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Advances in Pillared Clays and Similar Materials: Synthesis, Characterization and Applications

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

Deadline for manuscript submissions: closed (31 October 2017) | Viewed by 50073

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Special Issue Editors

INAMAT^2-Departamento de Ciencias, Edificio de los Acebos, Universidad Pública de Navarra, Campus de Arrosadía, 31006 Pamplona, Spain
Interests: preparation, characterization, and catalytic activity of metal-supported catalysts; surface properties of solids; pollutants adsorption; environmental management; industrial waste valorization
Special Issues, Collections and Topics in MDPI journals
GIR-QUESCAT, Departamento de Química Inorgánica, Universidad de Salamanca, E-37008 Salamanca, Spain
Interests: clay-based materials; preparation, characterization, and catalytic activity of metal supported nanocatalysts; surface properties of solids; pollutants adsorption; environmental management
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Since the first works introducing the aluminum intercalated clay family in the early 1970s, interest in the synthesis of Pillared InterLayered Clays (PILCs) has increased tremendously, especially research into the properties and energetic and environmental applications. After our comprehensive reviews and book on the synthesis and catalytic applications of these materials, new references have appeared in the literature and the interest in this field is continuously increasing. The aim of this Special Issue is to collect the recent advances developed considering this family of solids. Contributions on similar materials, as intercalated clays, clay-based nanocomposites or intercalated hydrotalcites, are welcome.

Prof. Dr. Antonio Gil
Prof. Dr. Miguel A. Vicente
Guest Editors

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Keywords

  • Pillared interlayered clay
  • Pillared clay
  • Clay
  • Pillaring
  • Montmorillonite
  • Saponite
  • Catalysis
  • Catalytic applications
  • Metal supported catalysts
  • Fenton
  • Wastewater treatment
  • Advanced oxidation processes
  • Photocatalysis
  • Volatile organic oxidation
  • Green oxidation reactions
  • Adsorption
  • Dyes adsorption
  • Emergent contaminants adsorption

Published Papers (12 papers)

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12 pages, 4042 KiB  
Article
Preparation of 1D Hierarchical Material Mesosilica/Pal Composite and Its Performance in the Adsorption of Methyl Orange
by Mei Wu, Haifeng Han, Lingli Ni, Daiyun Song, Shuang Li, Tao Hu, Jinlong Jiang and Jing Chen
Materials 2018, 11(1), 164; https://doi.org/10.3390/ma11010164 - 20 Jan 2018
Cited by 9 | Viewed by 3957
Abstract
This paper highlights the synthesis of a one-dimensional (1D) hierarchical material mesosilica/palygorskite (Pal) composite and evaluates its adsorption performance for anionic dye methyl orange (MO) in comparison with Pal and Mobile crystalline material-41 (MCM-41). The Mesosilica/Pal composite is consisted of mesosilica coated Pal [...] Read more.
This paper highlights the synthesis of a one-dimensional (1D) hierarchical material mesosilica/palygorskite (Pal) composite and evaluates its adsorption performance for anionic dye methyl orange (MO) in comparison with Pal and Mobile crystalline material-41 (MCM-41). The Mesosilica/Pal composite is consisted of mesosilica coated Pal nanorods and prepared through a dual template approach using cetyltrimethyl ammonium bromide (CTAB) and Pal as soft and hard templates, respectively. The composition and structure of the resultant material was characterized by a scanning electron microscope (SEM), transmissionelectron microscopy (TEM), N2 adsorption-desorption analysis, small-angle X-Ray powder diffraction (XRD), and zeta potential measurement. Adsorption experiments were carried out with different absorbents at different contact times and pH levels. Compared with Pal and MCM-41, the mesosilica/Pal composite exhibited the best efficiency for MO adsorption. Its adsorption ratio is as high as 70.4%. Its adsorption equilibrium time is as short as 30 min. Results testify that the MO retention is promoted for the micro-mesoporous hierarchical structure and positive surface charge electrostatic interactions of the mesosilica/Pal composite. The regenerability of the mesosilica/Pal composite absorbent was also assessed. 1D morphology makes it facile to separate from aqueous solutions. It can be effortlessly recovered and reused for up to nine cycles. Full article
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1957 KiB  
Article
Preparation of Al/Fe-Pillared Clays: Effect of the Starting Mineral
by Helir-Joseph Muñoz, Carolina Blanco, Antonio Gil, Miguel-Ángel Vicente and Luis-Alejandro Galeano
Materials 2017, 10(12), 1364; https://doi.org/10.3390/ma10121364 - 28 Nov 2017
Cited by 29 | Viewed by 4267
Abstract
Four natural clays were modified with mixed polyoxocations of Al/Fe for evaluating the effect of the physicochemical properties of the starting materials (chemical composition, abundance of expandable clay phases, cationic exchange capacity and textural properties) on final physicochemical and catalytic properties of Al/Fe-PILCs. [...] Read more.
Four natural clays were modified with mixed polyoxocations of Al/Fe for evaluating the effect of the physicochemical properties of the starting materials (chemical composition, abundance of expandable clay phases, cationic exchange capacity and textural properties) on final physicochemical and catalytic properties of Al/Fe-PILCs. The aluminosilicate denoted C2 exhibited the highest potential as starting material in the preparation of Al/Fe-PILC catalysts, mainly due to its starting cationic exchange capacity (192 meq/100 g) and the dioctahedral nature of the smectite phase. These characteristics favored the intercalation of the mixed (Al13−x/Fex)7+ Keggin-type polyoxocations, stabilizing a basal spacing of 17.4 Å and high increase of the BET surface (194 m2/g), mainly represented in microporous content. According to H2-TPR analyses, catalytic performance of the incorporated Fe in the Catalytic Wet Peroxide Oxidation (CWPO) reaction strongly depends on the level of location in mixed Al/Fe pillars. Altogether, such physicochemical characteristics promoted high performance in CWPO catalytic degradation of methyl orange in aqueous medium at very mild reaction temperatures (25.0 ± 1.0 °C) and pressure (76 kPa), achieving TOC removal of 52% and 70% of azo-dye decolourization in only 75 min of reaction under very low concentration of clay catalyst (0.05 g/L). Full article
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2759 KiB  
Article
Removal of Ciprofloxacin from Aqueous Solutions Using Pillared Clays
by Maria Eugenia Roca Jalil, Miria Baschini and Karim Sapag
Materials 2017, 10(12), 1345; https://doi.org/10.3390/ma10121345 - 23 Nov 2017
Cited by 58 | Viewed by 4626
Abstract
Emerging contaminants in the environment have caused enormous concern in the last few decades, and among them, antibiotics have received special attention. On the other hand, adsorption has shown to be a useful, low-cost, and eco-friendly method for the removal of this type [...] Read more.
Emerging contaminants in the environment have caused enormous concern in the last few decades, and among them, antibiotics have received special attention. On the other hand, adsorption has shown to be a useful, low-cost, and eco-friendly method for the removal of this type of contaminants from water. This work is focused on the study of ciprofloxacin (CPX) removal from water by adsorption on pillared clays (PILC) under basic pH conditions, where CPX is in its anionic form (CPX). Four different materials were synthetized, characterized, and studied as adsorbents of CPX (Al-, Fe-, Si-, and Zr-PILC). The highest CPX adsorption capacities of 100.6 and 122.1 mg g−1 were obtained for the Si- and Fe-PILC (respectively), and can be related to the porous structure of the PILCs. The suggested adsorption mechanism involves inner-sphere complexes formation as well as van der Waals interactions between CPX and the available adsorption sites on the PILC surfaces. Full article
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3100 KiB  
Article
Novel Montmorillonite/TiO2/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts
by Bogna D. Napruszewska, Alicja Michalik-Zym, Melania Rogowska, Elżbieta Bielańska, Wojciech Rojek, Adam Gaweł, Monika Wójcik-Bania, Krzysztof Bahranowski and Ewa M. Serwicka
Materials 2017, 10(11), 1326; https://doi.org/10.3390/ma10111326 - 19 Nov 2017
Cited by 10 | Viewed by 4024
Abstract
A novel design of combustion catalysts is proposed, in which clay/TiO2/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts’ [...] Read more.
A novel design of combustion catalysts is proposed, in which clay/TiO2/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts’ thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N2 adsorption/desorption at −196 °C, and H2 TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO2 component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH3 (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO2/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO2/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials’ composition and their structural, textural, and redox properties. Full article
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4403 KiB  
Article
Microstructural Modification and Characterization of Sericite
by Yu Liang, Hao Ding, Sijia Sun and Ying Chen
Materials 2017, 10(10), 1182; https://doi.org/10.3390/ma10101182 - 16 Oct 2017
Cited by 9 | Viewed by 3276
Abstract
Activated sericite was prepared by thermal modification, acid activation and sodium modification, and it was characterized by X-ray diffraction (XRD) analysis, differential scanning calorimetry (DSC), N2 adsorption test, thermo-gravimetric analysis (TGA), nuclear magnetic resonance (NMR), and scanning electron microscope (SEM). The results [...] Read more.
Activated sericite was prepared by thermal modification, acid activation and sodium modification, and it was characterized by X-ray diffraction (XRD) analysis, differential scanning calorimetry (DSC), N2 adsorption test, thermo-gravimetric analysis (TGA), nuclear magnetic resonance (NMR), and scanning electron microscope (SEM). The results indicated that the crystallinity of raw sericite decreased after thermal modification; the pores with sizes between 5 nm to 10 nm of thermal-modified sericite have collapsed and the surface area increased after thermal modification. The dissolving-out amount of Al3+ reached ca. 31 mg/g in the optimal processing conditions during acid activation; cation exchange capacity (CEC) of acid-treated sericite increased to 56.37 mmol/100 g meq/g after sodium modification compared with that of raw sericite (7.42 mmol/100 g). The activated sericite is a promising matrix for clay-polymer nanocomposites. Full article
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2583 KiB  
Article
The Application of Functionalized Pillared Porous Phosphate Heterostructures for the Removal of Textile Dyes from Wastewater
by José Jiménez-Jiménez, Manuel Algarra, Vanessa Guimarães, Iuliu Bobos and Enrique Rodríguez-Castellón
Materials 2017, 10(10), 1111; https://doi.org/10.3390/ma10101111 - 21 Sep 2017
Cited by 2 | Viewed by 3532
Abstract
A synthesized functionalized pillared porous phosphate heterostructure (PPH), surface functionalized phenyl group, has been used to remove the dye Acid Blue 113 from wastewater. X-ray photoemission spectroscopy XPS and X-ray diffraction (XRD) were used to study its structure. The specific surface area of [...] Read more.
A synthesized functionalized pillared porous phosphate heterostructure (PPH), surface functionalized phenyl group, has been used to remove the dye Acid Blue 113 from wastewater. X-ray photoemission spectroscopy XPS and X-ray diffraction (XRD) were used to study its structure. The specific surface area of this was 498 m2/g. The adsorption capacities of PPH and phenyl surface functionalized (Φ-PPH) were 0.0400 and 0.0967 mmol/g, respectively, with a dye concentration of 10−5 M when well fitted with SIPS and Langmuir isotherms respectively (pH 6.5, 25 °C). The incorporation of the dye to the adsorbent material was monitored by the S content of the dye. It is suggested as an alternative for Acid Blue 113 remediation. Full article
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3280 KiB  
Article
Modification of 13X Molecular Sieve by Chitosan for Adsorptive Removal of Cadmium from Simulated Wastewater
by Yan Shi, Ken Sun, Lixin Huo, Xiuxiu Li, Xuebin Qi and Zhaohui Li
Materials 2017, 10(9), 1101; https://doi.org/10.3390/ma10091101 - 19 Sep 2017
Cited by 8 | Viewed by 4082
Abstract
Chitosan was used to modify a 13X molecular sieve to improve its cadmium removal capability. After being modified with 2% chitosan-acetate for 2 h at 30 °C, significant uptake of Cd2+ could be achieved. The uptake of Cd2+ on the modified [...] Read more.
Chitosan was used to modify a 13X molecular sieve to improve its cadmium removal capability. After being modified with 2% chitosan-acetate for 2 h at 30 °C, significant uptake of Cd2+ could be achieved. The uptake of Cd2+ on the modified 13X molecular sieve followed the Langmuir isotherms with a capacity of 1 mg/g. The kinetics of Cd2+ removal by modified 13X molecular sieve followed a pseudo second-order reaction, suggesting chemisorption or surface complexation. The Cd2+ removal with a sorbent dose of 2 g/L from an initial concentration of 100 μg/L reached more than 95% in 90 min. The equilibrium Cd2+ concentration was <5 μg/L, which meets the requirements of “Standards for Irrigation Water Quality” (GB5084-2005) (10 μg/L) and MCL and MCLG for groundwater and drinking water (5 μg/L) set by United States Environmental Protection Agency. Full article
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7538 KiB  
Article
Ag-Coated Heterostructures of ZnO-TiO2/Delaminated Montmorillonite as Solar Photocatalysts
by Carolina Belver, Mariana Hinojosa, Jorge Bedia, Montserrat Tobajas, Maria Ariadna Alvarez, Vicente Rodríguez-González and Juan Jose Rodriguez
Materials 2017, 10(8), 960; https://doi.org/10.3390/ma10080960 - 17 Aug 2017
Cited by 38 | Viewed by 5638
Abstract
Heterostructures based on ZnO-TiO2/delaminated montmorillonite coated with Ag have been prepared by sol–gel and photoreduction procedures, varying the Ag and ZnO contents. They have been thoroughly characterized by XRD, WDXRF, UV–Vis, and XPS spectroscopies, and N2 adsorption, SEM, and TEM. [...] Read more.
Heterostructures based on ZnO-TiO2/delaminated montmorillonite coated with Ag have been prepared by sol–gel and photoreduction procedures, varying the Ag and ZnO contents. They have been thoroughly characterized by XRD, WDXRF, UV–Vis, and XPS spectroscopies, and N2 adsorption, SEM, and TEM. In all cases, the montmorillonite was effectively delaminated with the formation of TiO2 anatase particles anchored on the clay layer’s surface, yielding porous materials with high surface areas. The structural and textural properties of the heterostructures synthesized were unaffected by the ZnO incorporated. The photoreduction led to solids with Ag nanoparticles decorating the surface. These materials were tested as photocatalysts for the degradation of several emerging contaminants with different nitrogen-bearing chemical structures under solar light. The catalysts yielded high rates of disappearance of the starting pollutants and showed quite stable performance upon successive applications. Full article
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3670 KiB  
Article
Study of CeO2 Modified AlNi Mixed Pillared Clays Supported Palladium Catalysts for Benzene Adsorption/Desorption-Catalytic Combustion
by Jingrong Li, Shufeng Zuo, Peng Yang and Chenze Qi
Materials 2017, 10(8), 949; https://doi.org/10.3390/ma10080949 - 15 Aug 2017
Cited by 14 | Viewed by 4895
Abstract
A new functional AlNi-pillared clays (AlNi-PILC) with a large surface area and pore volume was synthesized. The performance of adsorption/desorption-catalytic combustion over CeO2-modified Pd/AlNi-PILC catalysts was also studied. The results showed that the d001-value and specific surface area ( [...] Read more.
A new functional AlNi-pillared clays (AlNi-PILC) with a large surface area and pore volume was synthesized. The performance of adsorption/desorption-catalytic combustion over CeO2-modified Pd/AlNi-PILC catalysts was also studied. The results showed that the d001-value and specific surface area (SBET) of AlNi-PILC reached 2.11 nm and 374.8 m2/g, respectively. The large SBET and the d001-value improved the high capacity for benzene adsorption. Also, the strong interaction between PdCe mixed oxides and AlNi-PILC led to the high dispersion of PdO and CeO2 on the support, which was responsible for the high catalytic performance. Especially, 0.2% Pd/12.5% Ce/AlNi-PILC presented high performance for benzene combustion at 240 °C and high CO2 selectivity. Also, the combustion temperatures were lower compared to the desorption temperatures, which demonstrated that it could accomplish benzene combustion during the desorption process. Furthermore, its activity did not decrease after continuous reaction for 1000 h in dry air, and it also displayed good resistance to water and the chlorinated compound, making it a promising catalytic material for the elimination of volatile organic compounds. Full article
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951 KiB  
Article
Microwave-Assisted Pillaring of a Montmorillonite with Al-Polycations in Concentrated Media
by Beatriz González, Alba Helena Pérez, Raquel Trujillano, Antonio Gil and Miguel A. Vicente
Materials 2017, 10(8), 886; https://doi.org/10.3390/ma10080886 - 01 Aug 2017
Cited by 15 | Viewed by 3511
Abstract
A montmorillonite has been intercalated with Al3+ polycations, using concentrated solutions and clay mineral dispersions. The reaction has been assisted by microwave radiation, yielding new intercalated solids and leading to Al-pillared solids after their calcination at 500 °C. The solids were characterized [...] Read more.
A montmorillonite has been intercalated with Al3+ polycations, using concentrated solutions and clay mineral dispersions. The reaction has been assisted by microwave radiation, yielding new intercalated solids and leading to Al-pillared solids after their calcination at 500 °C. The solids were characterized by elemental chemical analysis, X-ray diffraction, FTIR spectroscopy, thermal analyses, and nitrogen adsorption. The evolution of the properties of the materials was discussed as a function of the preparation conditions. Microwave treatment for 2.5 min provided correctly pillared solids. Full article
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968 KiB  
Article
Scale Up Pillaring: A Study of the Parameters That Influence the Process
by Francine Bertella and Sibele B. C. Pergher
Materials 2017, 10(7), 712; https://doi.org/10.3390/ma10070712 - 27 Jun 2017
Cited by 12 | Viewed by 3646
Abstract
Pillared clays (PILCs) are interesting materials mostly due to their high basal spacing and surface area, which make them suitable for adsorption and catalysis applications, for example. However, the production of these materials on industrial scale is dependent on research about what parameters [...] Read more.
Pillared clays (PILCs) are interesting materials mostly due to their high basal spacing and surface area, which make them suitable for adsorption and catalysis applications, for example. However, the production of these materials on industrial scale is dependent on research about what parameters influence the process. Thus, the objective of this work was to evaluate what parameters influence the pillaring procedure. For this, pillared clays were synthesized following three series of experiments. In the first series, the effect of the amount of water in a clay suspension was evaluated. The best results were obtained by using diluted suspensions (1 g of clay to 100 mL of water). In the second series, several pillaring methods were tested. In the third series, the amount of pillared clay was raised to 50 g. Fifty grams of pillared clay can be obtained using the pillaring agent synthesized at 60 °C with further aging for 24 h, and this material exhibited high basal spacing (17.6 Å) and surface area (233 m2/g). These values are comparable with the traditional pillaring method using only 3 g of clay. Full article
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2018 KiB  
Article
Reuse of Pillaring Agent in Sequential Bentonite Pillaring Processes
by Francine Bertella and Sibele B. C. Pergher
Materials 2017, 10(7), 705; https://doi.org/10.3390/ma10070705 - 27 Jun 2017
Cited by 6 | Viewed by 3428
Abstract
This work describes the synthesis and characterization of pillared clays using a new pillaring method: the reuse of the pillaring solution. First, an Al pillared clay (PILC) was synthesized, and after filtration, the pillaring agent was stored and reused for an additional three [...] Read more.
This work describes the synthesis and characterization of pillared clays using a new pillaring method: the reuse of the pillaring solution. First, an Al pillared clay (PILC) was synthesized, and after filtration, the pillaring agent was stored and reused for an additional three pillaring procedures (P1, P2, and P3). The filtered pillaring solution was stored for one year and then reused for one additional pillaring procedure (P4). The samples were analyzed using XRD, N2 physisorption measurements and chemical analysis (EDX). All of the samples exhibited basal spacings larger than 17 Å and BET surface areas greater than 160 m2/g. After the P4 pillaring, the pillaring agent was precipitated with a Na2SO4 solution, and the resulting solid was analyzed using XRD and SEM. The results indicated that even after a total of five pillaring procedures, Al13 ions were still present in solution. Therefore, it is possible to reuse the pillaring solution four times and to even store the solution for one year, which is important from an industrial perspective. Full article
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