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Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives

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

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 34763

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Dr. Ioan Balint

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Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy, 060021 Bucharest, Romania
Interests: surface science: non-isothermal gas desorption kinetic from supported-metal catalysts; solid defect chemistry; water–gas shift reaction on surface of simple and doped ionic oxides; material synthesis: mesoporous nano oxides; mono/bimetallic metal nanoparticles; catalysis: catalytic combustion of hydrocarbons; oxidative coupling of methane; hydrogenation and oxidative conversion of conversion hydrocarbons; denox reaction; structure-sensitive reactions; nitrate and nitrite abatement; photocatalysis/light harvesting: water and air depollution; water splitting; light-induced reactive oxygen species generation; solar cell
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Dr. Monica Pavel

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Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy, 060021 Bucharest, Romania
Interests: synthesis of catalysts by various techniques; photocatalysis; total oxidation of VOCs and light alkanes
Special Issues, Collections and Topics in MDPI journals

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Dear Colleagues,

The use of light as a free energy source to mineralize the recalcitrant contaminants contained in indoor air and various water sources into harmless CO₂ and H₂O is currently an important issue. The large-scale application of photocatalysis in depollution is impeded by the long-term stability of photocatalytic materials, formation of harmful intermediate products, low quantum efficiency, and low reaction rates. In many cases, published works have assessed photocatalyst activity from pollutant-degraded fraction data, whereas its identification and quantification in intermediates as well as CO₂ remains in the shadow. The degradation mechanism related to materials and organic substrates has been speculated upon in many cases, though without presentation of any solid experimental evidence. The relationship between ROS (reactive oxygen species, •OH, and O₂⁻) formed by photocatalysts under light exposure and degradation mechanism also need substantial clarification. The precise quantification of in situ ROS through dedicated experiments should be an important direction of investigations. This Special Issue will present a collection of original research papers and reviews focusing on photocatalysis as applied to indoor air and water treatment with emphasis on (i) newly developed photocatalytic materials for environmental applications, (ii) identification and quantification of degradation intermediates as well as of CO₂, (iii) identification and quantification of ROS through dedicated experiments, (iv) material- and light energy-related ROS generation, (v) identification of the precise role of ROS in reaction pollutant degradation mechanism and impact on selectivity, (vi) ROS-intermediated photocharge transfer mechanism from photocatalyst to organic substrate, and (vii) specific features of pollutant degradation mechanisms in aqueous and air media.

Dr. Ioan Balint
Dr. Monica Pavel
Guest Editors

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Keywords

indoor air treatment
water cleaning
photocatalysis
photocatalytic materials
semiconductors
surface reaction
reactive oxygen species
recalcitrant compounds mineralization

Published Papers (11 papers)

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Editorial

Jump to: Research, Review

4 pages, 185 KiB

Open AccessEditorial

Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives

by Ioan Balint and Monica Pavel

Catalysts 2023, 13(7), 1032; https://doi.org/10.3390/catal13071032 - 23 Jun 2023

Viewed by 797

Abstract

The detrimental effects of environmental pollution on human health, combined with global climate change, make it a critical contemporary problem [...] Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

Research

Jump to: Editorial, Review

15 pages, 4615 KiB

Open AccessArticle

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 - 02 Nov 2022

Cited by 3 | Viewed by 1336

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 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

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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16 pages, 6837 KiB

Open AccessArticle

One-Pot Synthesis of TiO₂/Hectorite Composite and Its Photocatalytic Degradation of Methylene Blue

by Dingqing Yang, Jinyang Chen, Xiaomin Hong, Jingying Cui and Lingzhen Li

Catalysts 2022, 12(3), 297; https://doi.org/10.3390/catal12030297 - 06 Mar 2022

Cited by 4 | Viewed by 2110

Abstract

TiO₂/hectorite composite photocatalysts with different molar ratios of lithium, magnesium, and silicon were synthesized by a one-pot hydrothermal method. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N₂ adsorption-desorption isotherms, and ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS). When the molar ratio of lithium, magnesium, and silicon was 1.32:5.34:8 (TH-2), the composite showed the highest UV photocatalytic degradation of methylene blue (MB). The apparent rate constant of TH-2 was 0.04361 min⁻¹, which was about 3.12 times that of EVONIK Degussa commercial TiO₂ of AEROXIDE P25. The improvement of photocatalytic efficiency of the composite was mainly due to its high specific surface area, light trapping ability, and effective separation of electrons (e⁻) and holes (h⁺). At the same time, the F element of hectorite is beneficial to the formation of Ti³⁺ in TiO₂, thus enhancing the photocatalytic activity. After five cycles, the removal rate of MB with TH-2 still reached 87.9%, indicating its excellent reusability. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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16 pages, 3913 KiB

Open AccessArticle

Identification of Active Species in Photodegradation of Aqueous Imidacloprid over g-C₃N₄/TiO₂ Nanocomposites

by Thawanrat Kobkeatthawin, Jirawat Trakulmututa, Taweechai Amornsakchai, Puangrat Kajitvichyanukul and Siwaporn Meejoo Smith

Catalysts 2022, 12(2), 120; https://doi.org/10.3390/catal12020120 - 19 Jan 2022

Cited by 22 | Viewed by 2283

Abstract

In this work, g-C₃N₄/TiO₂ composites were fabricated through a hydrothermal method for the efficient photocatalytic degradation of imidacloprid (IMI) pesticide. The composites were fabricated at varying loading of sonochemically exfoliated g-C₃N₄ (denoted as CNS). Complementary characterization results indicate that the heterojunction between the CNS and TiO₂ formed. Among the composites, the 0.5CNS/TiO₂ material gave the highest photocatalytic activity (93% IMI removal efficiency) under UV-Vis light irradiation, which was 2.2 times over the pristine g-C₃N₄. The high photocatalytic activity of the g-C₃N₄/TiO₂ composites could be ascribed to the band gap energy reduction and suppression of photo-induced charge carrier recombination on both TiO₂ and CNS surfaces. In addition, it was found that the active species involved in the photodegradation process are OH• and holes, and a possible mechanism was proposed. The g-C₃N₄/TiO₂ photocatalysts exhibited stable photocatalytic performance after regeneration, which shows that g-C₃N₄/TiO₂ is a promising material for the photodegradation of imidacloprid pesticide in wastewater. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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15 pages, 4863 KiB

Open AccessArticle

Synthesis, Characterization and Photoelectric Properties of Fe₂O₃ Incorporated TiO₂ Photocatalyst Nanocomposites

by Atif Mossad Ali, Mahmoud Ahmed Sayed, Hamed Algarni, Vanga Ganesh, Muhd Aslam, Adel Ali Ismail and Haitham Mohamed El-Bery

Catalysts 2021, 11(9), 1062; https://doi.org/10.3390/catal11091062 - 31 Aug 2021

Cited by 18 | Viewed by 2815

Abstract

In the present work we report the sol-gel synthesis of pure TiO₂ and (TiO₂)_1−x(Fe₂O₃)_x nanocomposites with different Fe₂O₃ contents (x = 0, 0.1, 0.5, and 1.0 for pure TiO₂ [...] Read more.

In the present work we report the sol-gel synthesis of pure TiO₂ and (TiO₂)_1−x(Fe₂O₃)_x nanocomposites with different Fe₂O₃ contents (x = 0, 0.1, 0.5, and 1.0 for pure TiO₂, Fe₂O₃ incorporated 0.1, 0.5, and pure Fe₂O₃ which are denoted as PT, 0.1F, 0.5F, and PF, respectively). The structural, morphological, optical, and surface texture of the prepared nanocomposites were characterized using various techniques. The structural studies confirm the strong influence of Fe₂O₃ contents on the crystallite sizes and dislocation values. The size of the crystallites was increased by the increase in Fe₂O₃ contents. The bandgap values elucidated from DRS analysis were decreased from 3.15 eV to 1.91 eV with increasing Fe₂O₃ contents. The N₂-Physorption analysis has confirmed the mesoporous nature of the samples with a comparable specific surface area of 35 m²/g. The photoelectrochemical measurements (CV, CA and EIS) were performed to assess the photoelectric properties of the prepared materials. It was found that the PT samples have the highest catalytic activity and photocurrent response compared to other composites. The reduction in current density was as follows: 2.8, 1.65, 1.5 and 0.9 mA/cm², while the photocurrent response was ca. 800, 450, 45, 35 µA/cm² for PT, 0.1F, 0.5F and PF samples, respectively. The EIS results showed that the (TiO₂)_1−x(Fe₂O₃)_x nanocomposites exhibit lower charge transfer resistance than pure titania and hematite samples. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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26 pages, 9490 KiB

Open AccessFeature PaperArticle

Solochrome Dark Blue Azo Dye Removal by Sonophotocatalysis Using Mn²⁺ Doped ZnS Quantum Dots

by Jyoti Patel, Ajaya K. Singh, Bhawana Jain, Sushma Yadav, Sónia A. C. Carabineiro and Md. Abu Bin Hasan Susan

Catalysts 2021, 11(9), 1025; https://doi.org/10.3390/catal11091025 - 24 Aug 2021

Cited by 11 | Viewed by 3782

Abstract

This work investigates the degradation of the azo dye solochrome dark blue (SDB) by measurement of the photocatalytic, sonocatalytic and sonophotocatalytic activities, under low ultrasonic frequency (40 kHz) and UV-C (254 nm) light, using Mn-doped ZnS semiconductor quantum dots (Mn²⁺:ZnS Qds) as catalysts, prepared by a simple chemical precipitation procedure. In order to study the different morphological and optical crystal properties, various characterization techniques were used, such as high resolution transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, N₂ adsorption-desorption at −196 °C and ultraviolet-visible spectroscopy. The average particle size of the semiconductor Qds was in the range of 3–4 nm. The optimal parameters affecting dye degradation, such as the catalyst loading, solution pH, time of irradiation, initial concentration of dye, dopant concentration, ultrasonic power and frequency effect were evaluated. The synthesized catalytic material exhibited a high activity for sonophotocatalytic degradation of SDB (89%), larger than that observed for sonocatalysis (69.7%) or photocatalysis (55.2%) alone, which was due to the improved electron-holes separation, formation of more reactive radicals and enhancement of the active surface area. Qds showed good stability and reusability after five repeated cycles. Finally, the degradation products were identified by liquid chromatography-mass spectrometry (LC-MS). Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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19 pages, 6592 KiB

Open AccessFeature PaperArticle

Advancements on Basic Working Principles of Photo-Driven Oxidative Degradation of Organic Substrates over Pristine and Noble Metal-Modified TiO₂. Model Case of Phenol Photo Oxidation

by Alexandra Sandulescu, Crina Anastasescu, Florica Papa, Monica Raciulete, Anca Vasile, Tanta Spataru, Monica Scarisoreanu, Claudiu Fleaca, Cristian N. Mihailescu, Valentin S. Teodorescu, Nicolae Spataru, Maria Zaharescu and Ioan Balint

Catalysts 2021, 11(4), 487; https://doi.org/10.3390/catal11040487 - 10 Apr 2021

Cited by 5 | Viewed by 2362

Abstract

The specific roles played by both support and noble metals in light absorption, charge separation, and the formation of ·OH and O₂⁻ (ROS) are analyzed for light-triggered oxidation of phenol (Ph) over pristine and over noble metal (Ag, Au, Pt) -loaded TiO₂. Experiments show that the supported noble metals act as a light visible absorber, assist the separation of photo-charges and reduction of O₂ to O₂⁻. The O₂⁻ oxidizes mildly Ph to oxygenated products (hydroquinone, benzoquinone, and 1,2-dihydroxibenzene). In a parallel process, ·OH radicals, yielded by TiO₂, mineralize Ph to CO₂ by fast reaction sequences. Radical quenching and photo electrochemical measurements (surface photovoltage) confirm independently that the production of ·OH and O₂⁻ scale with oxidative conversion of Ph. The selectivity to CO₂ and mild oxidation products is the result of the interplay between catalyst activity for ·OH and for O₂⁻ production. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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12 pages, 3167 KiB

Open AccessArticle

Using Gd-Enhanced β-NaYF₄:Yb,Er Fluorescent Nanorods Coupled to Reduced TiO₂ for the NIR-Triggered Photocatalytic Inactivation of Escherichia coli

by Huang Zhou and Fengjiao He

Catalysts 2021, 11(2), 184; https://doi.org/10.3390/catal11020184 - 31 Jan 2021

Cited by 5 | Viewed by 2117

Abstract

β-NaYF₄:Yb,Er,Gd fluorescent nanorods were successfully coupled to a reduced TiO₂ (UCNPs@R-TiO₂) nanocomposite and applied to visible-light catalytic sterilization under 980 nm near-infrared (NIR) light illumination. The UCNPs (β-NaYF₄:Yb,Er,Gd) absorb the NIR light and emit red and green light. The visible light can be absorbed by the R-TiO₂ (Eg = 2.8 eV) for the photocatalytic reaction. About 98.1% of Escherichia coli were effectively killed upon 12 min of NIR light irradiation at a minimum inhibitory concentration (MIC) of 40 μg/mL UCNPs@R-TiO₂ nanocomposite. The bactericidal properties were further evaluated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis. We found that the high bactericidal activity was due to the synergistic effect between the UCNPs and R-TiO₂. Moreover, the UCNPs show excellent upconversion luminance properties, and the introduction of visible-light-absorbed R-TiO₂ nanoparticles (2.8 eV) was conducive to the efficient separation and utilization of photogenerated electron-hole pairs. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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Review

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45 pages, 5422 KiB

Open AccessReview

Photocatalytic Degradation of Organic and Inorganic Pollutants to Harmless End Products: Assessment of Practical Application Potential for Water and Air Cleaning

by Monica Pavel, Crina Anastasescu, Razvan-Nicolae State, Anca Vasile, Florica Papa and Ioan Balint

Catalysts 2023, 13(2), 380; https://doi.org/10.3390/catal13020380 - 09 Feb 2023

Cited by 56 | Viewed by 8870

Abstract

It is well-documented that large-scale pollution generated by human activity has a dramatic impact on ecosystems. In this context, removing harmful chemicals via photocatalysis has tremendous potential as a depollution method, utilizing freely available solar light and catalytic materials with low or negligible ecotoxicity. The main drawbacks, which aren’t often addressed in the available literature, are the formation of harmful intermediate products, low reaction rates, limited catalyst stability, and difficult catalyst recovery. In most cases, published works assess the efficiency of tested photocatalysts from pollutant degradation studies, whereas identifying and quantifying by-products is not often conducted. This review summarizes the recent advances reported for the photocatalytic removal of some organic (e.g., alcohols, carboxylic acids, volatile organic compounds, phenol) and inorganic (e.g., NO₃⁻) contaminants. The efficiency of various UV- and visible-light active photocatalysts and the reaction degradation pathways were explained, emphasizing the main factors contributing to their mineralization. The reaction mechanisms, the identification and quantification of degradation intermediates, and the implication of reactive active species (ROS) were discussed and analyzed for each category of model target pollutant. Additionally, the actual challenges and future photocatalytic approaches to improve environmental remediation were presented. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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24 pages, 2120 KiB

Open AccessReview

Olive Mill Wastewater Remediation: From Conventional Approaches to Photocatalytic Processes by Easily Recoverable Materials

by Melissa G. Galloni, Elena Ferrara, Ermelinda Falletta and Claudia L. Bianchi

Catalysts 2022, 12(8), 923; https://doi.org/10.3390/catal12080923 - 21 Aug 2022

Cited by 15 | Viewed by 3008

Abstract

Olive oil production in Mediterranean countries represents a crucial market, especially for Spain, Italy, and Greece. However, although this sector plays a significant role in the European economy, it also leads to dramatic environmental consequences. Waste generated from olive oil production processes can be divided into solid waste and olive mill wastewaters (OMWW). These latter are characterized by high levels of organic compounds (i.e., polyphenols) that have been efficiently removed because of their hazardous environmental effects. Over the years, in this regard, several strategies have been primarily investigated, but all of them are characterized by advantages and weaknesses, which need to be overcome. Moreover, in recent years, each country has developed national legislation to regulate this type of waste, in line with the EU legislation. In this scenario, the present review provides an insight into the different methods used for treating olive mill wastewaters paying particular attention to the recent advances related to the development of more efficient photocatalytic approaches. In this regard, the most advanced photocatalysts should also be easily recoverable and considered valid alternatives to the currently used conventional systems. In this context, the optimization of innovative systems is today’s object of hard work by the research community due to the profound potential they can offer in real applications. This review provides an overview of OMWW treatment methods, highlighting advantages and disadvantages and discussing the still unresolved critical issues. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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29 pages, 5438 KiB

Open AccessReview

A Review: Photocatalysts Based on BiOCl and g-C₃N₄ for Water Purification

by Qiang Ren, Juming Liu, Qi Yang and Wei Shen

Catalysts 2021, 11(9), 1084; https://doi.org/10.3390/catal11091084 - 08 Sep 2021

Cited by 8 | Viewed by 3319

Abstract

Many organic pollutants are discharged into the environment, which results in the frequent detection of organic pollutants in surface water and underground water. Some of the organic pollutants can stay for a long time in the environment due to their recalcitrance. Advanced oxidation processes (AOPs) can effectively treat the recalcitrant organic compounds in water. Photocatalysis as one of the AOPs has attracted a lot of interest. BiOCl and g-C₃N₄ are nice photocatalysts. However, their catalytic activity should be further improved for industrial utilization. The construction of heterojunction between the two different components is deemed as an efficient strategy for developing a highly efficient photocatalyst. As a typical type-II heterojunction, g-C₃N₄/BiOCl heterojunctions showed better photocatalytic performance. To date, the g-C₃N₄/BiOCl composites were mainly studied in the field of water purification. The photoactivity of the pristine catalysts was greatly enhanced by the combination of the two materials. However, three kinds of proposed mechanisms were used to explain the improvement of the g-C₃N₄/BiOCl heterojunctions. But few researchers tried to explain why there were three different scenarios employed to explain the charge transfer. According to the articles reviewed, no direct evidence could indicate whether the band structures of the heterojunctions based on BiOCl and g-C₃N₄ were changed. Therefore, many more studies are needed to reveal the truth. Having a clearer understanding of the mechanism is beneficial for researchers to construct more efficient photocatalysts. This article is trying to start a new direction of research to inspire more researchers to prepare highly effective photocatalysts. Full article

(This article belongs to the Special Issue Light-Assisted Catalysis in Water and Indoor Air Cleaning: Challenges and Perspectives)

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