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Keywords = plasmon-driven photocatalysis

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54 pages, 15241 KiB  
Review
Heterogeneous Photocatalysis for Advanced Water Treatment: Materials, Mechanisms, Reactor Configurations, and Emerging Applications
by Maria Paiu, Doina Lutic, Lidia Favier and Maria Gavrilescu
Appl. Sci. 2025, 15(10), 5681; https://doi.org/10.3390/app15105681 - 19 May 2025
Cited by 2 | Viewed by 1584
Abstract
Heterogeneous photocatalysis has emerged as a versatile and sustainable technology for the degradation of emerging contaminants in water. This review highlights recent advancements in photocatalysts design, including band gap engineering, heterojunction formation, and plasmonic enhancement to enable visible-light activation. Various reactor configurations, such [...] Read more.
Heterogeneous photocatalysis has emerged as a versatile and sustainable technology for the degradation of emerging contaminants in water. This review highlights recent advancements in photocatalysts design, including band gap engineering, heterojunction formation, and plasmonic enhancement to enable visible-light activation. Various reactor configurations, such as slurry, immobilized, annular, flat plate, and membrane-based systems, are examined in terms of their efficiency, scalability, and operational challenges. Hybrid systems combining photocatalysis with membrane filtration, adsorption, Fenton processes, and biological treatments demonstrate improved removal efficiency and broader applicability. Energy performance metrics such as quantum yield and electrical energy per order are discussed as essential tools for evaluating system feasibility. Special attention is given to solar-driven reactors and smart responsive materials, which enhance adaptability and sustainability. Additionally, artificial intelligence and machine learning approaches are explored as accelerators for catalyst discovery and process optimization. Altogether, these advances position photocatalysis as a key component in future water treatment strategies, particularly in decentralized and low-resource contexts. The integration of material innovation, system design, and data-driven optimization underlines the potential of photocatalysis to contribute to global efforts in environmental protection and sustainable development. Full article
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37 pages, 31186 KiB  
Review
Application of Graphene-Based Solar Driven Interfacial Evaporation-Coupled Photocatalysis in Water Treatment
by Yining Zhang, Huiqin Wang and Jisheng Zhang
Catalysts 2025, 15(4), 336; https://doi.org/10.3390/catal15040336 - 31 Mar 2025
Cited by 1 | Viewed by 1308
Abstract
The global shortage of freshwater resources and the energy crisis have propelled solar-driven interfacial evaporation (SDIE) coupled with photocatalytic technology to become a research focus in efficient and low-carbon water treatment. Graphene-based materials demonstrate unique advantages in SDIE–photocatalysis integrated systems, owing to their [...] Read more.
The global shortage of freshwater resources and the energy crisis have propelled solar-driven interfacial evaporation (SDIE) coupled with photocatalytic technology to become a research focus in efficient and low-carbon water treatment. Graphene-based materials demonstrate unique advantages in SDIE–photocatalysis integrated systems, owing to their broadband light absorption, ultrafast thermal carrier dynamics, tunable electronic structure, and low evaporation enthalpy characteristics. This review systematically investigates the enhancement mechanisms of graphene photothermal conversion on photocatalytic processes, including (1) improving light absorption through surface morphology modulation, defect engineering, and plasmonic material compositing; (2) reducing water evaporation enthalpy via hydrophilic functional group modification and porous structure design; (3) suppressing heat loss through thermal insulation layers and 3D structural optimization; and (4) enhancing water transport efficiency via fluid channel engineering and wettability control. Furthermore, salt resistance strategies and structural optimization significantly improve system practicality and stability. In water treatment applications, graphene-based SDIE systems achieve synergistic “adsorption–catalysis–evaporation” effects, enabling efficient the degradation of organic pollutants, reduction in/fixation of heavy metal ions, and microbial inactivation. However, practical implementation still faces challenges including low steam condensation efficiency, insufficient long-term material durability, and high scaling-up costs. Future research should prioritize enhancing heat and mass transfer in condensation systems, optimizing material environmental adaptability, and developing low-cost manufacturing processes to promote widespread application of graphene-based SDIE–photocatalysis integrated systems. Full article
(This article belongs to the Special Issue Mineral-Based Composite Catalytic Materials)
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19 pages, 4137 KiB  
Article
Au Supported on Bovine-Bone-Derived Hydroxyapatite Catalyzes CO2 Photochemical Reduction toward Methanol
by Sergio Arturo Gama-Lara, Alfredo Rafael Vilchis-Néstor, Deysi Amado-Piña and Reyna Natividad
Catalysts 2024, 14(7), 417; https://doi.org/10.3390/catal14070417 - 29 Jun 2024
Cited by 3 | Viewed by 1516
Abstract
In this work, gold-photo-catalyzed CO2 transformation was conducted and the effect of three variables with two levels was investigated: support (TiO2 and hydroxyapatite from bovine bone (BB)), Au content (5 and 10%) and activation wavelength (254 and 380–700 nm). Reactions were [...] Read more.
In this work, gold-photo-catalyzed CO2 transformation was conducted and the effect of three variables with two levels was investigated: support (TiO2 and hydroxyapatite from bovine bone (BB)), Au content (5 and 10%) and activation wavelength (254 and 380–700 nm). Reactions were conducted in a stirred tank reactor by bubbling CO2 (9 × 10−3 dm3/min) in 0.1 dm3 of 0.5 M NaOH solution. The catalysts were synthesized using AuCl3, TiO2 and BB. Au nanoparticles were obtained by reduction with Hetheroteca inuloides, thus eliminating calcination and hydrogenation to reduce the gold species. By TEM, the particle size distribution was determined, and the synthesized nanoparticle sizes varied in the range of 9 to 19 nm, depending on the support and Au content. By UV–Vis spectroscopy, the energy band gaps of the prepared materials were 2.18 eV (10% Au/BB), 2.38 eV (5% Au/BB), 2.42 eV (BB), 3.39 eV (5% Au/TiO2), 3.41 eV (10% Au/TiO2) and 3.43 eV for pure TiO2. Methanol and formic and acetic acids were identified during the process. Selectivity toward methanol was found to be improved with the 10% Au/BB catalytic system. Full article
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20 pages, 2603 KiB  
Review
Recent Advances in Metal-Organic Framework (MOF)-Based Photocatalysts: Design Strategies and Applications in Heavy Metal Control
by Qiang Ma, Yunling Li, Yawen Tan, Bowen Xu, Jun Cai, Yingjie Zhang, Qingyuan Wang, Qihong Wu, Bowen Yang and Jin Huang
Molecules 2023, 28(18), 6681; https://doi.org/10.3390/molecules28186681 - 18 Sep 2023
Cited by 23 | Viewed by 5724
Abstract
The heavy metal contamination of water systems has become a major environmental concern worldwide. Photocatalysis using metal-organic frameworks (MOFs) has emerged as a promising approach for heavy metal remediation, owing to the ability of MOFs to fully degrade contaminants through redox reactions that [...] Read more.
The heavy metal contamination of water systems has become a major environmental concern worldwide. Photocatalysis using metal-organic frameworks (MOFs) has emerged as a promising approach for heavy metal remediation, owing to the ability of MOFs to fully degrade contaminants through redox reactions that are driven by photogenerated charge carriers. This review provides a comprehensive analysis of recent developments in MOF-based photocatalysts for removing and decontaminating heavy metals from water. The tunable nature of MOFs allows the rational design of composition and features to enhance light harvesting, charge separation, pollutant absorptivity, and photocatalytic activities. Key strategies employed include metal coordination tuning, organic ligand functionalization, heteroatom doping, plasmonic nanoparticle incorporation, defect engineering, and morphology control. The mechanisms involved in the interactions between MOF photocatalysts and heavy metal contaminants are discussed, including light absorption, charge carrier separation, metal ion adsorption, and photocatalytic redox reactions. The review highlights diverse applications of MOF photocatalysts in treating heavy metals such as lead, mercury, chromium, cadmium, silver, arsenic, nickel, etc. in water remediation. Kinetic modeling provides vital insights into the complex interplay between coupled processes such as adsorption and photocatalytic degradation that influence treatment efficiency. Life cycle assessment (LCA) is also crucial for evaluating the sustainability of MOF-based technologies. By elucidating the latest advances, current challenges, and future opportunities, this review provides insights into the potential of MOF-based photocatalysts as a sustainable technology for addressing the critical issue of heavy metal pollution in water systems. Ongoing efforts are needed to address the issues of stability, recyclability, scalable synthesis, and practical reactor engineering. Full article
(This article belongs to the Special Issue Design and Synthesis of Functional Materials for Photocatalysis)
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14 pages, 2744 KiB  
Article
Synthesis of Ag-OMS Catalyst for Sunlight-Assisted Photodegradation of Crystal Violet Dye
by Muhammad Saeed, Renzon Daniel Cosme Pecho, Sandeep Panchal, Sadeq K. Alhag, Laila A. Al-Shuraym, Khalid M. Al Syaad and Usman Hanif Bhutta
Water 2023, 15(13), 2480; https://doi.org/10.3390/w15132480 - 6 Jul 2023
Cited by 8 | Viewed by 2316
Abstract
The contamination of water with organic pollutants, such as dyes, has become a serious threat to the environment. Therefore, the development of a cost-effective, eco-friendly, proficient, and visible-light-driven catalyst for the treatment of organic dye-contaminated wastewater has been a burning issue recently. Photocatalysis [...] Read more.
The contamination of water with organic pollutants, such as dyes, has become a serious threat to the environment. Therefore, the development of a cost-effective, eco-friendly, proficient, and visible-light-driven catalyst for the treatment of organic dye-contaminated wastewater has been a burning issue recently. Photocatalysis is suggested as a potential treatment technique for the eradication of organic pollutants. The 1D tunnel-structured manganese oxide octahedral molecular sieve (OMS) is a suitable substance to be tested as a visible-light-driven photocatalyst for the degradation of organic contaminants. However, the fast recombination of photoinduced charges (h+/e) limits its photocatalytic application. The development of heterojunctions between OMS and other metals, such as Ag, is a suitable technique for improving the photocatalytic performance of OMS. In this study, Ag-OMS with plasmon-enhanced photocatalytic activity is reported for the photodegradation of crystal violet dye. Manganese oxide OMS was prepared by an acidic precipitation method using potassium permanganate, manganese acetate, and nitric acid as precursor materials. Ag nanoparticles were deposited on OMS using leaf extracts of Calotropis gigantea. The deposition of Ag enhanced the photocatalytic performance of OMS from 68 to 95%. The effects of Ag contents, catalyst dosage, and concentration of crystal violet dye on catalytic performance were explored as well. Approximately 100, 95, and 75% photodegradation of 50, 100, and 150 mg/L crystal violet dye was observed in 90, 120, and 120 min in the presence of 10% Ag-OMS, respectively. Excellent photocatalytic performance, low dose utilization, and reusability proved that Ag-OMS might have practical environmental applications. Full article
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15 pages, 4615 KiB  
Article
Novel Heterostructures of Noble Plasmonic Metals/Ga-Substituted Hydrotalcite for Solar Light Driven Photocatalysis toward Water Purification
by Eugenia Corina Ignat, Doina Lutic, Gabriel Ababei and Gabriela Carja
Catalysts 2022, 12(11), 1351; https://doi.org/10.3390/catal12111351 - 2 Nov 2022
Cited by 5 | Viewed by 2256
Abstract
Heterostructures formed by close conjunctions of plasmonic metal nanoparticles and non-plasmonic (2D) lamellar nanostructures are receiving extensive interest as solar-light-driven photocatalysts for environmental pollutant remediation. Herein, the conjunction of plasmonic Au or Ag and Ga-substituted hydrotalcite are obtained by exploiting the manifestation of [...] Read more.
Heterostructures formed by close conjunctions of plasmonic metal nanoparticles and non-plasmonic (2D) lamellar nanostructures are receiving extensive interest as solar-light-driven photocatalysts for environmental pollutant remediation. Herein, the conjunction of plasmonic Au or Ag and Ga-substituted hydrotalcite are obtained by exploiting the manifestation of the structural “memory effect” of Ga-substituted hydrotalcite in the aqueous solutions of Au(CH3COO)3 and Ag2SO4, respectively. The 2D layered matrix of MgGaAl plays a dual function; it is involved in the synthesis of the plasmonic metal nanoparticles, and further, is acting as a support. The compressive investigations using X-ray diffraction (XRD), UV-diffuse reflectance spectroscopy (UVDR), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM/HRTEM), high-angle annular dark-field imaging/scanning transmittance electron microscopy (HAADF/STEM) and X-ray photoelectron spectroscopy (XPS) describe structural, composition and nano/micromorphology characteristics of the novel heterostructures, while UVDR analysis afforded to study the features of their plasmonic responses. Results reveal that the catalysts are formed by close conjunction of small nanoparticles of Au or Ag (with a mean size less than 20 nm) that are formed on the larger particles of MgGaAl and own plasmonic features within the visible range. The catalysts performances were tested towards photocatalytic degradation of p-dichlorobenzene and 4-nitrophenol under solar light irradiation. Results revealed that the degradation of the pollutants is entangled to the plasmonic response of the heterostructured catalysts that is the key functionality in promoting photocatalysis and degrading the pollutants, under solar light irradiation. MgGaAl showed a very low photocatalytic activity when irradiated by UV or solar light. Notably, the heterostructured catalysts proceeded in good to excellent yield to remove the tested pollutants, under solar light irradiation. The sustainability of the novel catalysts was assessed through the kinetic analysis of the degradation processes of the tested pollutants and their mixture. Full article
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12 pages, 2822 KiB  
Article
Hot Electron-Driven Photocatalysis Using Sub-5 nm Gap Plasmonic Nanofinger Arrays
by Yunxiang Wang, Buyun Chen, Deming Meng, Boxiang Song, Zerui Liu, Pan Hu, Hao Yang, Tse-Hsien Ou, Fanxin Liu, Halton Pi, Irene Pi, Isleen Pi and Wei Wu
Nanomaterials 2022, 12(21), 3730; https://doi.org/10.3390/nano12213730 - 24 Oct 2022
Cited by 9 | Viewed by 2306
Abstract
Semiconductor photocatalysis has received increasing attention because of its potential to address problems related to the energy crisis and environmental issues. However, conventional semiconductor photocatalysts, such as TiO2 and ZnO, can only be activated by ultraviolet light due to their wide band [...] Read more.
Semiconductor photocatalysis has received increasing attention because of its potential to address problems related to the energy crisis and environmental issues. However, conventional semiconductor photocatalysts, such as TiO2 and ZnO, can only be activated by ultraviolet light due to their wide band gap. To extend the light absorption into the visible range, the localized surface plasmon resonance (LSPR) effect of noble metal nanoparticles (NPs) has been widely used. Noble metal NPs can couple incident visible light energy to strong LSPR, and the nonradiative decay of LSPR generates nonthermal hot carriers that can be injected into adjacent semiconductor material to enhance its photocatalytic activity. Here we demonstrate that nanoimprint-defined gap plasmonic nanofinger arrays can function as visible light-driven plasmonic photocatalysts. The sub-5 nm gaps between pairs of collapsed nanofingers can support ultra-strong plasmon resonance and thus boost the population of hot carriers. The semiconductor material is exactly placed at the hot spots, providing an efficient pathway for hot carrier injection from plasmonic metal to catalytic materials. This nanostructure thus exhibits high plasmon-enhanced photocatalytic activity under visible light. The hot carrier injection mechanism of this platform was systematically investigated. The plasmonic enhancement factor was calculated using the finite-difference time-domain (FDTD) method and was consistent with the measured improvement of the photocatalytic activity. This platform, benefiting from the precise controllable geometry, provides a deeper understanding of the mechanism of plasmonic photocatalysis. Full article
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11 pages, 4060 KiB  
Article
Enhancing Photocatalysis of Ag Nanoparticles Decorated BaTiO3 Nanofibers through Plasmon-Induced Resonance Energy Transfer Turned by Piezoelectric Field
by Peng Chen, Xiu Li, Zeqian Ren, Jizhou Wu, Yuqing Li, Wenliang Liu, Peng Li, Yongming Fu and Jie Ma
Catalysts 2022, 12(9), 987; https://doi.org/10.3390/catal12090987 - 1 Sep 2022
Cited by 17 | Viewed by 2837
Abstract
Revealing the charge transfer path is very important for studying the photocatalytic mechanism and improving photocatalytic performance. In this work, the charge transfer path turned by the piezoelectricity in Ag-BaTiO3 nanofibers is discussed through degrading methyl orange. The piezo-photocatalytic degradation rate of [...] Read more.
Revealing the charge transfer path is very important for studying the photocatalytic mechanism and improving photocatalytic performance. In this work, the charge transfer path turned by the piezoelectricity in Ag-BaTiO3 nanofibers is discussed through degrading methyl orange. The piezo-photocatalytic degradation rate of Ag-BaTiO3 is much higher than the photocatalysis of Ag-BaTiO3 and piezo-photocatalysis of BaTiO3, implying the coupling effect between Ag nanoparticle-induced localized surface plasmon resonance (LSPR), photoexcited electron-hole pairs, and deformation-induced piezoelectric field. With the distribution density of Ag nanoparticles doubling, the LSPR field increases by one order of magnitude. Combined with charge separation driven by the piezoelectric field, more electrons in BaTiO3 nanofibers are excited by plasmon-induced resonance energy transfer to improve the photocatalytic property. Full article
(This article belongs to the Special Issue Advances in Heterojunction Photocatalysts)
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21 pages, 6632 KiB  
Review
Mechanistic Insights into Graphene Oxide Driven Photocatalysis as Co-Catalyst and Sole Catalyst in Degradation of Organic Dye Pollutants
by Jai Prakash
Photochem 2022, 2(3), 651-671; https://doi.org/10.3390/photochem2030043 - 17 Aug 2022
Cited by 30 | Viewed by 4460
Abstract
Photocatalysis is a promising route to utilize sunlight, which has been potentially used to solve energy as well as environmental problems with an emphasis on fundamental understanding and technological applications in society. Semiconductors are excellent photocatalysts but often show less efficient activities due [...] Read more.
Photocatalysis is a promising route to utilize sunlight, which has been potentially used to solve energy as well as environmental problems with an emphasis on fundamental understanding and technological applications in society. Semiconductors are excellent photocatalysts but often show less efficient activities due to the fast recombination of photogenerated charge carriers and very slow kinetics of surface photochemical reactions. However, recent advancements show promising strategies to improve their photocatalytic activities, including surface modifications using suitable co-catalysts and the development of novel efficient photocatalysts. Graphene oxide (GO) is one of such nanomaterials which shows multifarious roles in photocatalysis with a great potential to act as an independent solar-driven sole photocatalyst. In this minireview, the photochemistry of GO has been discussed in view of its multifarious roles/mechanisms in improving the photocatalytic activity of metal oxide semiconductors, plasmonic nanomaterials, and also their nanocomposites. In addition, recent advancements and applications of such GO-based photocatalysts in photocatalytic degradation of organic dye pollutants, including engineering of GO as the sole photocatalyst, have been discussed. Furthermore, the challenges and future prospects for the development of GO-based photocatalysts are discussed. Full article
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12 pages, 3144 KiB  
Article
Enhanced Visible-Light-Driven Photocatalysis of Ag/Ag2O/ZnO Nanocomposite Heterostructures
by Chadrasekhar Loka and Kee-Sun Lee
Nanomaterials 2022, 12(15), 2528; https://doi.org/10.3390/nano12152528 - 23 Jul 2022
Cited by 37 | Viewed by 3902
Abstract
Visible-light-driven photocatalysis is one promising and efficient approach for decontaminating pollutants. Herein, we report the combination of localized surface plasmon resonance (LSPR) and p-n heterojunction structure Ag-Ag2O-ZnO nanocomposite synthesized by a hydrothermal process for the suppression of photogenerated electron-hole pair recombination [...] Read more.
Visible-light-driven photocatalysis is one promising and efficient approach for decontaminating pollutants. Herein, we report the combination of localized surface plasmon resonance (LSPR) and p-n heterojunction structure Ag-Ag2O-ZnO nanocomposite synthesized by a hydrothermal process for the suppression of photogenerated electron-hole pair recombination rates, the extension of the absorption edge to the visible region, and the enhancement of photocatalytic efficiency. The prepared nanocomposites were investigated by standard analytical techniques and the results revealed that the synthesized powders were comprised of Ag, Ag2O, and ZnO phases. Photocatalytic activity of the photocatalyst tested for methylene blue, methyl orange, and rhodamine B showed the highest photocatalytic degradation efficiency: 97.3%, 91.1%, and 94.8% within 60 min under visible-light irradiation. The average lifetime of the photogenerated charge carriers was increased twofold in the Ag-Ag2O-ZnO photocatalyst (~10 ns) compared to the pure ZnO (~5.2 ns). The enhanced photocatalytic activity resulted from a decrease of the charge carrier recombination rate as inferred from the steady-state and time-resolved photoluminescence investigations, and the increased photoabsorption ability. The Ag-Ag2O-ZnO photocatalyst was stable over five repeated cyclic photodegradation tests without showing any significant changes in performance. Additionally, the structure indicated a potential for application in environmental remediation. The present study showcases the robust design of highly efficient and reusable visible-light-active photocatalysts via the combination of p-n heterojunction and LSPR phenomena. Full article
(This article belongs to the Special Issue Nanomaterials for Energy Conversion and Catalytic Applications)
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12 pages, 3452 KiB  
Article
In-Situ Monitoring the SERS Spectra of para-Aminothiophenol Adsorbed on Plasmon-Tunable Au@Ag Core–Shell Nanostars
by Yan Ke, Bin Chen, Mengen Hu, Ningning Zhou, Zhulin Huang and Guowen Meng
Nanomaterials 2022, 12(7), 1156; https://doi.org/10.3390/nano12071156 - 31 Mar 2022
Cited by 10 | Viewed by 2568
Abstract
Plasmon-induced photocatalysis on noble metal surfaces has attracted broad attention due to its application in sunlight energy conversion, while the selectivity of plasmonic platforms remains unclear. Herein, we present the controlled plasmon-mediated oxidation of para-aminothiophenol (p-ATP) by employing Au@Ag core–shell nanostars [...] Read more.
Plasmon-induced photocatalysis on noble metal surfaces has attracted broad attention due to its application in sunlight energy conversion, while the selectivity of plasmonic platforms remains unclear. Herein, we present the controlled plasmon-mediated oxidation of para-aminothiophenol (p-ATP) by employing Au@Ag core–shell nanostars with tunable tip plasmons in visible–near-infrared range as reactors. In-situ Raman measurements indicate that Au@Ag core–shell nanostars essentially promote the conversion of p-ATP to 4,4′-dimercaptoazobenzene (DMAB) due to hot carriers excited by localized surface plasmon resonance. Au@Ag nanostars with plasmon modes under resonant light excitation suggested higher catalytic efficiency, as evidenced by the larger intensity ratios between 1440 cm−1 (N=N stretching of DMAB) and 1080 cm−1 shifts (C–S stretching of p-ATP). Importantly, the time-dependent surface-enhanced Raman scattering spectra showed that the conversion efficiency of p-ATP was mainly dictated by the resonance condition between the tip plasmon mode of Au@Ag core–shell nanostars and the excitation light, as well as the choice of excitation wavelength. These results show that plasmon bands of metal nanostructures play an important role in the efficiency of plasmon-driven photocatalysis. Full article
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7 pages, 1192 KiB  
Article
Plasma-Driven Photocatalysis Based on Gold Nanoporous Arrays
by Lisheng Zhang, Yiyuan Zhang, Xueyan Wang and Duan Zhang
Nanomaterials 2021, 11(10), 2710; https://doi.org/10.3390/nano11102710 - 14 Oct 2021
Cited by 4 | Viewed by 2371
Abstract
Various effects caused by surface plasmons including enhanced electromagnetic field, local heating, and excited electrons/holes can not only redistribute the electromagnetic field in the time domain and space but also redistribute the excited carriers and drive chemical reactions. In this study, firstly, an [...] Read more.
Various effects caused by surface plasmons including enhanced electromagnetic field, local heating, and excited electrons/holes can not only redistribute the electromagnetic field in the time domain and space but also redistribute the excited carriers and drive chemical reactions. In this study, firstly, an Au nanoporous array photocatalyst with the arrayed gauge was prepared by means of the anodic alumina template. Then, the formation of 4,4′-dimercaptoazobenzene (DMAB) by the surface plasmon-driven photocatalysis under 633 nm laser irradiation was investigated by means of Raman spectroscopy using aminothiophenol (PATP) as a probe molecule on gold nananoporous arrays. In addition, sodium borohydride was introduced in situ to realize the reverse photocatalytic reaction driven by the surface plasma. With the help of FDTD software, the plasma distribution characteristics on the surface of Au nanoporous arrays were simulated and analyzed. Through this practical method, it is expected to draw specific graphics, letters, and Chinese characters on the micro/nano scale, and realize the functions of graphics drawing, information encryption, reading, and erasing on the micro/nano scale. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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55 pages, 12892 KiB  
Review
Hot Electrons in TiO2–Noble Metal Nano-Heterojunctions: Fundamental Science and Applications in Photocatalysis
by Ajay P. Manuel and Karthik Shankar
Nanomaterials 2021, 11(5), 1249; https://doi.org/10.3390/nano11051249 - 10 May 2021
Cited by 63 | Viewed by 8352
Abstract
Plasmonic photocatalysis enables innovation by harnessing photonic energy across a broad swathe of the solar spectrum to drive chemical reactions. This review provides a comprehensive summary of the latest developments and issues for advanced research in plasmonic hot electron driven photocatalytic technologies focusing [...] Read more.
Plasmonic photocatalysis enables innovation by harnessing photonic energy across a broad swathe of the solar spectrum to drive chemical reactions. This review provides a comprehensive summary of the latest developments and issues for advanced research in plasmonic hot electron driven photocatalytic technologies focusing on TiO2–noble metal nanoparticle heterojunctions. In-depth discussions on fundamental hot electron phenomena in plasmonic photocatalysis is the focal point of this review. We summarize hot electron dynamics, elaborate on techniques to probe and measure said phenomena, and provide perspective on potential applications—photocatalytic degradation of organic pollutants, CO2 photoreduction, and photoelectrochemical water splitting—that benefit from this technology. A contentious and hitherto unexplained phenomenon is the wavelength dependence of plasmonic photocatalysis. Many published reports on noble metal-metal oxide nanostructures show action spectra where quantum yields closely follow the absorption corresponding to higher energy interband transitions, while an equal number also show quantum efficiencies that follow the optical response corresponding to the localized surface plasmon resonance (LSPR). We have provided a working hypothesis for the first time to reconcile these contradictory results and explain why photocatalytic action in certain plasmonic systems is mediated by interband transitions and in others by hot electrons produced by the decay of particle plasmons. Full article
(This article belongs to the Special Issue Advances in Nanostructured Semiconductors and Heterojunctions)
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10 pages, 1202 KiB  
Communication
Hot Electrons, Hot Holes, or Both? Tandem Synthesis of Imines Driven by the Plasmonic Excitation in Au/CeO2 Nanorods
by Ivo F. Teixeira, Mauricio S. Homsi, Rafael S. Geonmonond, Guilherme F. S. R. Rocha, Yung-Kang Peng, Ingrid F. Silva, Jhon Quiroz and Pedro H. C. Camargo
Nanomaterials 2020, 10(8), 1530; https://doi.org/10.3390/nano10081530 - 4 Aug 2020
Cited by 9 | Viewed by 4001
Abstract
Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel [...] Read more.
Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel the performance and underlying reaction pathway in the visible-light-driven tandem oxidative coupling of benzyl alcohol and aniline employing Au/CeO2 nanorods as catalysts. We propose an alternative reaction pathway for this transformation that leads to improved efficiencies relative to individual CeO2 nanorods, in which the localized surface plasmon resonance (LSPR) excitation in Au nanoparticles (NPs) plays an important role. Our data suggests a synergism between the hot electrons and holes generated from the LSPR excitation in Au NPs. While the oxygen vacancies in CeO2 nanorods trap the hot electrons and facilitate their transfer to adsorbed O2 at surface vacancy sites, the hot holes in the Au NPs facilitate the α-H abstraction from the adsorbed benzyl alcohol, evolving into benzaldehyde, which then couples with aniline in the next step to yield the corresponding imine. Finally, cerium-coordinated superoxide species abstract hydrogen from the Au surface, regenerating the catalyst surface. Full article
(This article belongs to the Special Issue Novel Nanomaterials for Energy Conversion)
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55 pages, 5870 KiB  
Review
Advances and Recent Trends in Heterogeneous Photo(Electro)-Catalysis for Solar Fuels and Chemicals
by James Highfield
Molecules 2015, 20(4), 6739-6793; https://doi.org/10.3390/molecules20046739 - 15 Apr 2015
Cited by 66 | Viewed by 22146
Abstract
In the context of a future renewable energy system based on hydrogen storage as energy-dense liquid alcohols co-synthesized from recycled CO2, this article reviews advances in photocatalysis and photoelectrocatalysis that exploit solar (photonic) primary energy in relevant endergonic processes, viz., H [...] Read more.
In the context of a future renewable energy system based on hydrogen storage as energy-dense liquid alcohols co-synthesized from recycled CO2, this article reviews advances in photocatalysis and photoelectrocatalysis that exploit solar (photonic) primary energy in relevant endergonic processes, viz., H2 generation by water splitting, bio-oxygenate photoreforming, and artificial photosynthesis (CO2 reduction). Attainment of the efficiency (>10%) mandated for viable techno-economics (USD 2.00–4.00 per kg H2) and implementation on a global scale hinges on the development of photo(electro)catalysts and co-catalysts composed of earth-abundant elements offering visible-light-driven charge separation and surface redox chemistry in high quantum yield, while retaining the chemical and photo-stability typical of titanium dioxide, a ubiquitous oxide semiconductor and performance “benchmark”. The dye-sensitized TiO2 solar cell and multi-junction Si are key “voltage-biasing” components in hybrid photovoltaic/photoelectrochemical (PV/PEC) devices that currently lead the field in performance. Prospects and limitations of visible-absorbing particulates, e.g., nanotextured crystalline α-Fe2O3, g-C3N4, and TiO2 sensitized by C/N-based dopants, multilayer composites, and plasmonic metals, are also considered. An interesting trend in water splitting is towards hydrogen peroxide as a solar fuel and value-added green reagent. Fundamental and technical hurdles impeding the advance towards pre-commercial solar fuels demonstration units are considered. Full article
(This article belongs to the Special Issue Photocatalysis)
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