Special Issue "Nanoporous Materials and Their Applications"

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Nanotechnology and Applied Nanosciences".

Deadline for manuscript submissions: 31 December 2018

Special Issue Editors

Guest Editor
Prof. Enrique Rodríguez-Castellón

Universidad de Málaga. Departamento de Química Inorgánica, Málaga, Spain
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Interests: nanoporous materials; combustion of VOCs; hydrodesulfurization (HDS); hydrodenitrogenation (HDN); hydrodeoxygenation (HDO)
Co-Guest Editor
Prof. Dr. Sibele B. C. Pergher

Departamento de Química, Universidade Federal do Rio Grande do Norte, Natal Caixa postal 1524, Brazil
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Interests: chemistry and materials with emphasis on synthesis and characterization of inorganic solids, synthesis catalysts, zeolites, clays, mesoporous materials, lamellar materials, adsorption, catalysis processes

Special Issue Information

Dear Colleagues,

This Special Issue will be dedicated to the preparation and characterization of nanoporous materials such as zeolitic type materials, mesoporous silica (SBA-15, MCM-41, HMS and similar), mesoporous metallic oxides, metal-organic framework structures (MOFs), carbons and pillared solids (pillared clays, pillared phosphates), and their applications in adsorption, catalysis, sensing, energy and other emerging areas. This Special Issue will give a global vision of researchers from the world-wide universities, research centers and industry working on nanoporous materials and share the latest results on synthesis and characterization giving rise a special interest in their applications in basic and industrial processes. 

Prof. Dr. Enrique Rodríguez-Castellón
Dr. Sibele Pergher
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 1400 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

  • Nanoporous materials

  • Zeolites

  • Pillared clays

  • Mesoporous materials

  • MOFs

  • Carbon porous

  • Catalysis

  • Adsorption

Published Papers (12 papers)

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Research

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Open AccessArticle The Influence of Quantum Confinement on Third-Order Nonlinearities in Porous Silicon Thin Films
Appl. Sci. 2018, 8(10), 1810; https://doi.org/10.3390/app8101810
Received: 14 September 2018 / Revised: 26 September 2018 / Accepted: 28 September 2018 / Published: 3 October 2018
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Abstract
We present an experimental investigation into the third-order nonlinearity of conventional crystalline (c-Si) and porous (p-Si) silicon with Z-scan technique at 800-nm and 2.4-μm wavelengths. The Gaussian decomposition method is applied to extract the nonlinear refractive index,
[...] Read more.
We present an experimental investigation into the third-order nonlinearity of conventional crystalline (c-Si) and porous (p-Si) silicon with Z-scan technique at 800-nm and 2.4- μ m wavelengths. The Gaussian decomposition method is applied to extract the nonlinear refractive index, n 2 , and the two-photon absorption (TPA) coefficient, β , from the experimental results. The nonlinear refractive index obtained for c-Si is 7 ± 2 × 10 6 cm 2 /GW and for p-Si is 9 ± 3 × 10 5 cm 2 /GW. The TPA coefficient was found to be 2.9 ± 0.9 cm/GW and 1.0 ± 0.3 cm/GW for c-Si and p-Si, respectively. We show an enhancement of the nonlinear refraction and a suppression of TPA in p-Si in comparison to c-Si, and the enhancement gets stronger as the wavelength increases. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Introduction of Al into the HPM-1 Framework by In Situ Generated Seeds as an Alternative Methodology
Appl. Sci. 2018, 8(9), 1634; https://doi.org/10.3390/app8091634
Received: 10 July 2018 / Revised: 26 July 2018 / Accepted: 29 July 2018 / Published: 13 September 2018
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Abstract
An alternative method for the introduction of aluminum into the STW zeolitic framework is presented. HPM-1, a chiral STW zeolite with helical pores, was synthesized in the pure silica form, and an aluminum source was added by in situ generated seeds. Displacements of
[...] Read more.
An alternative method for the introduction of aluminum into the STW zeolitic framework is presented. HPM-1, a chiral STW zeolite with helical pores, was synthesized in the pure silica form, and an aluminum source was added by in situ generated seeds. Displacements of the peak positions in the Al samples were found in the X-ray diffractograms, indicating the possible incorporation of the heteroatom into the framework. Using an analysis of the 29Si and 27Al magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra, we concluded that the aluminum was effectively introduced into the framework. The (AlTETRAHEDRAL/AlOCTAHEDRAL) ratio and its textural properties were studied to explain the catalytic ethanol conversion results at medium temperatures. The sample with the lowest Si/Al ratio showed the best results due to its higher surface area and pore volume, in comparison to those observed for the sample with the highest Si/Al ratio, and due to its higher bulk tetrahedral aluminum content, in comparison to the intermediate Si/Al ratio sample. All catalysts were selective to ethylene and diethyl ether, confirming the presence of acidic sites. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Silica Pillared Montmorillonites as Possible Adsorbents of Antibiotics from Water Media
Appl. Sci. 2018, 8(8), 1403; https://doi.org/10.3390/app8081403
Received: 18 July 2018 / Revised: 14 August 2018 / Accepted: 16 August 2018 / Published: 19 August 2018
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Abstract
In this work, three silica pillared clays (Si-PILC) were synthetized, characterized, and evaluated as possible adsorbents of ciprofloxacin (CPX) and tetracycline (TC) form alkaline aqueous media. The pillared clays obtained showed significant increases in their specific surface areas (SBET) and micropore
[...] Read more.
In this work, three silica pillared clays (Si-PILC) were synthetized, characterized, and evaluated as possible adsorbents of ciprofloxacin (CPX) and tetracycline (TC) form alkaline aqueous media. The pillared clays obtained showed significant increases in their specific surface areas (SBET) and micropore volumes (Vμp) regarding the raw material, resulting in microporosity percentages higher than 57% in all materials. The studies of CPX and TC removal using pillared clays were compared with the natural clay and showed that the Si-PILC adsorption capacities have a strong relationship with their porous structures. The highest adsorption capacities were obtained for CPX on Si-PILC due to the lower molecular size of CPX respect to the TC molecule, favoring the interaction between the CPX and the pillars adsorption sites. Tetracycline adsorption on silica pillared clays evidenced that for this molecule the porous structure limits the interaction between the TCH and the pillars, decreasing their adsorption capacities. However, the results obtained for both antibiotics suggested that their negative species interact with adsorption sites on the pillared structure by adsorption mechanisms that involve inner-sphere complex formation as well as van der Waals interactions. The adsorption mechanism proposed for the anionic species on Si-PILC could be considered mainly as negative cooperative phenomena where firstly there is a hydrophobic effect followed by other interactions, such as der Waals or inner-sphere complex formation. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Effects of Different Variables on the Formation of Mesopores in Y Zeolite by the Action of CTA+ Surfactant
Appl. Sci. 2018, 8(8), 1299; https://doi.org/10.3390/app8081299
Received: 25 June 2018 / Revised: 21 July 2018 / Accepted: 26 July 2018 / Published: 4 August 2018
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Abstract
Zeolites are microporous crystalline aluminosilicates with a number of useful properties including acidity, hydrothermal stability, and structural selectivity. However, the exclusive presence of micropores restricts diffusive mass transport and reduces the access of large molecules to active sites. In order to resolve this
[...] Read more.
Zeolites are microporous crystalline aluminosilicates with a number of useful properties including acidity, hydrothermal stability, and structural selectivity. However, the exclusive presence of micropores restricts diffusive mass transport and reduces the access of large molecules to active sites. In order to resolve this problem, mesopores can be created in the zeolite, combining the advantages of microporous and mesoporous materials. In this work, mesospores were created in the Ultrastable USY zeolite (silicon/aluminum ratio of 15) using alkaline treatment (NaOH) in the presence of cetyltrimethylammonium bromide surfactant, followed by hydrothermal treatment. The effects of the different concentrations of NaOH and the surfactant on the textural, chemical, and morphological characteristics of the modified zeolites were evaluated. Generating mesoporosity in the USY zeolite was possible through the simultaneous presence of surfactant and alkaline solution. Among the parameters studied, the concentration of the alkaline medium had the greatest influence on the textural properties of the zeolites. The presence of Cetyltrimethylammonium Bromide (CTA+) prevented the amorphization of the structure during the modification and also avoided desilication of the zeolite. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Effect of Degassing on the Stability and Reversibility of Glycerol/ZSM-5 Zeolite System
Appl. Sci. 2018, 8(7), 1065; https://doi.org/10.3390/app8071065
Received: 6 June 2018 / Revised: 25 June 2018 / Accepted: 26 June 2018 / Published: 29 June 2018
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Abstract
Gaseous phase plays roles in a liquid/nanoporous system during application that adequate attention should be paid to the gaseous effects and the nanoscale gas-liquid interaction. In the present study, two glycerol/ZSM-5 zeolite systems with different amount of residual gas are compared by performing
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Gaseous phase plays roles in a liquid/nanoporous system during application that adequate attention should be paid to the gaseous effects and the nanoscale gas-liquid interaction. In the present study, two glycerol/ZSM-5 zeolite systems with different amount of residual gas are compared by performing a series of experiments. Influences of loading rate, as well as system temperature on the gas-liquid interactions, are studied. Results show that vacuum degassing pretreatment is required to obtain a reversible and stable energy absorption system. Moreover, the influence of gas on a liquid/nanoporous system is found to mainly act on the liquid outflow. After the routine vacuum degassing pretreatment, the residual air that is left in the nanopores is around 0.9014 nm–3 per unit specific pore volume, as presented in the current study. During compression, the existing gas left in the nanochannel tends to gather into the gas cluster, which further promotes the liquid outflow during unloading. However, excessively dissolved gas may reduce the driving force for liquid outflow by breaking the continuity of the liquid molecular chain in nanochannel. Consequently, small bubbles as a labile factor in the system must be excluded for the steady use of the system. This work sheds some light on the effect of the amount of residual gas on the liquid/nanoporous system and gives guidance on the pretreatment of the liquid/nanoporous material mixture before encapsulating. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Mesoporous Niobium Oxyhydroxide Catalysts for Cyclohexene Epoxidation Reactions
Appl. Sci. 2018, 8(6), 881; https://doi.org/10.3390/app8060881
Received: 18 April 2018 / Revised: 15 May 2018 / Accepted: 18 May 2018 / Published: 28 May 2018
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Abstract
Mesoporous catalysts were synthesized from the precursor NbCl5 and surfactant CTAB (cetyltrimethylammonium bromide), using different synthesis routes of, in order to obtain materials with different properties which are capable of promoting the epoxidation of cyclohexene. The materials were characterized by X ray
[...] Read more.
Mesoporous catalysts were synthesized from the precursor NbCl5 and surfactant CTAB (cetyltrimethylammonium bromide), using different synthesis routes of, in order to obtain materials with different properties which are capable of promoting the epoxidation of cyclohexene. The materials were characterized by X ray diffractometry (XRD), thermogravimetry (TG), acidity via pyridine adsorption, Hammet titration and N2 adsorption/desorption. The characterization data indicate that the calcination process of the catalysts was efficient for elimination of the surfactant, but it caused a collapse of the structure, causing a Brunauer Emmett Teller (BET) specific area decrease (ClNbS-600, 44 and ClNbS-AC-600, 64 m2 g−1). The catalysts that have not been calcined showed high BET specific areas (ClNbS 198 and ClNbS-AC 153 m2 g−1). Catalytic studies have shown that mild reaction conditions promote high conversion. The catalysts ClNbS and ClNbS-AC showed high conversions of cyclohexene, 50 and 84%, respectively, while the calcined materials showed low conversion (<30%). The epoxide formation was confirmed by nuclear magnetic resonance (NMR). Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Influence of Synthesis Parameters in Obtaining KIT-6 Mesoporous Material
Appl. Sci. 2018, 8(5), 725; https://doi.org/10.3390/app8050725
Received: 16 April 2018 / Revised: 27 April 2018 / Accepted: 30 April 2018 / Published: 5 May 2018
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Abstract
In the present work, modifications were made in the typical synthesis of KIT-6 mesoporous material. The molar ratio of P123 and its dissolution time, the type of alcohol, the aging time, and the heat treatment time were varied. The materials obtained were characterized
[...] Read more.
In the present work, modifications were made in the typical synthesis of KIT-6 mesoporous material. The molar ratio of P123 and its dissolution time, the type of alcohol, the aging time, and the heat treatment time were varied. The materials obtained were characterized by X-ray diffraction (XRD), thermogravimetry and differential thermogravimetry (TG/DTG), Fourier-transform infrared spectroscopy (FTIR), adsorption and desorption of N2 and transmission electron microscopy (TEM). It was observed that the modifications interfered directly in the ordered structure of materials, displaying materials with cubic structures Ia3d (KIT-6 mesoporous material) and hexagonal structures P6mm, (SBA-15 mesoporous material). The type of alcohol probably acts on generation of the micelle, influencing the formation of the porous system and ordered structure. The results obtained indicate that the cubic structure of KIT-6 can be formed with a reduction of 30% in the P123 concentration, and decreases of 2, 6 and 12 h in times of P123 dissolution, aging and heat treatment, respectively. The modifications carried out in the synthesis procedure have resulted in ir being possible to employ materials with different characteristics, such as mesoscopic ordering and textural properties, in applications in the areas of catalysis and adsorption. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Nickel Complexes Immobilized in Modified Ionic Liquids Anchored in Structured Materials for Ethylene Oligomerization
Appl. Sci. 2018, 8(5), 717; https://doi.org/10.3390/app8050717
Received: 21 March 2018 / Revised: 23 April 2018 / Accepted: 24 April 2018 / Published: 4 May 2018
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Abstract
This work describes the study of ethylene oligomerization reactions catalyzed by nickel-β-diimine complexes immobilized on β-zeolite, [Si]-MCM-41 (Mobil Composition of Matter 41) and [Si,Al]-MCM-41 modified with an ionic liquid. XRD and N2 adsorption and desorption analyses were used to characterize the modified
[...] Read more.
This work describes the study of ethylene oligomerization reactions catalyzed by nickel-β-diimine complexes immobilized on β-zeolite, [Si]-MCM-41 (Mobil Composition of Matter 41) and [Si,Al]-MCM-41 modified with an ionic liquid. XRD and N2 adsorption and desorption analyses were used to characterize the modified supports—namely, IL-Zeoβ, IL-MCM-41 and IL-Al-MCM-41—and the data showed that material organization remained intact even after incorporation of ionic liquid. N2 adsorption and desorption analyses suggested that ionic liquid can be confined in pores of support materials. Catalytic properties of synthesized materials were tested under different conditions. The following parameters were varied: Al/Ni molar ratio, temperature, pressure and catalyst loading. The homogeneous catalysts were more active but less selective in ethylene oligomerization, relative to heterogeneous ones, which can be attributed to the effect of confinement suffered by catalyst within channels of the support materials. NiIL-Zeoβ complexes were active, with activities greater than 23 s−1 and selectivities higher than 80% for butenes, including more than 85% of 1-butene. On the other hand, the NiIL-MCM-41 system was less active than NiIL-Zeoβ complexes, with activities above 1 s−1 with 100% selectivity for butenes (96% in 1-butene). NiIL-Al-MCM-41 system was more active than NiIL-MCM-41 system and showed an activity of 2.3 s−1 with 90% selectivity in 1-butenes. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Synthesis of Zeolite A from Metakaolin and Its Application in the Adsorption of Cationic Dyes
Appl. Sci. 2018, 8(4), 608; https://doi.org/10.3390/app8040608
Received: 19 March 2018 / Revised: 5 April 2018 / Accepted: 9 April 2018 / Published: 11 April 2018
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Abstract
The present work reports the synthesis of zeolites from two metakaolins, one derived from the white kaolin and the other derived from the red kaolin, found in a deposit in the city of São Simão (Brazil). The metakaolins were prepared by calcination of
[...] Read more.
The present work reports the synthesis of zeolites from two metakaolins, one derived from the white kaolin and the other derived from the red kaolin, found in a deposit in the city of São Simão (Brazil). The metakaolins were prepared by calcination of the kaolins at 600 °C; zeolite A was obtained after alkali treatment of the metakaolins with NaOH. The resulting solids were characterized by powder X-ray diffraction, thermal analysis, scanning electron microscopy, and nitrogen adsorption/desorption at −196 °C, which confirmed formation of zeolite A. The zeolites were applied as adsorbents to remove methylene blue, safranine, and malachite green from aqueous solutions. The zeolites displayed high adsorption capacity within short times (between one and five minutes); qt was 0.96 mg/g. The equilibrium study showed that the zeolites had higher adsorption capacity for malachite green (qe = 55.00 mg/g) than for the other two cationic dyes, and that the Langmuir isotherm was the model that best explained the adsorption mechanism. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessFeature PaperArticle Separation of Light Liquid Paraffin C5–C9 with Cuban Volcanic Glass Previously Used in Copper Elimination from Water Solutions
Appl. Sci. 2018, 8(2), 295; https://doi.org/10.3390/app8020295
Received: 10 January 2018 / Revised: 2 February 2018 / Accepted: 13 February 2018 / Published: 17 February 2018
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Abstract
Featured Application: In this work, an inexpensive and available material, as volcanic glass, is used to absorb metals from wastewater and then it is used to the separation of light liquid-olefins.

Abstract
: Raw porous volcanic glass from Cuba was used as an
[...] Read more.
Featured Application: In this work, an inexpensive and available material, as volcanic glass, is used to absorb metals from wastewater and then it is used to the separation of light liquid-olefins.

Abstract
: Raw porous volcanic glass from Cuba was used as an adsorbent for Cu2+ removal from dyes after activation with an acid solution. After Cu2+ adsorption, it was also evaluated its capacity to separate n-paraffins from a mixture by inverse gas chromatography (IGC), and the results were compared with those obtained with bare volcanic glass without copper. The main goal of this work is to highlight the great applicability of natural volcanic glass, which can be reused without pretreatment as an adsorbent. The results from copper adsorption were quite promising, considering the availability and low cost of this material; the sample without acid treatment turned out to be the most adequate to remove copper. Moreover, the results from IGC revealed that the separation of paraffins from the mixture was achieved with both bare volcanic glass and glass containing Cu, although greater heat adsorption values were obtained when copper was present in the sample due to the stronger interaction between paraffin and copper. The high availability and low cost of this porous material make it a potential and attractive candidate to be used in both heavy metal removal and paraffin separation for industrial purposes. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Open AccessArticle Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74
Appl. Sci. 2018, 8(2), 270; https://doi.org/10.3390/app8020270
Received: 5 January 2018 / Revised: 31 January 2018 / Accepted: 1 February 2018 / Published: 12 February 2018
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Abstract
The confined porous environment of metal organic frameworks (MOFs) is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an
[...] Read more.
The confined porous environment of metal organic frameworks (MOFs) is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an example of an important reaction, we study here the dissociation of water—which plays a critical role in biology, chemistry, and materials science—in MOFs and show how the knowledge of the structure in this confined environment allows for an unprecedented level of understanding and control. In particular, combining in-situ infrared spectroscopy and first-principles calculations, we show that the water dissociation reaction can be selectively controlled inside Zn-MOF-74 by alcohol, through both chemical and physical interactions. Methanol is observed to speed up water dissociation by 25% to 100%, depending on the alcohol partial pressure. On the other hand, co-adsorption of isopropanol reduces the speed of the water reaction, due mostly to steric interactions. In addition, we also investigate the stability of the product state after the water dissociation has occurred and find that the presence of additional water significantly stabilizes the dissociated state. Our results show that precise control of reactions within nano-porous materials is possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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Review

Jump to: Research

Open AccessReview Lamellar MWW-Type Zeolites: Toward Elegant Nanoporous Materials
Appl. Sci. 2018, 8(9), 1636; https://doi.org/10.3390/app8091636
Received: 11 July 2018 / Revised: 31 July 2018 / Accepted: 7 August 2018 / Published: 13 September 2018
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Abstract
This article provides an overview of nanoporous materials with MWW (Mobil twenty two) topology. It covers aspects of the synthesis of the MWW precursor and the tridimensional zeolite MCM-22 (Mobil Composition of Matter number 22) as well as their physicochemical properties, such as
[...] Read more.
This article provides an overview of nanoporous materials with MWW (Mobil twenty two) topology. It covers aspects of the synthesis of the MWW precursor and the tridimensional zeolite MCM-22 (Mobil Composition of Matter number 22) as well as their physicochemical properties, such as the Si/Al molar ratio, acidity, and morphology. In addition, it discusses the use of directing agents (SDAs) to obtain the different MWW-type materials reported so far. The traditional post-synthesis modifications to obtain MWW-type materials with hierarchical architectures, such as expanded, swelling, pillaring, and delaminating structures, are shown together with recent routes to obtain materials with more open structures. New routes for the direct synthesis of MWW-type materials with hierarchical pore architecture are also covered. Full article
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
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