Special Issue "Plasmonic Photocatalysts"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Photocatalysis".

Deadline for manuscript submissions: closed (30 September 2020).

Special Issue Editor

Prof. Dr. Ewa Kowalska
Website
Guest Editor
Institute for Catalysis (ICAT), Hokkaido University, Sapporo, Hokkaido 060-0808, Japan
Interests: heterogeneous catalysis; photocatalysis; advanced oxidation technologies (AOTs); plasmonic photocatalyst; noble metals; antimicrobial properties; solar energy; solar fuel; faceted nanoparticles
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Special Issue Information

Dear Colleagues,

Over the last decade, plasmonic properties of noble metals, i.e., absorption of visible light due to plasmon resonance, have been used to activate wide band-gap semiconductors. Although plasmonic properties of noble metals were observed more than a century ago, scientifically explained ca. 30 years ago, and since then commercially used in many fields, the examination of their application for photocatalysis started a few years ago. Despite the novelty of plasmonic photocatalysis, many studies have already been performed to improve photocatalytic activity and stability, and to clarify the mechanism under irradiation with visible light.

Although desirable photoabsorption properties of plasmonic photocatalysts can be easily achieved by preparation of nanoparticles of different sizes and shapes, their photocatalytic activities (under visible light irradiation) are still low and must be improved for commercial usage. Therefore, various studies have been performed to get stable and highly active materials. Moreover, the mechanism of plasmonic photocatalysis has not been clarified yet, i.e., charge versus energy transfer. It is thought that the mechanism depends directly on the morphology of plasmonic photocatalysts and reaction conditions.

Despite the novelty and unclear mechanism, plasmonic photocatalysts have already proved to be highly efficient for environmental purification (water and wastewater treatment, air purification and self-cleaning surfaces for decomposition of both organic compounds and microorganisms), solar energy conversion (photocurrent generation and water splitting) and synthesis of organic compounds. Therefore, it is believed that plasmonic photocatalysts have the potential to be efficient solar photocatalysts for commercial application.

This Special Issue of Catalysts will be a collaborative effort to combine current research on plasmonic photocatalysis. Contributions on photocatalyst preparation and characterization, reaction mechanism, theoretical modeling and applications are all welcome.

Prof. Dr. Ewa Kowalska
Guest Editor

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Keywords

  • Plasmonic photocatalysis
  • Photocatalyst fabrication
  • Simulation and modeling of plasmon resonance
  • Mechanism study
  • Environmental purification
  • Energy conversion
  • Water splitting
  • New techniques of photocatalyst characterization
  • Morphology-governed activity
  • Removal of microbiological pollutants
  • Water/wastewater treatment
  • Air treatment
  • Self-cleaning surfaces
  • Theoretical study

Published Papers (10 papers)

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Research

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Open AccessFeature PaperArticle
Vis-Responsive Copper-Modified Titania for Decomposition of Organic Compounds and Microorganisms
Catalysts 2020, 10(10), 1194; https://doi.org/10.3390/catal10101194 - 16 Oct 2020
Abstract
Seven commercial titania (titanium(IV) oxide; TiO2) powders with different structural properties and crystalline compositions (anatase/rutile) were modified with copper by two variants of a photodeposition method, i.e., methanol dehydrogenation and water oxidation. The samples were characterized by diffuse reflectance spectroscopy (DRS), [...] Read more.
Seven commercial titania (titanium(IV) oxide; TiO2) powders with different structural properties and crystalline compositions (anatase/rutile) were modified with copper by two variants of a photodeposition method, i.e., methanol dehydrogenation and water oxidation. The samples were characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Although zero-valent copper was deposited on the surface of titania, oxidized forms of copper, post-formed in ambient conditions, were also detected in dried samples. All samples could absorb visible light (vis), due to localized surface plasmon resonance (LSPR) of zero-valent copper and by other copper species, including Cu2O, CuO and CuxO (x:1-2). The photocatalytic activities of samples were investigated under both ultraviolet (UV) and visible light irradiation (>450 nm) for oxidative decomposition of acetic acid. It was found that titania modification with copper significantly enhanced the photocatalytic activity, especially for anatase samples. The prolonged irradiation (from 1 to 5 h) during samples’ preparation resulted in aggregation of copper deposits, thus being detrimental for vis activity. It is proposed that oxidized forms of copper are more active under vis irradiation than plasmonic one. Antimicrobial properties against bacteria (Escherichia coli) and fungi (Aspergillus niger) under vis irradiation and in the dark confirmed that Cu/TiO2 exhibits a high antibacterial effect, mainly due to the intrinsic activity of copper species. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessFeature PaperArticle
Defective TiO2 Core-Shell Magnetic Photocatalyst Modified with Plasmonic Nanoparticles for Visible Light-Induced Photocatalytic Activity
Catalysts 2020, 10(6), 672; https://doi.org/10.3390/catal10060672 - 15 Jun 2020
Cited by 1
Abstract
In the presented work, for the first time, the metal-modified defective titanium(IV) oxide nanoparticles with well-defined titanium vacancies, was successfully obtained. Introducing platinum and copper nanoparticles (NPs) as surface modifiers of defective d-TiO2 significantly increased the photocatalytic activity in both UV-Vis and [...] Read more.
In the presented work, for the first time, the metal-modified defective titanium(IV) oxide nanoparticles with well-defined titanium vacancies, was successfully obtained. Introducing platinum and copper nanoparticles (NPs) as surface modifiers of defective d-TiO2 significantly increased the photocatalytic activity in both UV-Vis and Vis light ranges. Moreover, metal NPs deposition on the magnetic core allowed for the effective separation and reuse of the nanometer-sized photocatalyst from the suspension after the treatment process. The obtained Fe3O4@SiO2/d-TiO2-Pt/Cu photocatalysts were characterized by X-ray diffractometry (XRD) and specific surface area (BET) measurements, UV-Vis diffuse reflectance spectroscopy (DR-UV/Vis), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Further, the mechanism of phenol degradation and the role of four oxidative species (h+, e, OH, and O2) in the studied photocatalytic process were investigated. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessArticle
Synthesis of Au–Ag Alloy Nanoparticle-Incorporated AgBr Crystals
Catalysts 2019, 9(9), 745; https://doi.org/10.3390/catal9090745 - 03 Sep 2019
Abstract
Nanoscale composites consisting of silver and silver halide (Ag–AgX, X = Cl, Br, I) have attracted much attention as a novel type of visible-light photocatalyst (the so-called plasmonic photocatalysts), for solar-to-chemical transformations. Support-free Au–Ag alloy nanoparticle-incorporated AgBr crystals (Au–[email protected]) were synthesized by a [...] Read more.
Nanoscale composites consisting of silver and silver halide (Ag–AgX, X = Cl, Br, I) have attracted much attention as a novel type of visible-light photocatalyst (the so-called plasmonic photocatalysts), for solar-to-chemical transformations. Support-free Au–Ag alloy nanoparticle-incorporated AgBr crystals (Au–[email protected]) were synthesized by a photochemical method. At the initial step, Au ion-doped AgBr particles were prepared by adding an aqueous solution of AgNO3 to a mixed aqueous solution of KBr and HAuBr4. At the next step, UV-light illumination (λ = 365 nm) of a methanol suspension of the resulting solids yielded Au–Ag alloy nanoparticles with a mean size of approximately 5 nm in the micrometer-sized AgBr crystals. The mole percent of Au to all the Ag in Au–[email protected] was controlled below < 0.16 mol% by the HAuBr4 concentration in the first step. Finite-difference time-domain calculations indicated that the local electric field enhancement factor for the alloy nanoparticle drastically decreases with an increase in the Au content. Also, the peak of the localized surface plasmon resonance shifts towards longer wavelengths with increasing Au content. Au–[email protected] is a highly promising plasmonic photocatalyst for sunlight-driven chemical transformations due to the compatibility of the high local electric field enhancement and sunlight harvesting efficiency. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Review

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Open AccessReview
Morphology-Governed Performance of Plasmonic Photocatalysts
Catalysts 2020, 10(9), 1070; https://doi.org/10.3390/catal10091070 - 17 Sep 2020
Abstract
Plasmonic photocatalysts have been extensively studied for the past decade as a possible solution to energy crisis and environmental problems. Although various reports on plasmonic photocatalysts have been published, including synthesis methods, applications, and mechanism clarifications, the quantum yields of photochemical reactions are [...] Read more.
Plasmonic photocatalysts have been extensively studied for the past decade as a possible solution to energy crisis and environmental problems. Although various reports on plasmonic photocatalysts have been published, including synthesis methods, applications, and mechanism clarifications, the quantum yields of photochemical reactions are usually too low for commercialization. Accordingly, it has been proposed that preparation of plasmonic photocatalysts with efficient light harvesting and inhibition of charge carriers’ recombination might result in improvement of photocatalytic activity. Among various strategies, nano-architecture of plasmonic photocatalysts seems to be one of the best strategies, including the design of properties for both semiconductor and noble-metal-deposits, as well as the interactions between them. For example, faceted nanoparticles, nanotubes, aerogels, and super-nano structures of semiconductors have shown the improvement of photocatalytic activity and stability. Moreover, the selective deposition of noble metals on some parts of semiconductor nanostructures (e.g., specific facets, basal or lateral surfaces) results in an activity increase. Additionally, mono-, bi-, and ternary-metal-modifications have been proposed as the other ways of performance improvement. However, in some cases, the interactions between different noble metals might cause unwanted charge carriers’ recombination. Accordingly, this review discusses the recent strategies on the improvements of the photocatalytic performance of plasmonic photocatalysts. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessFeature PaperReview
Photonic Crystals for Plasmonic Photocatalysis
Catalysts 2020, 10(8), 827; https://doi.org/10.3390/catal10080827 - 23 Jul 2020
Cited by 2
Abstract
Noble metal (NM)-modified wide-bandgap semiconductors with activity under visible light (Vis) irradiation, due to localized surface plasmon resonance (LSPR), known as plasmonic photocatalysts, have been intensively studied over the last few years. Despite the novelty of the topic, a large number of reports [...] Read more.
Noble metal (NM)-modified wide-bandgap semiconductors with activity under visible light (Vis) irradiation, due to localized surface plasmon resonance (LSPR), known as plasmonic photocatalysts, have been intensively studied over the last few years. Despite the novelty of the topic, a large number of reports have already been published, discussing the optimal properties, synthesis methods and mechanism clarification. It has been proposed that both efficient light harvesting and charge carriers’ migration are detrimental for high and stable activity under Vis irradiation. Accordingly, photonic crystals (PCs) with photonic bandgap (PBG) and slow photon effects seem to be highly attractive for efficient use of incident photons. Therefore, the study on PCs-based plasmonic photocatalysts has been conducted, mainly on titania inverse opal (IO) modified with nanoparticles (NPs) of NM. Although, the research is quite new and only several reports have been published, it might be concluded that the matching between LSPR and PBG (especially at red edge) by tuning of NMNPs size and IO-void diameter, respectively, is the most crucial for the photocatalytic activity. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessFeature PaperReview
Plasmonic Photocatalysts for Microbiological Applications
Catalysts 2020, 10(8), 824; https://doi.org/10.3390/catal10080824 - 23 Jul 2020
Cited by 2
Abstract
Wide-bandgap semiconductors modified with nanostructures of noble metals for photocatalytic activity under vis irradiation due to localized surface plasmon resonance (LSPR), known as plasmonic photocatalysts, have been intensively investigated over the last decade. Most literature reports discuss the properties and activities of plasmonic [...] Read more.
Wide-bandgap semiconductors modified with nanostructures of noble metals for photocatalytic activity under vis irradiation due to localized surface plasmon resonance (LSPR), known as plasmonic photocatalysts, have been intensively investigated over the last decade. Most literature reports discuss the properties and activities of plasmonic photocatalysts for the decomposition of organic compounds and solar energy conversion. Although noble metals, especially silver and copper, have been known since ancient times as excellent antimicrobial agents, there are only limited studies on plasmonic photocatalysts for the inactivation of microorganisms (considering vis-excitation). Accordingly, this review has discussed the available literature reports on microbiological applications of plasmonic photocatalysis, including antibacterial, antiviral and antifungal properties, and also a novel study on other microbiological purposes, such as cancer treatment and drug delivery. Although some reports indicate high antimicrobial properties of these photocatalysts and their potential for medical/pharmaceutical applications, there is still a lack of comprehensive studies on the mechanism of their interactions with microbiological samples. Moreover, contradictory data have also been published, and thus more study is necessary for the final conclusions on the key-factor properties and the mechanisms of inactivation of microorganisms and the treatment of cancer cells. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessReview
Review of Experimental Setups for Plasmonic Photocatalytic Reactions
Catalysts 2020, 10(1), 46; https://doi.org/10.3390/catal10010046 - 31 Dec 2019
Cited by 1
Abstract
Plasmonic photocatalytic reactions have been substantially developed. However, the mechanism underlying the enhancement of such reactions is confusing in relevant studies. The plasmonic enhancements of photocatalytic reactions are hard to identify by processing chemically or physically. This review discusses the noteworthy experimental setups [...] Read more.
Plasmonic photocatalytic reactions have been substantially developed. However, the mechanism underlying the enhancement of such reactions is confusing in relevant studies. The plasmonic enhancements of photocatalytic reactions are hard to identify by processing chemically or physically. This review discusses the noteworthy experimental setups or designs for reactors that process various energy transformation paths for enhancing plasmonic photocatalytic reactions. Specially designed experimental setups can help characterize near-field optical responses in inducing plasmons and transformation of light energy. Electrochemical measurements, dark-field imaging, spectral measurements, and matched coupling of wavevectors lead to further understanding of the mechanism underlying plasmonic enhancement. The discussions herein can provide valuable ideas for advanced future studies. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessReview
Synthesis of Plasmonic Photocatalysts for Water Splitting
Catalysts 2019, 9(12), 982; https://doi.org/10.3390/catal9120982 - 22 Nov 2019
Cited by 1
Abstract
Production of H2, O2, and some useful chemicals by solar water splitting is widely expected to be one of the ultimate technologies in solving energy and environmental problems worldwide. Plasmonic enhancement of photocatalytic water splitting is attracting much attention. [...] Read more.
Production of H2, O2, and some useful chemicals by solar water splitting is widely expected to be one of the ultimate technologies in solving energy and environmental problems worldwide. Plasmonic enhancement of photocatalytic water splitting is attracting much attention. However, the enhancement factors reported so far are not as high as expected. Hence, further investigation of the plasmonic photocatalysts for water splitting is now needed. In this paper, recent work demonstrating plasmonic photocatalytic water splitting is reviewed. Particular emphasis is given to the fabrication process and the morphological features of the plasmonic photocatalysts. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessReview
Photocatalytic Reversible Reactions Driven by Localized Surface Plasmon Resonance
Catalysts 2019, 9(2), 193; https://doi.org/10.3390/catal9020193 - 20 Feb 2019
Cited by 3
Abstract
In this study, we review photocatalytic reversible surface catalytic reactions driven by localized surface plasmon resonance. Firstly, we briefly introduce the synthesis of 4,4′-dimercaptoazobenzene (DMAB) from 4-nitrobenzenethiol (4NBT) using surface-enhanced Raman scattering (SERS) technology. Furthermore, we study the photosynthetic and degradation processes of [...] Read more.
In this study, we review photocatalytic reversible surface catalytic reactions driven by localized surface plasmon resonance. Firstly, we briefly introduce the synthesis of 4,4′-dimercaptoazobenzene (DMAB) from 4-nitrobenzenethiol (4NBT) using surface-enhanced Raman scattering (SERS) technology. Furthermore, we study the photosynthetic and degradation processes of 4NBT to DMAB reduction, as well as factors associated with them, such as laser wavelength, reaction time, substrate, and pH. Last but not least, we reveal the competitive relationship between photosynthetic and degradation pathways for this reduction reaction by SERS technology on the substrate of Au film over a nanosphere. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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Open AccessReview
Plasmonic Photocatalysts Monitored by Tip-Enhanced Raman Spectroscopy
Catalysts 2019, 9(2), 109; https://doi.org/10.3390/catal9020109 - 22 Jan 2019
Cited by 1
Abstract
In this review, we first prove the resonance dissociation process by using time-dependent measurements of tip-enhanced resonance Raman spectroscopy (TERRS) under high vacuum conditions. Second, we show how to use thermal electrons to dissociate Malachite Green (MG) and the hot electrons in the [...] Read more.
In this review, we first prove the resonance dissociation process by using time-dependent measurements of tip-enhanced resonance Raman spectroscopy (TERRS) under high vacuum conditions. Second, we show how to use thermal electrons to dissociate Malachite Green (MG) and the hot electrons in the nanogap of the high vacuum tip-enhanced Raman spectroscopy (TERS) device that are generated by plasma decay. Malachite Green is excited by resonance and adsorbed on the Ag and Au surfaces. Finally, we describe real-world and real-time observations of plasmon-induced general chemical reactions of individual molecules. Full article
(This article belongs to the Special Issue Plasmonic Photocatalysts)
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