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Functional Hybrid Materials for Catalytic and Environmental Applications

A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (20 August 2022) | Viewed by 14966

Special Issue Editors

Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland
Interests: titanium dioxide, titania-based multicomponent oxide and hybrid systems, surface chemistry, inorganic pigments, photocatalysts, photocatalysis, electrode materials, environmental protection.
Special Issues, Collections and Topics in MDPI journals
Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland
Interests: inorganic materials (synthesis and characterization); immobilization of enzymes; catalysis

Special Issue Information

Dear Colleagues,

Over the last few years, a dynamic increase in interest in studies focused on the selection of the appropriate synthesis methods of multifunctional hybrid materials has been observed. The selection of proper components which form multifunctional hybrid materials with strictly defined physicochemical properties is known to be the crucial issue in the formation of a new generation of functional systems, which have applications as photocatalysts, biocides, or electrode materials. The development of methods for obtaining functional materials is very complex and requires several complicated experimental procedures for proper implementation. Furthermore, most challenging are assessments of the possible control of the physicochemical and structural properties of functional hybrid materials directly during the synthesis stage, and the determination of mechanisms of interactions at the selected component interface. Additionally, the key element is to understand the effects of the addition of an appropriate component on the properties exhibited by the synthesized multifunctional hybrid material. The concept of searching for functional combinations with appropriate materials is of high importance, especially due to the growing demand for active photocatalysts, especially those operating in visible light, as well as efficient electrode materials useful as substitutes for commonly used carbon precursors. Thus, this Special Issue focuses on recent advances in hybrid synthesis, functionalization, and applications.

Proposed scope of this Special Issue:

  • Synthesis of multifunctional hybrid materials;
  • Surface treatment and enhancement of the physicochemical properties (modification/grafting/ doping/immobilization);
  • Surface chemistry and functionality;
  • Physicochemical characterization of multifunctional materials;
  • Applications of hybrid materials in electrochemistry;
  • Applications of multifunctional hybrid materials in environmental protection—catalytic (e.g., photocatalytic) degradation of harmful inorganic and/or organic pollutants.

Dr. Katarzyna Siwińska-Ciesielczyk
Dr. Agnieszka Kołodziejczak-Radzimska
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 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

  • hybrid materials
  • synthesis methods of functional hybrid materials
  • surface chemistry
  • morphological and chemical modification
  • characterization techniques
  • photocatalysts and photocatalysis
  • antibacterial protection
  • environmental protection
  • electrochemistry

Published Papers (7 papers)

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Research

16 pages, 5219 KiB  
Article
Pilot-Scale Studies of WO3/S-Doped g-C3N4 Heterojunction toward Photocatalytic NOx Removal
by Marta Kowalkińska, Agnieszka Fiszka Borzyszkowska, Anna Grzegórska, Jakub Karczewski, Paweł Głuchowski, Marcin Łapiński, Mirosław Sawczak and Anna Zielińska-Jurek
Materials 2022, 15(2), 633; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15020633 - 14 Jan 2022
Cited by 10 | Viewed by 2241
Abstract
Due to the rising concentration of toxic nitrogen oxides (NOx) in the air, effective methods of NOx removal have been extensively studied recently. In the present study, the first developed WO3/S-doped g-C3N4 nanocomposite was synthesized [...] Read more.
Due to the rising concentration of toxic nitrogen oxides (NOx) in the air, effective methods of NOx removal have been extensively studied recently. In the present study, the first developed WO3/S-doped g-C3N4 nanocomposite was synthesized using a facile method to remove NOx in air efficiently. The photocatalytic tests performed in a newly designed continuous-flow photoreactor with an LED array and online monitored NO2 and NO system allowed the investigation of photocatalyst layers at the pilot scale. The WO3/S-doped-g-C3N4 nanocomposite, as well as single components, were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller surface area analysis (BET), X-ray fluorescence spectroscopy (XRF), X-ray photoemission spectroscopy method (XPS), UV–vis diffuse reflectance spectroscopy (DR/UV–vis), and photoluminescence spectroscopy with charge carriers’ lifetime measurements. All materials exhibited high efficiency in photocatalytic NO2 conversion, and 100% was reached in less than 5 min of illumination under simulated solar light. The effect of process parameters in the experimental setup together with WO3/S-doped g-C3N4 photocatalysts was studied in detail. Finally, the stability of the composite was tested in five subsequent cycles of photocatalytic degradation. The WO3/S-doped g-C3N4 was stable in time and did not undergo deactivation due to the blocking of active sites on the photocatalyst’s surface. Full article
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18 pages, 3878 KiB  
Article
The Studies on α-Pinene Oxidation over the TS-1. The Influence of the Temperature, Reaction Time, Titanium and Catalyst Content
by Agnieszka Wróblewska, Jadwiga Grzeszczak, Piotr Miądlicki, Karolina Kiełbasa, Marcin Kujbida, Adrianna Kamińska and Beata Michalkiewicz
Materials 2021, 14(24), 7799; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14247799 - 16 Dec 2021
Cited by 7 | Viewed by 2034
Abstract
The work presents the results of studies on α-pinene oxidation over the TS-1 catalysts with different Ti content (in wt%): TS-1_1 (9.92), TS-1_2 (5.42), TS-1_3 (3.39) and TS-1_4 (3.08). No solvent was used in the oxidation studies, and molecular oxygen was used as [...] Read more.
The work presents the results of studies on α-pinene oxidation over the TS-1 catalysts with different Ti content (in wt%): TS-1_1 (9.92), TS-1_2 (5.42), TS-1_3 (3.39) and TS-1_4 (3.08). No solvent was used in the oxidation studies, and molecular oxygen was used as the oxidizing agent. The effect of titanium content in the TS-1 catalyst, temperature, reaction time and amount of the catalyst in the reaction mixture on the conversion of α-pinene and the selectivities of appropriate products was investigated. It was found that it is most advantageous to carry out the process of α-pinene oxidation in the presence of the TS-1 catalyst with the titanium content of 5.42 wt% (TS-1_2), at the temperature of 85 °C, for 6 h and with the catalyst TS-1 content in the reaction mixture of 1 wt%. Under these conditions the conversion of α-pinene amounted to 34 mol%, and the selectivities of main products of α-pinene oxidation process were: α-pinene oxide (29 mol%), verbenol (15 mol%) and verbenone (12 mol%). In smaller quantities also campholenic aldehyde, trans-pinocarveol, myrtenal, myrtenol, L-carveol, carvone and 1,2-pinanediol were also formed. These products are of great practical importance in food, cosmetics, perfumery and medicine industries. Kinetic studies were also performed for the studied process. Full article
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18 pages, 7457 KiB  
Article
FeCl3-Modified Carbonaceous Catalysts from Orange Peel for Solvent-Free Alpha-Pinene Oxidation
by Adrianna Kamińska, Piotr Miądlicki, Karolina Kiełbasa, Jarosław Serafin, Joanna Sreńscek-Nazzal, Rafał Jan Wróbel and Agnieszka Wróblewska
Materials 2021, 14(24), 7729; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14247729 - 14 Dec 2021
Cited by 4 | Viewed by 2213
Abstract
The work presents the synthesis of FeCl3-modified carbonaceous catalysts obtained from waste orange peel and their application in the oxidation of alpha-pinene in solvent-free reaction conditions. The use of waste orange peel as presented here (not described in the literature) is [...] Read more.
The work presents the synthesis of FeCl3-modified carbonaceous catalysts obtained from waste orange peel and their application in the oxidation of alpha-pinene in solvent-free reaction conditions. The use of waste orange peel as presented here (not described in the literature) is an effective and cheap way of managing this valuable and renewable biomass. FeCl3-modified carbonaceous materials were obtained by a two-stage method: in the first stage, activated carbon was obtained, and in the second stage, it was modified by FeCl3 in the presence of H3PO4 (three different molar ratios of these two compounds were used in the studies). The obtained FeCl3-modified carbon materials were subjected to detailed instrumental studies using the methods FT-IR (Fourier-transform Infrared Spectroscopy), XRD (X-ray Diffraction), SEM (Scanning Electron Microscope), EDXRF (Energy Dispersive X-ray Fluorescence) and XPS (X-ray Photoelectron Spectroscopy), while the textural properties of these materials were also studied, such as the specific surface area and total pore volume. Catalytic tests with the three modified activated carbons showed that the catalyst obtained with the participation of 6 M of FeCl3 and 3 M aqueous solutions of H3PO4 was the most active in the oxidation of alpha-pinene. Further tests (influence of temperature, amount of catalyst, and reaction time) with this catalyst made it possible to determine the most favorable conditions for conducting oxidation on this type of catalyst, and allowed study of the kinetics of this process. The most favorable conditions for the process were: temperature of 100 °C, catalyst content of 0.5 wt% and reaction time 120 min (very mild process conditions). The conversion of the organic raw material obtained under these conditions was 40 mol%, and the selectivity of the transformation to alpha-pinene oxide reached the value of 35 mol%. In addition to the epoxy compound, other valuable products, such as verbenone and verbenol, were formed while carrying out the process. Full article
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27 pages, 3916 KiB  
Article
Activated Carbons Obtained from Orange Peels, Coffee Grounds, and Sunflower Husks—Comparison of Physicochemical Properties and Activity in the Alpha-Pinene Isomerization Process
by Adrianna Kamińska, Piotr Miądlicki, Karolina Kiełbasa, Marcin Kujbida, Joanna Sreńscek-Nazzal, Rafał Jan Wróbel and Agnieszka Wróblewska
Materials 2021, 14(23), 7448; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14237448 - 04 Dec 2021
Cited by 8 | Viewed by 2663
Abstract
This work presents studies on the preparation of porous carbon materials from waste biomass in the form of orange peels, coffee grounds, and sunflower seed husks. The preparation of activated carbons from these three waste materials involved activation with KOH followed by carbonization [...] Read more.
This work presents studies on the preparation of porous carbon materials from waste biomass in the form of orange peels, coffee grounds, and sunflower seed husks. The preparation of activated carbons from these three waste materials involved activation with KOH followed by carbonization at 800 °C in an N2 atmosphere. This way of obtaining the activated carbons is very simple and requires the application of only two reactants. Thus, this method is cheap, and it does not generate much chemical waste. The obtained activated carbons were characterized by XRD, SEM, XPS, and XRF methods. Moreover, the textural properties, acidity, and catalytic activity of these materials were descried. During catalytic tests carried out in the alpha-pinene isomerization process (the use of the activated carbons thus obtained in the process of alpha-pinene isomerization has not been described so far), the most active were activated carbons obtained from coffee grounds and orange peels. Generally, the catalytic activity of the obtained materials depended on the pore size, and the most active activated carbons had more pores with sizes of 0.7–1.0 and 1.1–1.4 nm. Moreover, the presence of potassium and chlorine ions in the pores may also be of key importance for the alpha-pinene isomerization process. On the other hand, the acidity of the surface of the tested active carbons did not affect their catalytic activity. The most favorable conditions for carrying out the alpha-pinene isomerization process were the same for the three tested activated carbons: temperature 160 °C, amount of the catalyst 5 wt.%, and reaction time 3 h. Kinetic studies were also carried out for the three tested catalysts. These studies showed that the isomerization over activated carbons from orange peels, coffee grounds, and sunflower seed husks is a first-order reaction. Full article
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17 pages, 4468 KiB  
Article
Catalytic and Physicochemical Evaluation of a TiO2/ZnO/Laccase Biocatalytic System: Application in the Decolorization of Azo and Anthraquinone Dyes
by Agnieszka Kołodziejczak-Radzimska, Joanna Zembrzuska, Katarzyna Siwińska-Ciesielczyk and Teofil Jesionowski
Materials 2021, 14(20), 6030; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14206030 - 13 Oct 2021
Cited by 5 | Viewed by 1414
Abstract
A TiO2/ZnO oxide system was proposed as a support for the immobilization of laccase from Trametes versicolor (LTV). The obtained TiO2/ZnO/LTV biocatalytic system was then applied in the decolorization/degradation of C.I. Reactive Black 5 and C.I. Acid Green 25 [...] Read more.
A TiO2/ZnO oxide system was proposed as a support for the immobilization of laccase from Trametes versicolor (LTV). The obtained TiO2/ZnO/LTV biocatalytic system was then applied in the decolorization/degradation of C.I. Reactive Black 5 and C.I. Acid Green 25 dyes. The efficiency of immobilization was evaluated based on catalytic properties (Bradford method, oxidation reaction of 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) and physicochemical (spectroscopic, porous, electrokinetic) analysis. The immobilization process was carried out with high performance (99.4%). Immobilized laccase retained about 40% of its activity in the whole analyzed temperature range and after 10 reaction cycles. Immobilization efficiency was also indirectly confirmed by the presence of characteristic functional groups (–C–H and –C–O), nitrogen and carbon on the TiO2/ZnO/LTV biocatalytic surface, identified by spectroscopic analyses. The increase in the surface area to 126 m2/g, change of isoelectric point (2.0) and zeta potential ranges (from +12.0 to −20.0 mV) after the immobilization process were also observed. The results show that the designed biocatalytic system enables the removal of acid dyes (C.I. Reactive Black 5 and C.I. Acid Green 25) with high efficiency (99% and 70%, respectively). Mass spectroscopy analysis indicated possible degradation products formed by the cleavage of N=N and C–N bonds. Full article
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19 pages, 2400 KiB  
Article
Synthesis of Selected Mixed Oxide Materials with Tailored Photocatalytic Activity in the Degradation of Tetracycline
by Katarzyna Siwińska-Ciesielczyk, Angelika Andrzejczak, Dominik Paukszta, Adam Piasecki, Dariusz Moszyński, Agnieszka Zgoła-Grześkowiak and Teofil Jesionowski
Materials 2021, 14(18), 5361; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14185361 - 17 Sep 2021
Cited by 9 | Viewed by 1511
Abstract
The elimination of antibiotics occurring in the natural environment has become a great challenge in recent years. Among other techniques, the photocatalytic degradation of this type of pollutant seems to be a promising approach. Thus, the search for new photoactive materials is currently [...] Read more.
The elimination of antibiotics occurring in the natural environment has become a great challenge in recent years. Among other techniques, the photocatalytic degradation of this type of pollutant seems to be a promising approach. Thus, the search for new photoactive materials is currently of great importance. The present study concerns the sol–gel synthesis of mono, binary and ternary TiO2-based materials, which are used as active photocatalysts. The main goal was to evaluate how the addition of selected components—zirconium dioxide (ZrO2) and/or zinc oxide (ZnO)—during the synthesis of TiO2-based materials and the temperature of thermal treatment affect the materials’ physicochemical and photocatalytic properties. The fabricated mixed oxide materials underwent detailed physicochemical analysis, utilizing scanning-electron microscopy (SEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), energy-dispersive X-ray spectroscopy (EDS), low-temperature N2 sorption (BET model), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The synthesized mixed oxide materials were used as photocatalysts in the heterogeneous photodegradation of tetracycline (TC). The physicochemical properties of the fabricated photocatalysts, including morphology, crystalline and textural structure, as well as the pH of the reaction system in the photocatalytic tests, were taken into account in determining their photo-oxidation activity. LC–MS/MS analysis was used to identify the possible degradation products of the selected antibiotic. Full article
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17 pages, 4850 KiB  
Article
The Impact of the Vanadium Oxide Addition on the Physicochemical Performance Stability and Intercalation of Lithium Ions of the TiO2-rGO-electrode in Lithium Ion Batteries
by Beata Kurc, Marcin Wysokowski, Łukasz Rymaniak, Piotr Lijewski, Adam Piasecki and Paweł Fuć
Materials 2020, 13(4), 1018; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13041018 - 24 Feb 2020
Cited by 7 | Viewed by 2269
Abstract
This work determines the effect of the addition of various amounts of vanadium oxide on the work of a cell built from a hybrid VxOy-TiO2-rGO system in a lithium-ion cell. Moreover, a new method based on solvothermal [...] Read more.
This work determines the effect of the addition of various amounts of vanadium oxide on the work of a cell built from a hybrid VxOy-TiO2-rGO system in a lithium-ion cell. Moreover, a new method based on solvothermal chemistry is proposed for the creation of a new type of composite material combining reduced graphene, vanadium oxide and crystalline anatase. The satisfactory electrochemical properties of VxOy-TiO2-rGO hybrids can be attributed to the perfect matching of the morphology and structure of VxOy-TiO2 and rGO. In addition, it is also responsible for the partial transfer of electrons from rGO to VxOy-TiO2, which increases the synergistic interaction of the VxOy-TiO2-rGO hybrid to the reversible storage of lithium. In addition a full cell was created LiFePO4/VxOy-TiO2-rGO. The cell showed good cyclability while providing a capacity of 120 mAh g−1. Full article
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