Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

Wang, Jun; Jae-young, Heo; Chen, Changqiang; Wilson, Andrew J.; Jain, Prashant K.

doi:10.1002/anie.202007202

Cited by 49 publications

(44 citation statements)

References 40 publications

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“…Thus, light-induced potentials appear to be effective means for enhancing the kinetics of electrochemical reactions and amplifying the activities of electrocatalysts. This principle has been found to be operative in electrochemical oxidation reactions as well, including NH 3 oxidation on Au–Pt NPs and methanol oxidation on Pd–Ag nanostructures, where an anodic photopotential generated on the NPs by LSPR excitation under a positive bias boosted the applied potential, resulting in enhanced activity. In fact, because of the light-induced boost, the plasmonic Au–Pt NP electrocatalyst, reported by our laboratory recently, appears to outperform other NH 3 oxidation electrocatalysts.…”

Section: Influence Of Photopotentials On Reactivitymentioning

confidence: 91%

“…The Jain laboratory has found photocharged metal NPs to be involved in redox conversions triggered or catalyzed by LSPR excitation. These include the reduction of CO 2 to hydrocarbons, ,,, alcohol oxidation, , water oxidation to H 2 O 2 , electrochemical H 2 evolution, electrochemical CH 3 OH oxidation, and electrochemical NH 3 oxidation . The potentials on the photocharged NPs play an important energetic role in these reactions, understanding of which will guide strategies for harnessing solar energy.…”

Section: Influence Of Photopotentials On Reactivitymentioning

confidence: 99%

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Light-Induced Voltages in Catalysis by Plasmonic Nanostructures

Wilson

Jain

2020

Acc. Chem. Res.

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Conspectus Plasmonic nanostructures have garnered widescale scientific interest because of their strong light–matter interactions and the tunability of their absorption across the solar spectrum. At the heart of their superlative interaction with light is the resonant excitation of a collective oscillation of electrons in the nanostructure by the incident electromagnetic field. These resonant oscillations are known as localized surface plasmon resonances (LSPRs). In recent years, the community has uncovered intriguing photochemical attributes of noble metal nanostructures arising from their LSPRs. Chemical reactions that are otherwise unfavorable or sluggish in the dark are induced on the nanostructure surface upon photoexcitation of LSPRs. This phenomenon has led to the birth of plasmonic catalysis. The rates of a variety of kinetically challenging reactions are enhanced by plasmon-excited nanostructures. While the potential utility for solar energy harvesting and chemical production is clear, there is a natural curiosity about the precise origin(s) of plasmonic catalysis. One explanation is that the reactions are facilitated by the action of the intensely concentrated and confined electric fields generated on the nanostructure upon LSPR excitation. Another mechanism of activation involves hot carriers transiently produced in the metal nanostructure by damping of LSPRs. In this Account, we visit a phenomenon that has received less attention but has a key role to play in plasmonic catalysis and chemistry. Under common chemical scenarios, plasmonic excitation induces a potential or a voltage on a nanoparticle. This photopotential modifies the energetics of a chemical reaction on noble metal nanoparticles. In a range of cases studied by our laboratory and others, light-induced potentials underlie the plasmonic enhancement of reaction kinetics. The photopotential model does not replace other known mechanisms, but it complements them. There are multiple ways in which an electrostatic photopotential is produced by LSPR excitation, such as optical rectification, but one that is most relevant in chemical media is asymmetric charge transfer to solution-phase acceptors. Electrons and holes produced in a nanostructure by damping of LSPRs are not removed at the same rate. As a result, the slower carrier accumulates on the nanostructure, and a steady-state charge is built up on the nanostructure, leading to a photopotential. Potentials of up to a few hundred millivolts have been measured by our laboratory and others. A photocharged nanoparticle is a source of carriers of a higher potential than an uncharged one. As a result, redox chemical reactions on noble metal nanoparticles exhibit lower activation barriers under photoexcitation. In electrochemical reactions on noble metal nanoparticles, the photopotential supplements the applied potential. In a diverse set of reactions, the photopotential model explains the photoenhancement of rates as well as the trends as a function of light intensity and photon energy. With further g...

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Section: Influence Of Photopotentials On Reactivitymentioning

confidence: 91%

Section: Influence Of Photopotentials On Reactivitymentioning

confidence: 99%

Light-Induced Voltages in Catalysis by Plasmonic Nanostructures

Wilson

Jain

2020

Acc. Chem. Res.

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“…The influence of photopotentials on reactivity extends to electrochemical reactions at PMNs under illumination ( Wang et al., 2020 ; Huang et al., 2019 ). In electrochemical reactions, the onset overpotential ( η ) and current density signify the apparent activation barrier and total reaction rate, respectively.…”

Section: Plasmon-induced Potentialsmentioning

confidence: 99%

“…In addition, the specific mechanism by which energetic charge carriers interact with molecules that undergo chemical reactions needs to be further elucidated ( Kale et al., 2013 ; Brongersma et al., 2015 ; Mubeen et al., 2013 ). Apart from the photothermal effects and energetic charge carriers, plasmon-induced potential was proposed to be responsible for the enhancement of reaction kinetics at illuminated PMNs in newly published studies ( Wilson et al., 2019 ; Wang et al., 2020 ; Wilson and Jain, 2020 ). Herein, we give a brief introduction of pioneering and representative works about PMCRs and focus on three major aspects of the mechanism explanation, i.e., thermal and nonthermal effects, direct and indirect charge transfer, and plasmon-induced potentials.…”

Section: Introductionmentioning

confidence: 99%

Plasmonic metal nanostructures: concepts, challenges and opportunities in photo-mediated chemical transformations

Zhou

Shen

et al. 2021

iScience

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“…Recently, H 2 O 2 synthesis via PEC water splitting has achieved a high conversion efficiency, [ 121 ] and the feasibility of using PEC system to realize solar ammonia splitting has also begun to attract attention. [ 122 ] Based on the achievements, we present the remaining challenges and future perspectives in the development of metal oxide‐based heterostructures. With regard to photoelectrodes like PEC water‐splitting cells and PCs, each of them faces unique challenges.…”

Section: Conclusion and Prospectivementioning

confidence: 99%

Rational Design of Metal Oxide‐Based Heterostructure for Efficient Photocatalytic and Photoelectrochemical Systems

Xia

Wang

Kim

et al. 2020

Adv Funct Materials

112

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Solar‐driven photo‐to‐chemical conversion is an interesting approach for energy harvesting and storage with high sustainability. To achieve high photo‐to‐chemical conversion efficiency, it is important to develop cost‐effective and stable catalysts with high activity. Metal oxides provide an interesting platform for the development of efficient catalysts owing to their abundance, high stability, and tunable band edges. Their performance highly depends on the rational design of heterostructures with engineered electronic structures, modified charge migration behavior, tailored interfacial properties, and amplified electromagnetic fields. All these enable the achievement of efficient light harvesting, promoted charge separation and transport, and accelerated surface reactions. Herein, a recent study on rationally designed metal oxide heterostructures for enhancing photo‐to‐chemical energy conversion via photocatalytic and photoelectrochemical systems is reviewed. The approaches to enhance their conversion efficiency are as follows: 1) surface modification via loading of plasmonic metals and other photosensitizers; 2) surface regulation, including morphology, defect, and dopants; 3) interfacial assembly with metal oxides, other metal compounds, and metal‐free materials. Moreover, the underlying reaction mechanisms of metal oxide‐based heterostructures and how they affect the energy conversion efficiency are discussed. Finally, the challenges and perspectives on the development of metal oxide‐based heterostructures and associated photo‐to‐chemical devices are presented.

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Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

Cited by 49 publications

References 40 publications

Light-Induced Voltages in Catalysis by Plasmonic Nanostructures

Light-Induced Voltages in Catalysis by Plasmonic Nanostructures

Plasmonic metal nanostructures: concepts, challenges and opportunities in photo-mediated chemical transformations

Rational Design of Metal Oxide‐Based Heterostructure for Efficient Photocatalytic and Photoelectrochemical Systems

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