlights the potential for tuning hot carrier generation in strongly coupled plasmon–molecule systems for enhanced energy generation or excited state chemistry, such as for enhanced solar harvesting efficiency 12 or plasmon-assisted electrocatalysis for CO 2 reduction, 50 to name a few. The predicted hot carrier spectra, in the present or similar strongly coupled systems, could be investigated for their real time dynamics and/or lifetimes via transient absorption spectroscopy, 70,71 two-colour time-resolved pump–probe measurements 72 or time-resolved two photon emission.…”

“…Such an approach is beneficial in the study of plasmon-mediated processes such as hot carrier transfer across metal–semiconductor interfaces 46,47 or to an adsorbed molecule, 48,49 differentiation between charge-transfer and localized surface plasmon resonance (LSPR), 45 or plasmon-assisted electrocatalysis for CO 2 reduction. 50 Hence, TDDFT offers the possibility of investigating the interplay of shape, material, orientation, and chemical species on plasmon–adsorbate interactions, here specifically in the strong coupling regime.…”

Origin of Macroscopic Observables of Strongly Coupled Metal Nanoparticle–Molecule Systems from Microscopic Electronic Properties

“…26−28 In this context, the strong coupling regime is especially promising, since the initial eigenstates become thoroughly mixed, which leads to the formation of new energy states and potentially favorable electron transition possibilities. 29 These changes of the electronic landscape yield modifications of reaction pathways, 30−33 allowing for modified chemistry, 24 catalytic applications, 34 or enhanced selectivity. 35 When two moieties are placed in close proximity and are energetically tuned to each other's transitions, as is the case in the strong coupling regime, resonance energy transfer occurs, 36 which can aid in the extraction of hot carriers generated during plasmon decay in plasmonic-molecular systems.…”

“…An interesting avenue of research is the excited state dynamics and energy transfer processes between metal NPs and adsorbed molecules under various conditions. − In this context, the strong coupling regime is especially promising, since the initial eigenstates become thoroughly mixed, which leads to the formation of new energy states and potentially favorable electron transition possibilities . These changes of the electronic landscape yield modifications of reaction pathways, − allowing for modified chemistry, catalytic applications, or enhanced selectivity . When two moieties are placed in close proximity and are energetically tuned to each other’s transitions, as is the case in the strong coupling regime, resonance energy transfer occurs, which can aid in the extraction of hot carriers generated during plasmon decay in plasmonic-molecular systems. , This macroscale coupling thus becomes an important tool in tailoring excited-state properties, such as hot carrier transfer across metal–semiconductor interfaces , or to an adsorbed molecule. , Polariton modification of energy transport is also observed at lower energies in the vibrational regime by coupling molecules to macroscopic Fabry–Perot cavities.…”