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Latest Developments in Photocatalytic Materials and Processes
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Latest Developments in Photocatalytic Materials and Processes

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 29727

Special Issue Editors

Dr. Imre Miklós Szilágyi

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Guest Editor
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Budapest, Hungary
Interests: materials science; nanotechnology; analytical chemistry; photocatalysis; gas sensing; nanofluids; atomic layer deposition; nanocomposites
Special Issues, Collections and Topics in MDPI journals
Dr. Klára Hernádi

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Guest Editor
1. Institute of Physical Metallurgy, Metal Forming and Nanotechnology, University of Miskolc, C/2-5 Building 209, H-3515 Miskolc-Egyetemvaros, Hungary
2. Department of Applied and Environmental Chemistry, University of Szeged, Szeged, Hungary
Interests: heterogeneous catalysis; photocatalytic materials; carbon nanotubes; nanocomposite materials; immobilization of biologically active units
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Photocatalysis, which uses solar energy as a renewable source, is one of the most promising technologies for the elimination of toxic compounds from water, due to its advantages of high activity, photochemical stability, and cost-efficiency. Beside aqueous applications, it can also significantly increase indoor air quality, addressing the so-called “sick building syndrome” and contribute to eliminating pollutants like VOCs both indoors and outdoors. Besides oxidation, photocatalytic reduction of harmful molecules (e.g., NOx) is an emerging field.

Photocatalytic synthesis is also a major green chemistry field, ranging from artificial photosynthesis of converting CO2 and H2O into organic raw molecules to performing photocatalytic synthetic versions of more sophisticated organic processes.

Many exciting materials and processes have recently appeared in photocatalytic research, including photonic bandgap structures and all-organic photocatalysts.

Using computational chemistry and applying extreme laser infrastructure to understanding the photon absorption, excitation, and dissipation processes as well as the occurring photochemical reactions are also hot topics in this field.

A great challenge of photocatalytic materials is to increase their selectivity, robustness, and electron–hole lifetime as well as to achieve a more optimal use of the solar spectrum.

Although there are already some practical, real-life applications, major breakthroughs leading to the everyday use of photocatalysis are still awaited. For this, new laboratory and scaled-up setups and processes are needed, with robust catalysts and reactors.

The present Special Issue aims to collect studies and results detailing the latest developments in the field of photocatalysis.

Dr. Imre Miklós Szilágyi
Dr. Klára Hernádi
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • photocatalysis
  • decontamination
  • synthesis
  • nanotechnology
  • nanocomposites
  • visible
  • UV

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Published Papers (10 papers)

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Research

22 pages, 24430 KiB  
Article
Fabrication of TiO2/NiO p-n Nanocomposite for Enhancement Dye Photodegradation under Solar Radiation
by Mohamed Zayed, Salsbeel Samy, Mohamed Shaban, Abeer S. Altowyan, Hany Hamdy and Ashour M. Ahmed
Nanomaterials 2022, 12(6), 989; https://doi.org/10.3390/nano12060989 - 17 Mar 2022
Cited by 13 | Viewed by 3175
Abstract
A p-n nanocomposite based on TiO2 nanotubes (NTs) and NiO nanoparticles (NPs) was designed and optimized in this study to improve the photocatalytic performance of methylene blue (MB). The hydrothermal technique has been used to produce TiO2/NiO nanocomposites with different [...] Read more.
A p-n nanocomposite based on TiO2 nanotubes (NTs) and NiO nanoparticles (NPs) was designed and optimized in this study to improve the photocatalytic performance of methylene blue (MB). The hydrothermal technique has been used to produce TiO2/NiO nanocomposites with different NiO NPs weight ratios; 1TiO2:1NiO, 1TiO2:2NiO, and 1TiO2:3NiO. The crystal phase, chemical composition, optical properties, and morphology of TiO2/NiO were explored by various techniques. TiO2 NTs have a monoclinic structure, while NiO NPs have a cubic structure, according to the structural study. The bandgap of TiO2 NTs was reduced from 3.54 eV to 2.69 eV after controlling the NiO NPs weight ratio. The TiO2/2NiO nanocomposite showed the best photodegradation efficiency. Within 45 min of solar light irradiation, the efficiency of MB dye degradation using TiO2/2NiO hits 99.5% versus 73% using pure TiO2 NTs. Furthermore, the catalytic photodegradation efficiency did not deteriorate significantly even after five reusability cycles, intimating the high stability of the TiO2/2NiO nanocomposite. This suggests that the loading of NiO NPs into TiO2 NTs lowers the recombination of photo-produced electron/hole pairs and enlarged solar spectral response range, which results in improved photocatalytic activity. The mechanism of charge transfer in the TiO2/NiO and kinetic models were discussed for the photodegradation of MB. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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21 pages, 7762 KiB  
Article
Photocatalytic Degradation of Dissolved Phenol by Immobilized Zinc Oxide Nanoparticles: Batch Studies, Continuous Flow Experiments, and Numerical Modeling
by Michalis V. Karavasilis, Maria A. Theodoropoulou and Christos D. Tsakiroglou
Nanomaterials 2022, 12(1), 69; https://doi.org/10.3390/nano12010069 - 28 Dec 2021
Cited by 7 | Viewed by 1996
Abstract
In spite of the progress achieved on the photo-catalytic treatment of water streams, there is still a gap of knowledge on the optimization of the performance of continuous-flow photo-reactors. Zinc-oxide (ZnO) nanoparticles were immobilized on Duranit (80% silica + 20% alumina) inert balls [...] Read more.
In spite of the progress achieved on the photo-catalytic treatment of water streams, there is still a gap of knowledge on the optimization of the performance of continuous-flow photo-reactors. Zinc-oxide (ZnO) nanoparticles were immobilized on Duranit (80% silica + 20% alumina) inert balls with dip-coating and thermal annealing. The immobilized ZnO nanoparticles were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy, and Raman spectroscopy. To assess the stability and photocatalytic capacity of immobilized ZnO, degradation tests of phenol were performed in batch mode in a 22 W UV-oven with an emission peak at 375 nm by varying the temperature, the initial phenol concentration, and the ratio of photocatalyst mass to initial phenol mass. Continuous flow tests were conducted on two types of annular photo-reactors, made of poly(methyl)methacrylate (PMMA) and stainless steel (STST), equipped with a 6 W UV-lamp with emission at 375 nm, packed with ZnO-coated Duranit beads. Experiments were conducted by recirculating the phenol solution between the annular space of reactor and an external tank and varying the flow rate and the liquid volume in the tank. A one-dimensional dynamic mathematical model was developed by combining reactive with mass-transfer processes and used to estimate the overall reaction kinetic constant with inverse modeling. The results revealed that the ZnO losses might be discernible in batch mode due to the intense stirring caused by the bubbles of injected air, while an insignificant loss of ZnO mass occurs under continuous flow conditions, even after several cycles of reuse; the order of the overall phenol photodegradation reaction is lower than unity; the pseudo-1st order kinetic constant scales positively with the ratio of photocatalyst mass to the initial phenol mass and Peclet number. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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21 pages, 3962 KiB  
Article
Impact of Reaction Parameters and Water Matrices on the Removal of Organic Pollutants by TiO2/LED and ZnO/LED Heterogeneous Photocatalysis Using 365 and 398 nm Radiation
by Máté Náfrádi, Tünde Alapi, Gábor Bencsik and Csaba Janáky
Nanomaterials 2022, 12(1), 5; https://doi.org/10.3390/nano12010005 - 21 Dec 2021
Cited by 18 | Viewed by 3488
Abstract
In this work, the application of high-power LED365nm and commercial, low-price LED398nm for heterogeneous photocatalysis with TiO2 and ZnO photocatalysts are studied and compared, focusing on the effect of light intensity, photon energy, quantum yield, electrical energy consumption, and effect [...] Read more.
In this work, the application of high-power LED365nm and commercial, low-price LED398nm for heterogeneous photocatalysis with TiO2 and ZnO photocatalysts are studied and compared, focusing on the effect of light intensity, photon energy, quantum yield, electrical energy consumption, and effect of matrices and inorganic components on radical formation. Coumarin (COU) and its hydroxylated product (7-HC) were used to investigate operating parameters on the •OH formation rate. In addition to COU, two neonicotinoids, imidacloprid and thiacloprid, were also used to study the effect of various LEDs, matrices, and inorganic ions. The transformation of COU was slower for LED398nm than for LED365nm, but r07-HC/r0COU ratio was significantly higher for LED398nm. The COU mineralization rate was the same for both photocatalysts using LED365nm, but a significant difference was observed using LED398nm. The impact of matrices and their main inorganic components Cl− and HCO3− were significantly different for ZnO and TiO2. The negative effect of HCO3− was evident, however, in the case of high-power LED365nm and TiO2, and the formation of CO3•− almost doubled the r07-HC and contributes to the conversion of neonicotinoids by altering the product distribution and mineralization rate. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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18 pages, 3120 KiB  
Article
Nanoporous TiN/TiO2/Alumina Membrane for Photoelectrochemical Hydrogen Production from Sewage Water
by Abdullah Almohammedi, Mohamed Shaban, Huda Mostafa and Mohamed Rabia
Nanomaterials 2021, 11(10), 2617; https://doi.org/10.3390/nano11102617 - 6 Oct 2021
Cited by 31 | Viewed by 3045
Abstract
An aluminum oxide, Al2O3, template is prepared using a novel Ni imprinting method with high hexagonal pore accuracy and order. The pore diameter after the widening process is about 320 nm. TiO2 layer is deposited inside the template [...] Read more.
An aluminum oxide, Al2O3, template is prepared using a novel Ni imprinting method with high hexagonal pore accuracy and order. The pore diameter after the widening process is about 320 nm. TiO2 layer is deposited inside the template using atomic layer deposition (ALD) followed by the deposition of 6 nm TiN thin film over the TiO2 using a direct current (DC) sputtering unit. The prepared nanotubular TiN/TiO2/Al2O3 was fully characterized using different analytical tools such as X-ray diffraction (XRD), Energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM), and optical UV-Vis spectroscopy. Exploring the current-voltage relationships under different light intensities, wavelengths, and temperatures was used to investigate the electrode’s application before and after Au coating for H2 production from sewage water splitting without the use of any sacrificing agents. All thermodynamic parameters were determined, as well as quantum efficiency (QE) and incident photon to current conversion efficiency (IPCE). The QE was 0.25% and 0.34% at 400 mW·cm−2 for the photoelectrode before and after Au coating, respectively. Also, the activation energy was 27.22 and 18.84 kJ·mol−1, the enthalpy was 24.26 and 15.77 J·mol−1, and the entropy was 238.1 and 211.5 kJ−1·mol−1 before and after Au coating, respectively. Because of its high stability and low cost, the prepared photoelectrode may be suitable for industrial applications. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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16 pages, 3577 KiB  
Article
Effect of Silver Modification on the Photoactivity of Titania Coatings with Different Pore Structures
by Borbála Tegze, Emőke Albert, Boglárka Dikó, Norbert Nagy, Adél Rácz, György Sáfrán, Attila Sulyok and Zoltán Hórvölgyi
Nanomaterials 2021, 11(9), 2240; https://doi.org/10.3390/nano11092240 - 30 Aug 2021
Cited by 4 | Viewed by 1935
Abstract
Nanostructured photoactive systems are promising for applications such as air and water purification, including self-cleaning coatings. In this study, mesoporous TiO2 sol-gel coatings with different pore structures were prepared and modified with silver by two methods: the “mixing” method by adding AgNO [...] Read more.
Nanostructured photoactive systems are promising for applications such as air and water purification, including self-cleaning coatings. In this study, mesoporous TiO2 sol-gel coatings with different pore structures were prepared and modified with silver by two methods: the “mixing” method by adding AgNO3 to the precursor sol, and the “impregnation” method by immersing the samples in AgNO3 solution (0.03 and 1 M) followed by heat treatment. Our aim was to investigate the effects that silver modification has on the functional properties (e.g., those that are important for self-cleaning coatings). Transmittance, band gap energy, refractive index, porosity and thickness values were determined from UV-Vis spectroscopy measurements. Silver content and structure of the silver modified samples were characterized by X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, High-resolution transmission electron microscopy and Energy Dispersive X-ray Spectrometry elemental mapping measurements. Wettability properties, including photoinduced wettability conversion behavior were investigated by water contact angle measurements. Photoactivity was studied under both UV and visible light with rhodamine 6G and methylene blue dye molecules, at the liquid–solid and air–solid interfaces modeling the operating conditions of self-cleaning coatings. Samples made with “impregnation” method showed better functional properties, in spite of their significantly lower silver content. The pore structure influenced the Ag content achieved by the “impregnation” method, and consequently affected their photoactivity. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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20 pages, 5036 KiB  
Article
Optimization Method of the Solvothermal Parameters Using Box–Behnken Experimental Design—The Case Study of ZnO Structural and Catalytic Tailoring
by Zoltán Kovács, Csanád Molnár, Urška Lavrenčič Štangar, Vasile-Mircea Cristea, Zsolt Pap, Klara Hernadi and Lucian Baia
Nanomaterials 2021, 11(5), 1334; https://doi.org/10.3390/nano11051334 - 19 May 2021
Cited by 11 | Viewed by 2991
Abstract
ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box–Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were [...] Read more.
ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box–Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were correlated with photocatalytic degradation of methyl orange and the ratio of two crystallographic facets ((002) and (100)) using a quadratic model. The quadratic model shows good fit for both responses. The optimization experimental results validated the models. The ratio of the crystal facets shows similar variation as the photocatalytic activity of the samples. The water content of the solvent is the primary factor, which predominantly influence both responses. An explanation was proposed for the effect of the parameters and how the ratio of (002) and (100) crystal facets is influenced and its relation to the photocatalytic activity. The present research laconically describes a case study for an original experimental work, in order to serve as guideline to deal with such complicated subjects as quantifying influence of synthesis parameters upon the catalytic activity of the obtained ZnO. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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17 pages, 2531 KiB  
Article
Synthesis, Characterization and Visible-Light Photocatalytic Activity of Solid and TiO2-Supported Uranium Oxycompounds
by Mikhail Lyulyukin, Tikhon Filippov, Svetlana Cherepanova, Maria Solovyeva, Igor Prosvirin, Andrey Bukhtiyarov, Denis Kozlov and Dmitry Selishchev
Nanomaterials 2021, 11(4), 1036; https://doi.org/10.3390/nano11041036 - 19 Apr 2021
Cited by 8 | Viewed by 2608
Abstract
In this study, various solid uranium oxycompounds and TiO2-supported materials based on nanocrystalline anatase TiO2 are synthesized using uranyl nitrate hexahydrate as a precursor. All uranium-contained samples are characterized using N2 adsorption, XRD, UV–vis, Raman, TEM, XPS and tested [...] Read more.
In this study, various solid uranium oxycompounds and TiO2-supported materials based on nanocrystalline anatase TiO2 are synthesized using uranyl nitrate hexahydrate as a precursor. All uranium-contained samples are characterized using N2 adsorption, XRD, UV–vis, Raman, TEM, XPS and tested in the oxidation of a volatile organic compound under visible light of the blue region to find correlations between their physicochemical characteristics and photocatalytic activity. Both uranium oxycompounds and TiO2-supported materials are photocatalytically active and are able to completely oxidize gaseous organic compounds under visible light. If compared to the commercial visible-light TiO2 KRONOS® vlp 7000 photocatalyst used as a benchmark, solid uranium oxycompounds exhibit lower or comparable photocatalytic activity under blue light. At the same time, uranium compounds contained uranyl ion with a uranium charge state of 6+, exhibiting much higher activity than other compounds with a lower charge state of uranium. Immobilization of uranyl ions on the surface of nanocrystalline anatase TiO2 allows for substantial increase in visible-light activity. The photonic efficiency of reaction over uranyl-grafted TiO2, 12.2%, is 17 times higher than the efficiency for commercial vlp 7000 photocatalyst. Uranyl-grafted TiO2 has the potential as a visible-light photocatalyst for special areas of application where there is no strict control for use of uranium compounds (e.g., in spaceships or submarines). Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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18 pages, 6872 KiB  
Article
Comparing the Degradation Potential of Copper(II), Iron(II), Iron(III) Oxides, and Their Composite Nanoparticles in a Heterogeneous Photo-Fenton System
by Asfandyar Khan, Zsolt Valicsek and Ottó Horváth
Nanomaterials 2021, 11(1), 225; https://doi.org/10.3390/nano11010225 - 16 Jan 2021
Cited by 5 | Viewed by 3236
Abstract
Heterogeneous photo-Fenton systems offer efficient solutions for the treatment of wastewaters in the textile industry. This study investigated the fabrication and structural characterization of novel peculiar-shaped CuIIO, FeIII2O3, and FeIIO nanoparticles (NPs) compared to [...] Read more.
Heterogeneous photo-Fenton systems offer efficient solutions for the treatment of wastewaters in the textile industry. This study investigated the fabrication and structural characterization of novel peculiar-shaped CuIIO, FeIII2O3, and FeIIO nanoparticles (NPs) compared to the properties of the iron(II)-doped copper ferrite CuII0.4FeII0.6FeIII2O4. The photocatalytic efficiencies of these NPs and the composite of the simple oxides (CuIIO/FeIIO/FeIII2O3) regarding the degradation of methylene blue (MB) and rhodamine B (RhB) as model dyes were also determined. The catalysts were synthesized via simple co-precipitation and calcination technique. X-ray diffractometry (XRD), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS) were utilized for structural characterization. The structure of CuIIO was bead-like connected into threads, FeIII2O3 was rod-like, while FeIIO pallet-like, with average crystallite sizes of 18.9, 36.9, and 37.1 nm, respectively. The highest degradation efficiency was achieved by CuIIO for RhB and by CuII0.4FeII0.6FeIII2O4 for MB. The CuIIO/FeIIO/FeIII2O3 composite proved to be the second-best catalyst in both cases, with excellent reusability. Hence, these NPs can be successfully applied as heterogeneous photo-Fenton catalysts for the removal of hazardous pollutants. Moreover, the simple metal oxides and the iron(II)-doped copper ferrite displayed a sufficient antibacterial activity against Gram-negative Vibrio fischeri. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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14 pages, 5691 KiB  
Article
Electric and Photocatalytic Properties of Graphene Oxide Depending on the Degree of Its Reduction
by László Péter Bakos, Lőrinc Sárvári, Krisztina László, János Mizsei, Zoltán Kónya, Gyula Halasi, Klára Hernádi, Anna Szabó, Dániel Berkesi, István Bakos and Imre Miklós Szilágyi
Nanomaterials 2020, 10(11), 2313; https://doi.org/10.3390/nano10112313 - 22 Nov 2020
Cited by 8 | Viewed by 2907
Abstract
When graphene oxide is reduced, the functional groups are released and the structure becomes more ordered. The degree of reduction might be tunable with the process parameters. In our work, graphene oxide is prepared and the effect of thermal and chemical reduction is [...] Read more.
When graphene oxide is reduced, the functional groups are released and the structure becomes more ordered. The degree of reduction might be tunable with the process parameters. In our work, graphene oxide is prepared and the effect of thermal and chemical reduction is investigated. The samples are characterized with TG/DTA-MS, SEM-EDX, TEM, XPS, ATR-FTIR, Raman spectroscopy and XRD. Their electrical resistance, cyclic voltammetry and photocatalytic activity data are investigated. The conductivity can be varied by several orders of magnitude, offering a tool to match its electrical properties to certain applications. Low temperature reduction in air offers a material with the highest capacitance, which might be used in supercapacitors. The bare graphene oxide has considerably larger photocatalytic activity than P25 TiO2. Reduction decreases the activity, meaning that reduced graphene oxide can be used as an electron sink in composite photocatalysts, but does not contribute to the photocatalytic activity by itself. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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18 pages, 5757 KiB  
Article
Innovative and Cost-Efficient BiOI Immobilization Technique on Ceramic Paper—Total Coverage and High Photocatalytic Activity
by Zsolt Kása, Eszter Orbán, Zsolt Pap, Imre Ábrahám, Klára Magyari, Seema Garg and Klara Hernadi
Nanomaterials 2020, 10(10), 1959; https://doi.org/10.3390/nano10101959 - 1 Oct 2020
Cited by 12 | Viewed by 3009
Abstract
In the present work, visible light active bismuth oxyiodide (BiOI) was immobilized on a commercial, non-conductive support (an Al2O3 based ceramic paper) using a novel two-step spray coating technique and investigated with different characterization methods (e.g., SEM, Raman, XPS). Our [...] Read more.
In the present work, visible light active bismuth oxyiodide (BiOI) was immobilized on a commercial, non-conductive support (an Al2O3 based ceramic paper) using a novel two-step spray coating technique and investigated with different characterization methods (e.g., SEM, Raman, XPS). Our main goal was to eliminate the separation costs after the photocatalytic measurement and investigate the chemical relevance and opportunity to use this technique in the industry. Our as-prepared uniform BiOI layer had similar properties to the well-known reference BiOI powder. The Raman and XPS measurements confirmed that the enriched amount of the surface iodine defined the color and as well the band gap of the BiOI layer. The durable BiOI layers have prominent photocatalytic activity under UV and visible light irradiation as well. The scale-up procedure proved that the designed BiOI coated paper was reusable and potentially applicable in the industry by straightforward scale-up, which is due to the elaborated non-conventional BiOI coverage estimation method. This immobilization technique could open several opportunities for immobilizing many other visible light active photocatalysts with simple materials and low cost. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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