Visible‐Light‐Driven Plasmonic Photocatalysis Enhanced by Charge Accumulation

Kao, Kun‐Che; Nishi, Hidetaka; Tatsuma, Tetsu

doi:10.1002/cnma.201900187

Cited by 9 publications

(13 citation statements)

References 41 publications

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“…We recently developed a PICS photoanode consisting of a fluorine‐doped tin oxide (FTO) electrode, TiO 2 (cp), AuNPs, and Ni(OH) 2 (FTO/TiO 2 (cp)/AuNP/Ni(OH) 2 , Figure f) for oxygen evolution . The Faradaic efficiency for this photoanode was estimated to be ∼40% at +0.2 V vs. Ag|AgCl in a three‐electrode system with a Pt counter electrode and a N 2 ‐saturated 0.1 M KOH electrolyte.…”

Section: Figurementioning

confidence: 99%

“…Ni(OH) 2 is known to be a good catalyst for oxygen evolution . It can also store positive charges, and therefore has been applied to photocatalysts with the oxidative energy storage ability and a photoanode for multi‐electron oxidation . The AuNP size and the Ni(OH) 2 thickness were optimized (47 nm and ∼100 nm, respectively) in terms of the efficiency (Figure S3).…”

Section: Figurementioning

confidence: 99%

“…[28][29][30] It can also store positive charges, [31][32][33] and therefore has been applied to photocatalysts with the oxidative energy storage ability [34] and a photoanode for multielectron oxidation. [27] The AuNP size and the Ni(OH) 2 thickness were optimized (47 nm and~100 nm, respectively) in terms of the efficiency ( Figure S3). Figure 4a shows LSVs of the fabricated photocathode and photoanode in N 2 -purged 0.5 M aqueous Na 2 SO 4 (pH~7) and 0.1 M aqueous KOH (pH~12), respectively.…”

Section: A Dual Plasmonic Photoelectrode System For Visible-light Phomentioning

confidence: 99%

“…Figure a shows LSVs of the fabricated photocathode and photoanode in N 2 ‐purged 0.5 M aqueous Na 2 SO 4 (pH∼7) and 0.1 M aqueous KOH (pH ∼12), respectively. Anodic and cathodic currents, which might be derived from oxidation of water and reduction of water or residual oxygen, respectively, were observed under visible light. The maximum current density of both photoelectrodes was around 15 μA cm −2 .…”

Section: Figurementioning

confidence: 99%

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A Dual Plasmonic Photoelectrode System for Visible‐Light Photocatalysis

et al. 2020

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Plasmonic photocathodes based on plasmon‐induced charge separation (PICS) were prepared by depositing an Au nanoparticle (AuNP) ensemble on a transparent electrode and coating it with compact TiO2. Its PICS efficiency was improved by coating it further with porous TiO2 or introducing a NiO blocking layer as an underlayer of the AuNP ensemble. The former photocathode was modified further with Pt co‐catalyst nanoparticles, and combined with a PICS photoanode fabricated by depositing a AuNP ensemble on compact TiO2 and coating it with a Ni(OH)2 charge accumulation layer. The dual plasmonic photoelectrode system thus obtained exhibited a higher efficiency than the sum of the efficiencies of the single photoanode and single photocathode.

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Section: A Dual Plasmonic Photoelectrode System For Visible-light Phomentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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A Dual Plasmonic Photoelectrode System for Visible‐Light Photocatalysis

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“…Besides the hole ejection, a hole injection into a HTM has been reported for ETM–metal–HTM (E-M-H) type solid-state photovoltaic cells ,,, or photoelectrodes, ,, in which plasmonic nanoparticles are introduced in between an ETM and an HTM. If the work function of the metal ( E M ) is larger than, or close to the ionization energy of the HTM ( E H ), ,− both of the holes and relaxed positive charges are transferred from the metal to the VB or HOMO of the HTM (Figure b).…”

Section: Introductionmentioning

confidence: 99%

Stepwise Injection of Energetic Electrons and Holes in Plasmon-Induced Charge Separation

2019

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Although there are many mechanistic studies for plasmon-induced charge separation (PICS), most of them have been devoted to energetic electron injection (or hot electron injection) from plasmonic metal nanoparticles into electron transport materials (ETMs) including n-type semiconductors. Here we also studied energetic hole injection (or hot hole injection) into five different organic hole transport materials (HTMs) with different ionization energies, by using solid-state photovoltaic cells fabricated by introducing gold nanoparticles (AuNPs) in between TiO2, which is an ETM, and a HTM. As a result, photocurrents based on PICS are obtained even if the height of the energy barrier at the Au–HTM interface is 0.9 eV. Therefore, the present PICS processes involve both energetic electron injection from AuNPs to TiO2 and hole injection from AuNPs to the HTMs. In this case, simultaneous electron–hole injection, in which one electron–hole pair gives simultaneous electron injection into TiO2 and hole injection into a HTM, is often postulated. However, there is another possibility of stepwise electron–hole injection, in which one electron–hole pair leads to electron injection into TiO2 and another pair gives hole injection into a HTM. The stepwise injection process is accompanied by recombination of the residual hole of the former pair and the electron of the latter. The present cells generated the photocurrents even if the incident photon energy was lower than the sum of the TiO2–Au and Au–HTM barrier energies (≤2.1 eV). In addition, experimentally obtained photocurrent action spectra of the cells can be reproduced on the basis of plasmonic light absorption and theoretically analyzed carrier injection efficiencies, when the stepwise injection is assumed. It was therefore concluded that the stepwise carrier injection chiefly contributes to the present PICS processes.

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Effect of Nanoparticle Size on Plasmonic Heat‐Driven Organic Transformation

2022

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Plasmonic nanomaterials have the potential to convert light to heat energy in an efficient and localized fashion. Here, we report the use of plasmonic heat from gold nanoparticles (AuNPs) in performing an important chemical transformation of pyrone to pyridinone in water. The yield obtained using plasmonic heat (∼75%) is comparable to that obtained from normal heating at ∼90 °C. Further, this photothermally driven organic reaction is used as a tool to study the effect of NP size on the practical utilization of the plasmonic heat dissipated. AuNPs in the size regime of 10–24 nm are found to be most efficient in driving the pyrone to pyridinone conversion, which is attributed to the dependence of absorption cross‐section and heat capacity on the NP size. The results obtained are validated using conventional plasmonically driven solar‐vapor generation experiments. Our study proves the suitability of a thermally driven organic reaction for qualitatively comparing the effect of various NP parameters on the chemical effectiveness of the plasmonic heat, which can be crucial in our efforts to understand the role of thermalization process in different plasmonically powered processes.

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Visible‐Light‐Driven Plasmonic Photocatalysis Enhanced by Charge Accumulation

Cited by 9 publications

References 41 publications

A Dual Plasmonic Photoelectrode System for Visible‐Light Photocatalysis

A Dual Plasmonic Photoelectrode System for Visible‐Light Photocatalysis

Stepwise Injection of Energetic Electrons and Holes in Plasmon-Induced Charge Separation

Effect of Nanoparticle Size on Plasmonic Heat‐Driven Organic Transformation

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