Special Issue "Functional Mineral Materials: Sorption, Catalytic and Photofunctional Properties"

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

Deadline for manuscript submissions: closed (31 July 2020).

Special Issue Editor

Prof. Dr. Tomasz Bajda
Website
Guest Editor
Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, 30-059 Krakow, al. A. Mickiewicza 30, Poland
Interests: functionalized mineral materials, sorption, zeolites, clay minerals, organo-minerals, fly ashes, apatites

Special Issue Information

Dear Colleagues,

Functional minerals are the materials inspired by geological systems originating from the billion years long history of the Earth. Each of them has a unique chemical composition and a structure that determines its interesting properties and possible functions. Natural, synthetic, and anthropogenic minerals, both in the original and modified form, serve as useful agents in environmental and industrial applications. The functions of mineral materials include cation- and anion-exchange, sorption, immobilization, energy storage, catalysts, and photo-activity. Layered clay minerals, zeolites and zeolite-like structures, and layered double hydroxides (LDHs) are particularly suited to such a defined functionalization. The modification of minerals in order to obtain functional mineral materials includes surface modification, functional loading, intercalation, grafting, doping and structure reformation.

This Special Issue, collecting interdisciplinary studies, will provide the current top trends in the innovative functionalization techniques of mineral materials. Reports on the unique properties of functionalized materials and their expected applications are also welcome.

I believe that this collection will contribute to the development of functionalization techniques of mineral materials and will become a source of new ideas for the design, research and use of functionalized minerals.

Prof. Dr. Tomasz Bajda
Guest Editor

Manuscript Submission Information

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Keywords

  • mineral materials
  • functionalization
  • modification
  • sorption
  • catalysts
  • photoactivity
  • layered minerals
  • mesoporous materials
  • analytical methods

Published Papers (11 papers)

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Research

Open AccessArticle
Interactions of Fe–N–S Co-Doped Porous Carbons with Bacteria: Sorption Effect and Enzyme-Like Properties
Materials 2020, 13(17), 3707; https://doi.org/10.3390/ma13173707 - 21 Aug 2020
Abstract
Carbon-based (nano)materials doped with transition metals, nitrogen and other heteroatoms are considered active heterogeneous catalysts in a wide range of chemical processes. Recently they have been scrutinized as artificial enzymes since they can catalyze proton-coupled electron transfer reactions vital for living organisms. Herein, [...] Read more.
Carbon-based (nano)materials doped with transition metals, nitrogen and other heteroatoms are considered active heterogeneous catalysts in a wide range of chemical processes. Recently they have been scrutinized as artificial enzymes since they can catalyze proton-coupled electron transfer reactions vital for living organisms. Herein, interactions between Gram-positive and Gram-negative bacteria and either metal-free N and/or S doped or metal containing Fe–N–S co-doped porous carbons are studied. The Fe- and N-co-doped porous carbons (Fe–N–C) exhibit enhanced affinity toward bacteria as they show the highest adsorption capacity. Fe–N–C materials also show the strongest influence on the bacteria viability with visible toxic effect. Both types of bacteria studied reacted to the presence of Fe-doped carbons in a similar manner, showing a decrease in dehydrogenases activity in comparison to controls. The N-coordinated iron-doped carbons (Fe–N–C) may exhibit oxidase/peroxidase-like activity and activate O2 dissolved in the solution and/or oxygen-containing species released by the bacteria (e.g., H2O2) to yield highly bactericidal reactive oxygen species. As Fe/N/ and/or S-doped carbon materials efficiently adsorb bacteria exhibiting simultaneously antibacterial properties, they can be applied, inter alia, as microbiological filters with enhanced biofouling resistance. Full article
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Open AccessArticle
White and Red Brazilian São Simão’s Kaolinite–TiO2 Nanocomposites as Catalysts for Toluene Photodegradation from Aqueous Solutions
Materials 2019, 12(23), 3943; https://doi.org/10.3390/ma12233943 - 28 Nov 2019
Abstract
The presence of volatile organic compounds in groundwater is a major concern when it is used as a drinking water source because many of these compounds can adversely affect human health. This work reports on the preparation and characterization of white and red [...] Read more.
The presence of volatile organic compounds in groundwater is a major concern when it is used as a drinking water source because many of these compounds can adversely affect human health. This work reports on the preparation and characterization of white and red Brazilian São Simão’s kaolinite-TiO2 nanocomposites and their use as catalysts in the photochemical degradation of toluene, a significant volatile organic compound. The nanocomposites were prepared by a sol-gel procedure, using titanium bis(triethanolaminate)diisopropoxide as a precursor. Thermal treatments of the nanocomposites led to different polymorphic titania phases, while the clay changed from kaolinite to metakaolinite. This structural evolution strongly affected the photocatalytic degradation behavior—all the solids efficiently degraded toluene and the solid calcined at 400 °C, formed by kaolinite and anatase, showed the best behavior (90% degradation). On extending the photochemical treatment up to 48 h, high mineralization levels were reached. The advantage of photodegradation using the nanocomposites was confirmed by comparing the results from isolated components (titanium dioxide and kaolinite) to observe that the nanocomposites displayed fundamental importance to the photodegradation pathways of toluene. Full article
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Open AccessArticle
Nanopowders of Yttria-Stabilized Zirconia Doped with Rare Earth Elements as Adsorbents of Humic Acids
Materials 2019, 12(23), 3915; https://doi.org/10.3390/ma12233915 - 27 Nov 2019
Cited by 1
Abstract
The aim of the investigations was to use, for the first time, zirconia nanopowders stabilized with yttria (YSZ) and rare element oxides (YSZ-Nd, YSZ-Gd) for removal of humic acids (HA) from aqueous solutions. Nanopowders were synthesized by means of hydrothermal crystallization and characterized [...] Read more.
The aim of the investigations was to use, for the first time, zirconia nanopowders stabilized with yttria (YSZ) and rare element oxides (YSZ-Nd, YSZ-Gd) for removal of humic acids (HA) from aqueous solutions. Nanopowders were synthesized by means of hydrothermal crystallization and characterized using scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) methods and analysis of zeta potential. The adsorption processes analysis was carried out in a series of experiments depending on: initial concentration of humic acids, contact time, pH and mass of the used adsorbent. It was found, that the YSZ-Nd exhibits strong and much higher effectiveness of HA adsorption than YSZ and YSZ-Gd. The HA adsorption rate reached 96.8% for YSZ-Nd dosage of 100 mg, pH 4, and 15 min reaction time and for HA initial concentration equal to 25 mg/L. According to the Langmuir model simulation, the maximum adsorption capacity of HA on YSZ-Nd at pH 4 was calculated to be 2.95 mg/g. Changes in the FT-IR spectra of YSZ-Nd confirmed humic acids’ adsorption on the tested nanopowders, by the presence of additional bands representing carboxylic, alcohol, carbonyl and amino groups in humic acid structure. These functional groups could represent humic acids binding on the YSZ, YSZ-Nd or YSZ-Gd surfaces. Full article
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Open AccessArticle
Modification of Bentonite with Cationic and Nonionic Surfactants: Structural and Textural Features
Materials 2019, 12(22), 3772; https://doi.org/10.3390/ma12223772 - 17 Nov 2019
Cited by 3
Abstract
Surfactant-modified clay minerals are known for their good sorption properties of both organic and inorganic compounds from aqueous solutions. However, the current knowledge regarding the effect of both cationic and nonionic surfactants on the properties of bentonite is still insufficient. Bentonite, with montmorillonite [...] Read more.
Surfactant-modified clay minerals are known for their good sorption properties of both organic and inorganic compounds from aqueous solutions. However, the current knowledge regarding the effect of both cationic and nonionic surfactants on the properties of bentonite is still insufficient. Bentonite, with montmorillonite as the base clay, was modified with hexadecethyltrimethylammonium bromide (a cationic surfactant) in the amount of 1.0 cation exchange capacity (CEC) of bentonite and varying concentrations of t-octylphenoxypolyethoxyethanol (Triton X-100, a nonionic surfactant). We aimed to improve the understanding of the effect of nonionic and cationic surfactants on clay minerals. The modified bentonites were characterized by X-ray diffraction (XRD), thermogravimetric analysis/differential thermal analysis (TG/DTA), Fourier transform infrared spectrometry (FTIR), field emission scanning electron microscopy (SEM) and specific surface area and pore volume (BET). According to our results, the presence of a cationic surfactant significantly increased the amount of the adsorbed nonionic surfactant. Moreover, an increase in the concentration of nonionic surfactants is also associated with an increase in the effectiveness of the modification process. Our results indicate that the amount of nonionic surfactant used has a significant effect on the properties of the obtained hybrid material. Modification of bentonite with a nonionic surfactant did not cause an expansion of the interlayer space of smectite, regardless of the presence of a cationic surfactant. The modification process was found to significantly decrease the specific surface area of bentonite. Improvement of hydrophobic properties and thermal stability was also observed. Full article
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Open AccessArticle
Sorption of Heavy Metal Cations on Mesoporous ZSM-5 and Mordenite Zeolites
Materials 2019, 12(19), 3271; https://doi.org/10.3390/ma12193271 - 08 Oct 2019
Cited by 3
Abstract
Desilication and dealumination techniques were used to obtain mesoporous ZSM-5 and mordenite zeolites. The study provides insight into specific structural, textural, and sorption properties of obtained materials with different Si/Al ratios. Subsequent dealumination and desilication procedures were found to be efficient methods of [...] Read more.
Desilication and dealumination techniques were used to obtain mesoporous ZSM-5 and mordenite zeolites. The study provides insight into specific structural, textural, and sorption properties of obtained materials with different Si/Al ratios. Subsequent dealumination and desilication procedures were found to be efficient methods of generating a secondary system of mesopores in mordenite and ZSM-5 crystals while preserving their microporous character. The investigated materials were evaluated in terms of their sorption properties of selected heavy metal cations (Cd2+, Cr3+, and Pb2+). Particular emphasis was placed on the structural examination of the materials via infrared spectroscopy (FT-IR). Other research methods included X-ray diffraction (XRD), X-ray fluorescence (XRF), nuclear magnetic resonance (NMR) and atomic absorption spectrometry (AAS). Full article
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Open AccessArticle
The Triple Mechanisms of Atenolol Adsorption on Ca-Montmorillonite: Implication in Pharmaceutical Wastewater Treatment
Materials 2019, 12(18), 2858; https://doi.org/10.3390/ma12182858 - 05 Sep 2019
Cited by 1
Abstract
The adsorption of atenolol (AT) from aqueous solutions by Ca-montmorillonite (SAz-2) was investigated in batch studies under different physicochemical conditions. The AT existed in neutral un-dissociated form at pH 10, and was adsorbed on dioctahedral smectite (SAz-2) obeying the Langmuir isotherm with a [...] Read more.
The adsorption of atenolol (AT) from aqueous solutions by Ca-montmorillonite (SAz-2) was investigated in batch studies under different physicochemical conditions. The AT existed in neutral un-dissociated form at pH 10, and was adsorbed on dioctahedral smectite (SAz-2) obeying the Langmuir isotherm with a maximum adsorption capacity of 330 mmol/kg. The kinetic adsorption suggested that both strong and weak adsorption sites existed on SAz-2 and participated in the adsorption mechanisms. The amount of exchangeable cations desorbed from SAz-2 during AT adsorption was linearly correlated with the amounts of adsorbed AT having slopes of 0.43, which implied that a cation exchange based adsorption mechanism was also in place. A comprehensive basal spacing change of SAz-2 was observed after AT adsorption on the clay mineral when tested with or without AT recrystallization. The intercalation of AT into the SAz-2 interlayers did not result in swelling due to the low adsorption capacity of the drug. Prominent interactions between the pharmaceutical molecule and SAz-2 were evidenced by apparent shifts of the infrared absorption bands after adsorption. The interlayer configurations and hydrogen bonding of AT on SAz-2 were also supported by infrared, X-ray diffraction and thermogravimetric analyses. This study suggested that SAz-2 is an excellent material to remove not only AT from pharmaceutical wastewater, but can potentially remove many other β-receptor blocker drugs. The results helped us to understand the possible interlayer configurations and adsorption mechanisms of the drugs on natural clay mineral based adsorbents. Full article
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Open AccessArticle
Calcined Post-Production Waste as Materials Suitable for the Hydrothermal Synthesis of Zeolites
Materials 2019, 12(17), 2742; https://doi.org/10.3390/ma12172742 - 27 Aug 2019
Abstract
The zeolite production process is currently being very intensively researched. Due to environmental protection, as well as issues related to the guidelines of a zero-waste economy, all activities aimed at obtaining such materials from post-processed waste are extremely important. This article presents an [...] Read more.
The zeolite production process is currently being very intensively researched. Due to environmental protection, as well as issues related to the guidelines of a zero-waste economy, all activities aimed at obtaining such materials from post-processed waste are extremely important. This article presents an innovative method of utilising calcined carboniferous shale in order to produce synthetic zeolites. The raw material for testing came from two Polish hard coal mines. Both the chemical and phase composition of the coal shale were characterised. Based on the recorded thermal analysis results coupled with the mass spectrometer, the processes occurring during the heating of raw materials were interpreted and the calcination temperatures were determined. The changes in the phase composition of raw materials resulting from the calcination process used were also analysed. The heat-treated raw materials were subjected to the synthesis of zeolites in an aqueous solution of sodium hydroxide by means of the hydrothermal method at a concentration of 2.75 M. The results of water leaching and structural parameters are presented for both raw materials, as well as the produced synthesis. The conducted research confirmed that after the application of the synthetic process on coal shale, a zeolite with a surface area of SBET equal to 172 m2/g can be obtained. Full article
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Open AccessArticle
Influence of Waste Engine Oil Addition on the Properties of Zeolite-Foamed Asphalt
Materials 2019, 12(14), 2265; https://doi.org/10.3390/ma12142265 - 15 Jul 2019
Cited by 15
Abstract
The previous studies on asphalt mix and asphalt with waste engine oil addition indicate the possibility of using this type of waste material for the construction of road pavements. The research presented in this paper aimed at the preliminary assessment of possible waste [...] Read more.
The previous studies on asphalt mix and asphalt with waste engine oil addition indicate the possibility of using this type of waste material for the construction of road pavements. The research presented in this paper aimed at the preliminary assessment of possible waste engine oil (WEO) addition to the asphalts foamed with water-soaked zeolites. In this research, synthetic zeolite Na-P1 and natural clinoptilolite were used. In order to improve the foaming effect, the zeolites were soaked with water before dispensing to the asphalt, in the amount of 75% asphalt weight for Na-P1 and 25% for clinoptilolite. The tests were performed for one type of waste engine oil—5W40 and two type of binders: 20/30 and polymer modified 25/55-60. The asphalt parameters such as the dynamic viscosity, penetration and softening point were determined with the addition of WEO and zeolites in the concentration of 0%, 3%, 5%, 7% for both materials. It was found that the WEO addition lowers the viscosity and softening point of asphalt but increases penetration. The zeolite addition affected the change of these parameters to a minor extent or was statistically irrelevant. The chemical analysis of the asphalt samples with WEO addition performed with the X-ray Fluorescence method did not show a significant amount of heavy metals which would increase the probability of low-temperature cracking. The analysis of the results indicates the possibility of using zeolite-foamed asphalt technology with WEO addition. Full article
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Open AccessArticle
Sorption of Molybdates and Tungstates on Functionalized Montmorillonites: Structural and Textural Features
Materials 2019, 12(14), 2253; https://doi.org/10.3390/ma12142253 - 13 Jul 2019
Cited by 2
Abstract
Montmorillonite—the most popular mineral of the smectite group—has been recognized as a low-cost, easily available mineral sorbent of heavy metals and other organic and inorganic compounds that pollute water. The aim of this work was to determine the sorption mechanism and to identify [...] Read more.
Montmorillonite—the most popular mineral of the smectite group—has been recognized as a low-cost, easily available mineral sorbent of heavy metals and other organic and inorganic compounds that pollute water. The aim of this work was to determine the sorption mechanism and to identify the reaction products formed on the surface of montmorillonite and organo-montmorillonite after sorption of molybdates (Mo(VI)) and tungstates (W(VI)). Montmorillonites are often modified to generate a negative charge on the surface. The main objective of the study was to investigate and compare the features of Na-montmorillonite (Na-M), montmorillonite modified with dodecyl trimethyl ammonium bromide (DDTMA-M), and montmorillonite modified with didodecyl dimethyl ammonium bromide (DDDDMA-M) before and after sorption experiments. The material obtained after sorption was studied by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The XRD pattern showed the presence of a new crystallic phase in the sample that was observed under an SEM as an accumulation of crystals. The FTIR spectra showed bands related to Mo–O and W–O vibration (840 and 940 cm−1, respectively). The obtained results suggest that molybdenum(VI) and tungsten(VI) ions sorb onto the organo-montmorillonite in the form of alkylammonium molybdates and tungstates. Full article
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Open AccessArticle
The Nature of Interactions and UV-Induced Response within α-Zirconium Phosphate Intercalation Compounds with Azobenzenes
Materials 2019, 12(9), 1436; https://doi.org/10.3390/ma12091436 - 02 May 2019
Cited by 2
Abstract
Azobenzenes immobilization on a solid support enables the usage of their trans-cis isomerization ability for preparation of functional materials. The behavior of azobenzenes in the interlayer space of α-zirconium phosphate (ZrP) upon the UV–Vis irradiation was investigated. Two experimental approaches were performed: (1) [...] Read more.
Azobenzenes immobilization on a solid support enables the usage of their trans-cis isomerization ability for preparation of functional materials. The behavior of azobenzenes in the interlayer space of α-zirconium phosphate (ZrP) upon the UV–Vis irradiation was investigated. Two experimental approaches were performed: (1) co-intercalation of benzylalkylammonium surfactants and azobenzene in the interlayers of ZrP (ZBCnA), and (2) intercalation of p-aminoazobenzene (ZpA). The materials were characterized with XRD, FTIR, UV–Vis, CHN analysis, and the molecular modeling. The molecules in ZBCnA samples were sparsely packed and held by weak hydrophobic interactions. Conversely, the molecules in ZpA sample were strongly H-bonded to the ZrP, well-ordered, and densely packed. These structural features determined the samples’ photoresponsive behavior. Low density of molecules in the ZBCnA samples, allowed the effective, fast, and reversible isomerization of azobenzene. Whereas the ZpA sample did not react to the UV irradiation because of the steric hindrance of tightly packed molecules. Full article
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Open AccessArticle
Removal of Chromates and Sulphates by Mg/Fe LDH and Heterostructured LDH/Halloysite Materials: Efficiency, Selectivity, and Stability of Adsorbents in Single- and Multi-Element Systems
Materials 2019, 12(9), 1373; https://doi.org/10.3390/ma12091373 - 28 Apr 2019
Cited by 9
Abstract
Industrial wastewaters often contain mobile and toxic anions that cannot be removed by precipitation techniques and most known adsorbents. Layered double hydroxides (LDH) are excellent scavengers of anions; however, their use in real applications is of minor importance owing to their swelling behavior [...] Read more.
Industrial wastewaters often contain mobile and toxic anions that cannot be removed by precipitation techniques and most known adsorbents. Layered double hydroxides (LDH) are excellent scavengers of anions; however, their use in real applications is of minor importance owing to their swelling behavior and high cost of production. The performed research shows the possibility of obtaining Mg/Fe LDH using natural magnesite. Moreover, heterostructured LDH/halloysite materials were synthesized. The adsorption efficiency of these materials was very high in both single- and multi-element systems, confirming the LDH selectivity. This was with the exception of wastewaters containing a high concentration of chlorides, which clearly hampered the removal of Cr(VI) and S(VI). The measurements indicated that LDH dissolution took place to a small extent (<10 wt%). The LDH/halloysite materials showed lower efficiency than the raw LDH; however, the clay presence has several benefits in terms of future applications: (i) it significantly reduces the pH, especially in contrast to the calcined LDH, which enables the reuse or safe disposal of purified water; (ii) it reduces swelling of the composite, which opens the possibility for applications in column adsorption; (iii) it induces dual adsorption properties through additional cation adsorption; and (iv) it substantially lowers the price of the adsorbent. Full article
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