Visible Light Active Photocatalysts for Environmental Remediation and Organic Synthesis

A special issue of Photochem (ISSN 2673-7256).

Deadline for manuscript submissions: closed (23 December 2021) | Viewed by 40255

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Department of Industrial Engineering, University Salerno, Via Giovanni Paolo 2, 132, I-84084 Fisciano, Italy
Interests: photocatalysis for sustainable chemistry; photocatalytic and photo-Fenton processes for pollutants removal in wastewater; catalytic combustion of sewage sludge; decomposition and oxidative decomposition of H2S; hydrolysis of COS in the liquid phase
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Dear Colleagues,

In recent years the formulation of innovative photocatalysts activated by visible or solar light has been attracting increasing attention because of their interesting potential for environmental remediation and in organic synthesis reactions. Generally, the strategies for the development of visible light active photocatalysts are mainly focused on enhancing the degradation efficiency (in the case of environmental remediation) or increasing the selectivity towards the desired product (in the case of organic synthesis). These goals can be achieved by doping the semiconductor lattice with metal and/or non-metal elements in order to reduce the band gap energy, making the semiconductor able to absorb light at a wavelength higher than the UV range. Other interesting options are the formulation of different types of heterojunctions (to increase visible absorption properties and the concentration of photoactive surface sites), or to develop alternative catalytic materials, such as metal-organic frameworks (MOFs). This Special Issue is focused on “Visible Light Active Photocatalysts for environmental remediation and organic synthesis”, featuring the state-of-the-art in this field. Research and review papers related to the preparation and characterization of novel catalytic materials and their use in the visible (or solar light) driven photocatalytic removal of pollutants from liquid and gaseous phases are welcome in this Special Issue. Moreover, innovative photocatalyst formulations studied in chemical reactions devoted to the selective synthesis of organic compounds (e.g., phenol from benzene, aniline from nitrobenzene, methanol from methane, etc.) will be considered.

Dr. Vincenzo Vaiano
Guest Editor

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Keywords

  • photocatalysis
  • visible or solar light
  • doped and co-doped semiconductors
  • heterojunctions
  • Metal-Organic Framework (MOFs)
  • water and wastewater treatment
  • gaseous pollutant removal
  • organic synthesis

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Published Papers (12 papers)

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Editorial

Jump to: Research, Review

2 pages, 149 KiB  
Editorial
Visible-Light-Active Photocatalysts for Environmental Remediation and Organic Synthesis
by Vincenzo Vaiano
Photochem 2021, 1(3), 460-461; https://doi.org/10.3390/photochem1030029 - 11 Nov 2021
Cited by 2 | Viewed by 2103
Abstract
In recent years, the formulation of innovative photocatalysts activated by visible or solar light has been attracting increasing attention because of their notable potential for environmental remediation and use in organic synthesis reactions [...] Full article

Research

Jump to: Editorial, Review

12 pages, 2474 KiB  
Article
Study of the Response Surface in the Photocatalytic Degradation of Acetaminophen Using TiO2
by Adriana Marizcal-Barba, Jorge Alberto Sanchez-Burgos, Victor Zamora-Gasga and Alejandro Perez Larios
Photochem 2022, 2(1), 225-236; https://doi.org/10.3390/photochem2010017 - 10 Mar 2022
Cited by 6 | Viewed by 2249
Abstract
An effective way to obtain the optimal parameters of a process or experiment is the response surface method. Using the Box–Behnken design further decreases the number of experiments needed to obtain sufficient data to obtain a reliable equation. From the equation, it is [...] Read more.
An effective way to obtain the optimal parameters of a process or experiment is the response surface method. Using the Box–Behnken design further decreases the number of experiments needed to obtain sufficient data to obtain a reliable equation. From the equation, it is possible to predict the behavior of the response with respect to the combination of variables involved. In this study we evaluated the photocatalytic activity of the synthesized TiO2 for the degradation of acetaminophen, a frequently used and uncontrolled drug that has been detected with increasing frequency in wastewater effluents. The variables used for this study were pH, contaminant concentration (acetaminophen) and catalyst dose. We found, with a 95% confidence level, that 99% of the contaminant can be degraded to pH 10, contaminant to 35 mg/L and a catalyst dose of 0.15 g TiO2. Full article
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12 pages, 15283 KiB  
Article
Enhanced Photocatalytic Activity of TiO2 Thin Film Deposited by Reactive RF Sputtering under Oxygen-Rich Conditions
by Takaya Ogawa, Yuekai Zhao, Hideyuki Okumura and Keiichi N. Ishihara
Photochem 2022, 2(1), 138-149; https://doi.org/10.3390/photochem2010011 - 18 Feb 2022
Cited by 3 | Viewed by 2637
Abstract
TiO2 thin films are promising as photocatalysts to decompose organic compounds. In this study, TiO2 thin films were deposited by reactive radio-frequency (RF) magnetron sputtering under various flow rates of oxygen and argon gas. The results show that the photocatalytic activity [...] Read more.
TiO2 thin films are promising as photocatalysts to decompose organic compounds. In this study, TiO2 thin films were deposited by reactive radio-frequency (RF) magnetron sputtering under various flow rates of oxygen and argon gas. The results show that the photocatalytic activity decreases as the oxygen-gas ratio is increased to 30% or less, while the activity increases under oxygen-rich conditions. It was observed that the crystal structure changed from anatase to a composite of anatase and rutile, where the oxygen-gas ratio during RF sputtering is more than 40%. Interestingly, the oxygen vacancy concentration increased under oxygen-rich conditions, where the oxygen-gas ratio is more than 40%. The sample prepared under the most enriched oxygen condition, 70%, among our experiments exhibited the highest concentration of oxygen vacancy and the highest photocatalytic activity. Both the oxygen vacancies and the composite of anatase and rutile structure in the TiO2 films deposited under oxygen-rich conditions are considered responsible for the enhanced photocatalysis. Full article
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11 pages, 8119 KiB  
Article
Effect of Photolysis on Zirconium Amino Phenoxides for the Hydrophosphination of Alkenes: Improving Catalysis
by Bryan T. Novas, Jacob A. Morris, Matthew D. Liptak and Rory Waterman
Photochem 2022, 2(1), 77-87; https://doi.org/10.3390/photochem2010007 - 18 Jan 2022
Cited by 3 | Viewed by 2686
Abstract
A comparative study of amino phenoxide zirconium catalysts in the hydrophosphination of alkenes with diphenylphosphine reveals enhanced activity upon irradiation during catalysis, with conversions up to 10-fold greater than reactions in ambient light. The origin of improved reactivity is hypothesized to result from [...] Read more.
A comparative study of amino phenoxide zirconium catalysts in the hydrophosphination of alkenes with diphenylphosphine reveals enhanced activity upon irradiation during catalysis, with conversions up to 10-fold greater than reactions in ambient light. The origin of improved reactivity is hypothesized to result from substrate insertion upon an n→d charge transfer of a Zr–P bond in the excited state of putative phosphido (Zr–PR2) intermediates. TD-DFT analysis reveals the lowest lying excited state in the proposed active catalysts are dominated by a P 3p→Zr 4d MLCT, presumably leading to enhanced catalysis. This hypothesis follows from triamidoamine-supported zirconium catalysts but demonstrates the generality of photocatalytic hydrophosphination with d0 metals. Full article
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17 pages, 3251 KiB  
Article
Remazol Black Decontamination Study Using a Novel One-Pot Synthesized S and Co Co-Doped TiO2 Photocatalyst
by Riska Dwiyanna, Roto Roto and Endang Tri Wahyuni
Photochem 2021, 1(3), 488-504; https://doi.org/10.3390/photochem1030032 - 26 Nov 2021
Cited by 3 | Viewed by 2328
Abstract
This study investigated the decolorization of Remazol Black (RBB) using a TiO2 photocatalyst modified by S and Co co-doped TiO2 (S-Co-TiO2) from a single precursor. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–Vis specular reflectance spectroscopy [...] Read more.
This study investigated the decolorization of Remazol Black (RBB) using a TiO2 photocatalyst modified by S and Co co-doped TiO2 (S-Co-TiO2) from a single precursor. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–Vis specular reflectance spectroscopy were used to characterize the photocatalysts. The results revealed that the band-gap energy of the doped and co-doped TiO2 decreased, with the S-Co-TiO2 8% showing the greatest one, and was found to be 2.78 eV while undoped TiO2 was 3.20 eV. The presence of S and Co was also identified through SEM-EDX. An activity study on RBB removal revealed that the S-Co-TiO2 photocatalyst showed the best result compared to undoped TiO2, S-TiO2, and Co-TiO2. The S-Co-TiO2 8% photocatalyst reduced RBB concentration (20 mg L−1) up to 96% after 90 min of visible light irradiation, whereas S-TiO2, Co-TiO2, and undoped TiO2 reduced it to 89%, 56%, and 39%, respectively. A pH optimization study showed that the optimum pH of RBB decolorization by S-Co-TiO2 was 3.0, the optimum mass was 0.6 g L−1, and reuse studies show that S-Co-TiO2 8% has the potential to be used repeatedly to remove colored pollutants. The results obtained indicate that the modification of S, Co co-doped titania synthesized using a single precursor has been successfully carried out and showed excellent characteristics and activity compared to undoped or doped TiO2. Full article
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13 pages, 5949 KiB  
Article
g-C3N4/MoS2 Heterojunction for Photocatalytic Removal of Phenol and Cr(VI)
by Ilaeira Rapti, Feidias Bairamis and Ioannis Konstantinou
Photochem 2021, 1(3), 358-370; https://doi.org/10.3390/photochem1030023 - 15 Oct 2021
Cited by 20 | Viewed by 3503
Abstract
In this study, molybdenum disulfide (MoS2) decorated on graphitic carbon nitride (g-C3N4) heterostructure catalysts at various weight ratios (0.5%, 1%, 3%, 10%, w/w) were successfully prepared via a two-step hydrothermal synthesis preparation method. The [...] Read more.
In this study, molybdenum disulfide (MoS2) decorated on graphitic carbon nitride (g-C3N4) heterostructure catalysts at various weight ratios (0.5%, 1%, 3%, 10%, w/w) were successfully prepared via a two-step hydrothermal synthesis preparation method. The properties of the synthesized materials were studied by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FT-IR), UV–Vis diffuse reflection spectroscopy (DRS), scanning electron microscopy (SEM) and N2 porosimetry. MoS2 was successfully loaded on the g-C3N4 forming heterojunction composite materials. N2 porosimetry results showed mesoporous materials, with surface areas up to 93.7 m2g−1, while determined band gaps ranging between 1.31 and 2.66 eV showed absorption over a wide band of solar light. The photocatalytic performance was evaluated towards phenol oxidation and of Cr(VI) reduction in single and binary systems under simulated sunlight irradiation. The optimum mass loading ratio of MoS2 in g-C3N4 was 1%, showing higher photocatalytic activity under simulated solar light in comparison with bare g-C3N4 and MoS2 for both oxidation and reduction processes. Based on scavenging experiments a type-II photocatalytic mechanism is proposed. Finally, the catalysts presented satisfactory stability (7.8% loss) within three catalytic cycles. Such composite materials can receive further applications as well as energy conversion. Full article
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13 pages, 7979 KiB  
Article
Electrospun Carbon Nanofibers Decorated with Ag3PO4 Nanoparticles: Visible-Light-Driven Photocatalyst for the Photodegradation of Methylene Blue
by Gopal Panthi and Mira Park
Photochem 2021, 1(3), 345-357; https://doi.org/10.3390/photochem1030022 - 10 Oct 2021
Cited by 6 | Viewed by 3799
Abstract
For the first time, heterostructures of electrospun carbon nanofibers decorated with Ag3PO4 nanoparticles (Ag3PO4/CNFs) were successfully fabricated by the combination of simple and versatile electrospinning technique followed by carbonization and incorporation of Ag3PO4 [...] Read more.
For the first time, heterostructures of electrospun carbon nanofibers decorated with Ag3PO4 nanoparticles (Ag3PO4/CNFs) were successfully fabricated by the combination of simple and versatile electrospinning technique followed by carbonization and incorporation of Ag3PO4 nanoparticles via colloidal and precipitation synthesis approaches. The as-fabricated heterostructures were characterized by FESEM with EDS, XRD, TEM with HRTEM, FTIR and UV-vis diffuse reflectance spectroscopy. Experimental results revealed that the heterostructure obtained by colloidal synthesis approach (Ag3PO4/CNFs-1) was decorated with small-sized (~20 nm) and uniformly distributed Ag3PO4 nanoparticles on the surface of CNFs without any evident agglomeration, while in the heterostructure obtained by the precipitation synthesis approach (Ag3PO4/CNFs-2), CNFs were decorated with agglomerated and bigger-sized Ag3PO4 nanoparticles. The visible-light-driven photocatalytic investigation signified that the Ag3PO4/CNFs-1 heterostructure can exhibit higher performance towards the photodegradation of MB dye solution compared to the Ag3PO4/CNFs-2 heterostructure, which could be attributed to the synergistic effect between the uniformity and small size of Ag3PO4 nanoparticles and CNFs that can serve as a conductivity network to prevent the recombination of charge carriers. Moreover, the mechanism of the photocatalytic activity as-prepared heterostructure is proposed. Full article
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11 pages, 2491 KiB  
Article
Structural and Optical Properties of Bi12NiO19 Sillenite Crystals: Application for the Removal of Basic Blue 41 from Wastewater
by Billal Brahimi, Hamza Kenfoud, Yasmine Benrighi and Oussama Baaloudj
Photochem 2021, 1(3), 319-329; https://doi.org/10.3390/photochem1030020 - 27 Sep 2021
Cited by 12 | Viewed by 3175
Abstract
This article covers the structural and optical property analysis of the sillenite Bi12NiO19 (BNO) in order to characterize a new catalyst that could be used for environmental applications. BNO crystals were produced by the combustion method using Polyvinylpyrrolidone as a [...] Read more.
This article covers the structural and optical property analysis of the sillenite Bi12NiO19 (BNO) in order to characterize a new catalyst that could be used for environmental applications. BNO crystals were produced by the combustion method using Polyvinylpyrrolidone as a combustion reagent. Different approaches were used to characterize the resulting catalyst. Starting with X-ray diffraction (XRD), the structure was refined from XRD data using the Rietveld method and then the structural form of this sillenite was illustrated for the first time. This catalyst has a space group of I23 with a lattice parameter of a = 10.24 Å. In addition, the special surface area (SSA) of BNO was determined by the Brunauer-Emmett-Teller (BET) method. It was found in the range between 14.56 and 20.56 cm2·g−1. Then, the morphology of the nanoparticles was visualized by Scanning Electron Microscope (SEM). For the optical properties of BNO, UV-VIS diffusion reflectance spectroscopy (DRS) was used, and a 2.1 eV optical bandgap was discovered. This sillenite′s narrow bandgap makes it an effective catalyst for environmental applications. The photocatalytic performance of the synthesized Bi12NiO19 was examined for the degradation of Basic blue 41. The degradation efficiency of BB41 achieved 98% within just 180 min at pH ~9 and with a catalyst dose of 1 g/L under visible irradiation. The relevant reaction mechanism and pathways were also proposed in this work. Full article
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18 pages, 4729 KiB  
Article
Metal-Free g-C3N4/Nanodiamond Heterostructures for Enhanced Photocatalytic Pollutant Removal and Bacteria Photoinactivation
by Natalya Kublik, Luiz E. Gomes, Luiz F. Plaça, Thalita H. N. Lima, Thais F. Abelha, Julio A. P. Ferencz, Anderson R. L. Caires and Heberton Wender
Photochem 2021, 1(2), 302-318; https://doi.org/10.3390/photochem1020019 - 14 Sep 2021
Cited by 9 | Viewed by 3707
Abstract
Heterogeneous photocatalysis has emerged as a promising alternative for both micropollutant removal and bacterial inactivation under solar irradiation. Among a variety of photocatalysts explored in the literature, graphite carbon nitride (g-C3N4) is a metal-free semiconductor with acceptable chemical stability, [...] Read more.
Heterogeneous photocatalysis has emerged as a promising alternative for both micropollutant removal and bacterial inactivation under solar irradiation. Among a variety of photocatalysts explored in the literature, graphite carbon nitride (g-C3N4) is a metal-free semiconductor with acceptable chemical stability, low toxicity, and excellent cost-effectiveness. To minimize its high charge recombination rate and increase the photocatalyst adsorption capacity whilst keeping the metal-free photocatalyst system idea, we proposed the heterojunction formation of g-C3N4 with diamond nanocrystals (DNCs), also known as nanodiamonds. Samples containing different amounts of DNCs were assessed as photocatalysts for pollutant removal from water and as light-activated antibacterial agents against Staphylococcus sureus. The sample containing 28.3 wt.% of DNCs presented the best photocatalytic efficiency against methylene blue, removing 71% of the initial dye concentration after 120 min, with a pseudo-first-order kinetic and a constant rate of 0.0104 min−1, which is nearly twice the value of pure g-C3N4 (0.0059 min−1). The best metal-free photocatalyst was able to promote an enhanced reduction in bacterial growth under illumination, demonstrating its capability of photocatalytic inactivation of Staphylococcus aureus. The enhanced photocatalytic activity was discussed and attributed to (i) the increased adsorption capacity promoted by the presence of DNCs; (ii) the reduced charge recombination rate due to a type-II heterojunction formation; (iii) the enhanced light absorption effectiveness; and (iv) the better charge transfer resistance. These results show that g-C3N4/DNC are low-cost and metal-free photoactive catalysts for wastewater treatment and inactivation of bacteria. Full article
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17 pages, 4563 KiB  
Article
Photocatalytic Decomposition of Nitrobenzene in Aqueous Solution by Ag/Cu2O Assisted with Persulfate under Visible Light Irradiation
by Wen-Shing Chen and Jyun-Yang Chen
Photochem 2021, 1(2), 220-236; https://doi.org/10.3390/photochem1020013 - 27 Aug 2021
Cited by 3 | Viewed by 2575
Abstract
The mineralization of nitrobenzene was executed using an innovative method, wherein Ag/Cu2O semiconductors stimulated by visible light irradiation were supported with persulfate anions. Batch-wise experiments were performed for the evaluation of effects of silver metal contents impregnated, persulfate concentrations and Ag/Cu [...] Read more.
The mineralization of nitrobenzene was executed using an innovative method, wherein Ag/Cu2O semiconductors stimulated by visible light irradiation were supported with persulfate anions. Batch-wise experiments were performed for the evaluation of effects of silver metal contents impregnated, persulfate concentrations and Ag/Cu2O dosages on the nitrobenzene removal efficiency. The physicochemical properties of fresh and reacted Ag/Cu2O were illustrated by X-ray diffraction analyses, FE-SEM images, EDS Mapping analyses, UV–Vis diffuse reflectance spectra, transient photocurrent analyses and X-ray photoelectron spectra, respectively. Because of intense scavenging effects caused by benzene, 1-propanol and methanol individually, the predominant oxidant was considered to be sulfate radicals, originated from persulfate anions via the photocatalysis of Ag/Cu2O. As regards oxidation pathways, nitrobenzene was initially transformed into hydroxycyclohexadienyl radicals, followed with the production of 2-nitrophenol, 3-nitrophenol or 4-nitrophenol. Afterwards, phenol compounds descended from denitration of nitrophenols were converted into hydroquinone and p-benzoquinone. Full article
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13 pages, 5575 KiB  
Article
Preparation of Activated Carbon/TiO2 Nanohybrids for Photodegradation of Reactive Red-35 Dye Using Sunlight
by Bappy Mondol, Anupam Sarker, A. M. Shareque, Shaikat Chandra Dey, Mohammad Tariqul Islam, Ajoy Kumar Das, Sayed Md. Shamsuddin, Md. Ashraful Islam Molla and Mithun Sarker
Photochem 2021, 1(1), 54-66; https://doi.org/10.3390/photochem1010006 - 18 May 2021
Cited by 43 | Viewed by 4414
Abstract
Activated carbon/titanium dioxide (AC/TiO2) nanohybrids were synthesized by a hydrothermal technique using various weight percent of commercial AC and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA). The synthesized [...] Read more.
Activated carbon/titanium dioxide (AC/TiO2) nanohybrids were synthesized by a hydrothermal technique using various weight percent of commercial AC and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA). The synthesized nanohybrids were applied to photodegradation of Reactive Red-35 (RR-35) dye in aqueous solution using sunlight. Due to the synergistic effect of adsorption and photodegradation activity, AC/TiO2 nanohybrids were more efficient in treating the aqueous dye solution than that of AC and TiO2. The maximum (95%) RR-35 dye removal from the water was obtained with 20 wt% AC/TiO2 within 30 min at natural pH of 5.6. The possible photodegradation mechanism of RR-35 dye with AC/TiO2 was discussed from the scavenger test. Moreover, AC/TiO2 was found to be suitable for long-term repeated applications through recyclability experiments. Therefore, AC/TiO2 nanohybrid is a promising photocatalyst for treating azo dyes especially RR-35 from water. Full article
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Review

Jump to: Editorial, Research

20 pages, 3576 KiB  
Review
Green Synthesis of Heterogeneous Visible-Light-Active Photocatalysts: Recent Advances
by Alessio Zuliani and Camilla Maria Cova
Photochem 2021, 1(2), 147-166; https://doi.org/10.3390/photochem1020009 - 27 Jul 2021
Cited by 16 | Viewed by 4676
Abstract
The exploitation of visible-light active photocatalytic materials can potentially change the supply of energy and deeply transform our world, giving access to a carbon neutral society. Currently, most photocatalysts are produced through low-ecofriendly, energy dispersive, and fossil-based synthesis. Over the last few years, [...] Read more.
The exploitation of visible-light active photocatalytic materials can potentially change the supply of energy and deeply transform our world, giving access to a carbon neutral society. Currently, most photocatalysts are produced through low-ecofriendly, energy dispersive, and fossil-based synthesis. Over the last few years, research has focused on the development of innovative heterogeneous photocatalysts by the design of sustainable and green synthetic approaches. These strategies range from the use of plant extracts, to the valorization and recycling of metals inside industrial sludges or from the use of solventless techniques to the elaboration of mild-reaction condition synthetic tools. This mini-review highlights progresses in the development of visible-light-active heterogeneous photocatalysts based on two different approaches: the design of sustainable synthetic methodologies and the use of biomass and waste as sources of chemicals embedded in the final photoactive materials. Full article
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