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Development of Novel Porous Materials
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Development of Novel Porous Materials

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (30 November 2022) | Viewed by 49752

Special Issue Editor

Dr. Irina Savina

E-Mail Website
Guest Editor
Pharmacy and Biomolecular SciencesUniversity of Brighton, Brighton BN2 4GJ, UK
Interests: synthesis of functional porous polymer gels; hybrid polymer-inorganic and nanocomposite materials; smart polymer systems; biomaterials; drug delivery systems; nanoparticles; characterisation of soft porous materials; novel materials for contaminated water remediation
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Porous materials have always attracted considerable attention from scientists and engineers. Porosity has a considerable impact on the properties of materials, as it changes the materials’ physic-mechanical properties, and increases surface area, permeability, diffusion, and ligands accessibility, which are key parameters for many applications. Porous materials have the potential to address many global challenges in areas such as energy, the environment, and health. Polymer-based porous materials are of particular interest due to a variety of polymers with different properties and versatility related to the design of novel advanced materials. Energy storage and conversion; adsorption; separation; catalysis; and biomedical applications, such as drug delivery and tissue engineering, are just some examples of the current applications of the porous materials.

This Special Issue invites original papers and reviews reporting on recent progress in the development of novel porous polymer materials, with a particular focus on advances in the synthesis, characterization, and application of porous polymers in biomedical, biotechnological, and environmental areas. This Issue welcomes focused review articles that examine the state of the art, identify emerging trends, and suggest future directions for developing porous polymers.

Dr. Irina Savina
Guest Editor

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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 2700 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

  • Porous polymer
  • Porous material
  • Porosity characterization
  • Porous hydrogels
  • Polymer composites
  • Biomedical, biotechnological, and environmental applications

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Published Papers (11 papers)

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Research

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12 pages, 2712 KiB  
Article
Hierarchical Porous and Three-Dimensional MXene/SiO2 Hybrid Aerogel through a Sol-Gel Approach for Lithium–Sulfur Batteries
by Jianping Zhou, Ziyuan Pei, Zhuyin Sui, Ying Liang, Xiufeng Xu, Yongpeng Li, Yulin Li, Jingyi Qiu and Qi Chen
Molecules 2022, 27(20), 7073; https://doi.org/10.3390/molecules27207073 - 20 Oct 2022
Cited by 6 | Viewed by 2456
Abstract
A unique porous material, namely, MXene/SiO2 hybrid aerogel, with a high surface area, was prepared via sol-gel and freeze-drying methods. The hierarchical porous hybrid aerogel possesses a three-dimensional integrated network structure of SiO2 cross-link with two-dimensional MXene; it is used not [...] Read more.
A unique porous material, namely, MXene/SiO2 hybrid aerogel, with a high surface area, was prepared via sol-gel and freeze-drying methods. The hierarchical porous hybrid aerogel possesses a three-dimensional integrated network structure of SiO2 cross-link with two-dimensional MXene; it is used not only as a scaffold to prepare sulfur-based cathode material, but also as an efficient functional separator to block the polysulfides shuttle. MXene/SiO2 hybrid aerogel as sulfur carrier exhibits good electrochemical performance, such as high discharge capacities (1007 mAh g–1 at 0.1 C) and stable cycling performance (823 mA h g–1 over 200 cycles at 0.5 C). Furthermore, the battery assembled with hybrid aerogel-modified separator remains at 623 mA h g–1 over 200 cycles at 0.5 C based on the conductive porous framework and abundant functional groups in hybrid aerogel. This work might provide further impetus to explore other applications of MXene-based composite aerogel. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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17 pages, 3285 KiB  
Article
Synthetic Amphoteric Cryogels as an Antidote against Acute Heavy Metal Poisoning
by Alzhan Z. Baimenov, Ildar R. Fakhradiyev, Dmitriy A. Berillo, Timur Saliev, Sergey V. Mikhalovsky, Talgat S. Nurgozhin and Vassilis J. Inglezakis
Molecules 2021, 26(24), 7601; https://doi.org/10.3390/molecules26247601 - 15 Dec 2021
Cited by 3 | Viewed by 3163
Abstract
The effectiveness of an amphoteric cryogel (AAC) as an oral sorbent (enerosorbent) for the treatment of acute poisoning of small animals (rats) with heavy metals (HMs) was studied in in vivo experiments. The morphological structure of the cryogel was examined using scanning electron [...] Read more.
The effectiveness of an amphoteric cryogel (AAC) as an oral sorbent (enerosorbent) for the treatment of acute poisoning of small animals (rats) with heavy metals (HMs) was studied in in vivo experiments. The morphological structure of the cryogel was examined using scanning electron microscopy/energy-dispersive X-ray analysis and confocal microscopy. The use of the cryogel in the treatment of rats administered an LD50 dose of Cd(NO3)2, CsNO3, Sr(NO3)2, or HgCl2 in aqueous solution showed their high survival rate compared to the control group, which did not receive such treatment. The histological and chemical analysis of internal tissues and the biochemical analysis of the blood of the experimental animals showed the effectiveness of the cryogel in protecting the animals against the damaging effect of HMs on the organism comparable with unithiol, a chelating agent based on 2,3-dimercapto-1-propane sulfonic acid sodium salt (DMPS) approved for the treatment of acute poisoning with some heavy metals. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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11 pages, 3326 KiB  
Article
Highly Elastic Super-Macroporous Cryogels Fabricated by Thermally Induced Crosslinking of 2-Hydroxyethylcellulose with Citric Acid in Solid State
by Nadegda Bozova and Petar D. Petrov
Molecules 2021, 26(21), 6370; https://doi.org/10.3390/molecules26216370 - 21 Oct 2021
Cited by 5 | Viewed by 2310
Abstract
Biopolymer materials have been considered a “green” alternative to petroleum-based polymeric materials. Biopolymers cannot completely replace synthetic polymers, but their application should be extended as much as possible, exploiting the benefits of their low toxicity and biodegradability. This contribution describes a novel strategy [...] Read more.
Biopolymer materials have been considered a “green” alternative to petroleum-based polymeric materials. Biopolymers cannot completely replace synthetic polymers, but their application should be extended as much as possible, exploiting the benefits of their low toxicity and biodegradability. This contribution describes a novel strategy for the synthesis of super-macroporous 2-hydroxyethylcellulose (HEC) cryogels. The method involves cryogenic treatment of an aqueous solution of HEC and citric acid (CA), freeze drying, and thermally induced crosslinking of HEC macrochains by CA in a solid state. The effect of reaction temperature (70–180 °C) and CA concentration (5–20 mass % to HEC) on the reaction efficacy and physico-mechanical properties of materials was investigated. Highly elastic cryogels were fabricated, with crosslinking carried out at ≥100 °C. The storage modulus of the newly obtained HEC cryogels was ca. 20 times higher than the modulus of pure HEC cryogels prepared by photochemical crosslinking. HEC cryogels possess an open porous structure, as confirmed by scanning electron microscopy (SEM), and uptake a relatively large amount of water. The swelling degree varied between 17 and 40, depending on the experimental conditions. The degradability of HEC cryogels was demonstrated by acid hydrolysis experiments. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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11 pages, 2545 KiB  
Article
Formation of Copper Oxide Nanotextures on Porous Calcium Carbonate Templates for Water Treatment
by Mahmud Diab, Karam Shreteh, Michael Volokh and Taleb Mokari
Molecules 2021, 26(19), 6067; https://doi.org/10.3390/molecules26196067 - 7 Oct 2021
Cited by 4 | Viewed by 5096
Abstract
The necessity of providing clean water sources increases the demand to develop catalytic systems for water treatment. Good pollutants adsorbers are a key ingredient, and CuO is one of the candidate materials for this task. Among the different approaches for CuO synthesis, precipitation [...] Read more.
The necessity of providing clean water sources increases the demand to develop catalytic systems for water treatment. Good pollutants adsorbers are a key ingredient, and CuO is one of the candidate materials for this task. Among the different approaches for CuO synthesis, precipitation out of aqueous solutions is a leading candidate due to the facile synthesis, high yield, sustainability, and the reported shape control by adjustment of the counter anions. We harness this effect to investigate the formation of copper oxide-based 3D structures. Specifically, the counter anion (chloride, nitrate, and acetate) affects the formation of copper-based hydroxides and the final structure following their conversion into copper oxide nanostructures over porous templates. The formation of a 3D structure is obtained when copper chloride or nitrate reacts with a Sorites scaffold (marine-based calcium carbonate template) without external hydroxide addition. The transformation into copper oxides occurs after calcination or reduction of the obtained Cu2(OH)3X (X = Cl− or NO3−) while preserving the porous morphology. Finally, the formed Sorites@CuO structure is examined for water treatment to remove heavy metal cations and degrade organic contaminant molecules. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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14 pages, 5477 KiB  
Article
Composite Zn(II) Ferrocyanide/Polyethylenimine Cryogels for Point-of-Use Selective Removal of Cs-137 Radionuclides
by Irina Malakhova, Yuliya Parotkina, Marina Palamarchuk, Marina Eliseikina, Aleksandr Mironenko, Alexey Golikov and Svetlana Bratskaya
Molecules 2021, 26(15), 4604; https://doi.org/10.3390/molecules26154604 - 29 Jul 2021
Cited by 6 | Viewed by 2317
Abstract
The feasibility of several approaches to the fabrication of monolith composite cryogels containing transition-metal ferrocyanides for Cs+ ion uptake has been evaluated. Although in the series of investigated metal ion precursors (Cu(II), Zn(II), Ni(II), and Co(II)), in situ formation of the sorption [...] Read more.
The feasibility of several approaches to the fabrication of monolith composite cryogels containing transition-metal ferrocyanides for Cs+ ion uptake has been evaluated. Although in the series of investigated metal ion precursors (Cu(II), Zn(II), Ni(II), and Co(II)), in situ formation of the sorption active phase in polyethyleneimine (PEI) cryogel was feasible only in the case of Zn(II) ferrocyanide, this approach has shown significant advantages over the immobilization of ex situ synthesized ferrocyanide nanoparticles. Nanoparticles of the mixed ferrocyanide Zn1.85K0.33[Fe(CN)6] formed in situ had an average size of 516 ± 146 nm and were homogeneously distributed in the monolith located at the polymer surface rather than embedded in the matrix. The Young modulus of the PEI cryogel increased after modification from 25 to 57 kPa, but composites maintained high permeability to the flow. Sorption of Cs+ ions has been investigated at superficial velocity up to 8 m/h. Steep breakthrough profiles and uptake efficiency of >99.5% until breakthrough point confirmed that a supermacroporous structure of the monolith composite assured good mass transfer, so that intraparticle diffusion was not the limiting stage of sorption kinetics. Application of the rate-constant distribution model (RCD model) to analyze the breakthrough curves of Cs+ sorption allowed the identification of two types of sorption sites with a difference in sorption rate constants of ~1 log unit. Most likely, sorption on “fast” sorption sites was governed by ion exchange between Cs+ ions in solution and K+ ions in the ferrocyanide lattice. Cs-137 radionuclide removal was investigated using the monolith composite columns of various geometries at superficial velocity up to the 6.6 m/h; specific gamma activity was reduced from 265 kBq/L to the background level, showing high potential of these materials for POU application. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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25 pages, 3391 KiB  
Article
Hydrodechlorination of 4-Chlorophenol on Pd-Fe Catalysts on Mesoporous ZrO2SiO2 Support
by Ekaterina S. Lokteva, Vera V. Shishova, Nikolay N. Tolkachev, Andrey N. Kharlanov, Konstantin I. Maslakov, Alexey O. Kamaev, Igor Yu. Kaplin, Irina N. Savina and Elena V. Golubina
Molecules 2021, 26(1), 141; https://doi.org/10.3390/molecules26010141 - 30 Dec 2020
Cited by 8 | Viewed by 3280
Abstract
A mesoporous support based on silica and zirconia (ZS) was used to prepare monometallic 1 wt% Pd/ZS, 10 wt% Fe/ZS, and bimetallic FePd/ZS catalysts. The catalysts were characterized by TPR-H2, XRD, SEM-EDS, TEM, AAS, and DRIFT spectroscopy of adsorbed CO after [...] Read more.
A mesoporous support based on silica and zirconia (ZS) was used to prepare monometallic 1 wt% Pd/ZS, 10 wt% Fe/ZS, and bimetallic FePd/ZS catalysts. The catalysts were characterized by TPR-H2, XRD, SEM-EDS, TEM, AAS, and DRIFT spectroscopy of adsorbed CO after H2 reduction in situ and tested in hydrodechlorination of environmental pollutant 4-chlorophelol in aqueous solution at 30 °C. The bimetallic catalyst demonstrated an excellent activity, selectivity to phenol and stability in 10 consecutive runs. FePd/ZS has exceptional reducibility due to the high dispersion of palladium and strong interaction between FeOx and palladium, confirmed by TPR-H2, DRIFT spectroscopy, XRD, and TEM. Its reduction occurs during short-time treatment with hydrogen in an aqueous solution at RT. The Pd/ZS was more resistant to reduction but can be activated by aqueous phenol solution and H2. The study by DRIFT spectroscopy of CO adsorbed on Pd/ZS reduced in harsh (H2, 330 °C), medium (H2, 200 °C) and mild conditions (H2 + aqueous solution of phenol) helped to identify the reasons of the reducing action of phenol solution. It was found that phenol provided fast transformation of Pd+ to Pd0. Pd/ZS also can serve as an active and stable catalyst for 4-PhCl transformation to phenol after proper reduction. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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16 pages, 3836 KiB  
Article
Chemical Modifications of Porous Shape Memory Polymers for Enhanced X-ray and MRI Visibility
by Grace K. Fletcher, Landon D. Nash, Lance M. Graul, Lindy K. Jang, Scott M. Herting, Matthew D. Wilcox, Tyler J. Touchet, Ana Katarina Sweatt, Mary P. McDougall, Steven M. Wright and Duncan J. Maitland
Molecules 2020, 25(20), 4660; https://doi.org/10.3390/molecules25204660 - 13 Oct 2020
Cited by 2 | Viewed by 3122
Abstract
The goal of this work was to develop a shape memory polymer (SMP) foam with visibility under both X-ray and magnetic resonance imaging (MRI) modalities. A porous polymeric material with these properties is desirable in medical device development for applications requiring thermoresponsive tissue [...] Read more.
The goal of this work was to develop a shape memory polymer (SMP) foam with visibility under both X-ray and magnetic resonance imaging (MRI) modalities. A porous polymeric material with these properties is desirable in medical device development for applications requiring thermoresponsive tissue scaffolds with clinical imaging capabilities. Dual modality visibility was achieved by chemically incorporating monomers with X-ray visible iodine-motifs and MRI visible monomers with gadolinium content. Physical and thermomechanical characterization showed the effect of increased gadopentetic acid (GPA) on shape memory behavior. Multiple compositions showed brightening effects in pilot, T1-weighted MR imaging. There was a correlation between the polymeric density and X-ray visibility on expanded and compressed SMP foams. Additionally, extractions and indirect cytocompatibility studies were performed to address toxicity concerns of gadolinium-based contrast agents (GBCAs). This material platform has the potential to be used in a variety of medical devices. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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22 pages, 13977 KiB  
Article
Cryostructuring of Polymeric Systems †: Application of Deep Neural Networks for the Classification of Structural Features Peculiar to Macroporous Poly(vinyl alcohol) Cryogels Prepared without and with the Additives of Chaotropes or Kosmotropes
by Ilya I. Kurochkin, Ilya N. Kurochkin, Olga Yu. Kolosova and Vladimir I. Lozinsky
Molecules 2020, 25(19), 4480; https://doi.org/10.3390/molecules25194480 - 29 Sep 2020
Cited by 7 | Viewed by 4716
Abstract
Macroporous poly(vinyl alcohol) cryogels (PVACGs) are physical gels formed via cryogenic processing of polymer solutions. The properties of PVACGs depend on many factors: the characteristics and concentration of PVA, the absence or presence of foreign solutes, and the freezing-thawing conditions. These factors also [...] Read more.
Macroporous poly(vinyl alcohol) cryogels (PVACGs) are physical gels formed via cryogenic processing of polymer solutions. The properties of PVACGs depend on many factors: the characteristics and concentration of PVA, the absence or presence of foreign solutes, and the freezing-thawing conditions. These factors also affect the macroporous morphology of PVACGs, their total porosity, pore size and size distribution, etc. In this respect, there is the problem with developing a scientifically-grounded classification of the morphological features inherent in various PVACGs. In this study PVA cryogels have been prepared at different temperatures when the initial polymer solutions contained chaotropic or kosmotropic additives. After the completion of gelation, the rigidity and heat endurance of the resultant PVACGs were evaluated, and their macroporous structure was investigated using optical microscopy. The images obtained were treated mathematically, and deep neural networks were used for the classification of these images. Training and test sets were used for their classification. The results of this classification for the specific deep neural network architecture are presented, and the morphometric parameters of the macroporous structure are discussed. It was found that deep neural networks allow us to reliably classify the type of additive or its absence when using a combined dataset. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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11 pages, 5755 KiB  
Article
Porous V2O5/TiO2 Nanoheterostructure Films with Enhanced Visible-Light Photocatalytic Performance Prepared by the Sparking Method
by Porntipa Pooseekheaw, Winai Thongpan, Arisara Panthawan, Ekkapong Kantarak, Wattikon Sroila and Pisith Singjai
Molecules 2020, 25(15), 3327; https://doi.org/10.3390/molecules25153327 - 22 Jul 2020
Cited by 20 | Viewed by 3634
Abstract
Porous V2O5/TiO2 nanoheterostructure films with different atomic ratios of Ti/V (4:1, 2:1, 1:1, and 1:2) were synthesized by a sparking method for the first time. The sparking method, which is a simple and cost-effective process, can synthesize highly [...] Read more.
Porous V2O5/TiO2 nanoheterostructure films with different atomic ratios of Ti/V (4:1, 2:1, 1:1, and 1:2) were synthesized by a sparking method for the first time. The sparking method, which is a simple and cost-effective process, can synthesize highly porous and composite films in one step. Field-emission scanning electron microscope (FE-SEM) images revealed the porosity morphology of all prepared samples. V2O5/TiO2 nanoheterostructure films were confirmed by Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). The secondary particle size and band gap of the samples were highly correlated to the V2O5 proportion, resulting in enhanced visible-light absorbance. V2O5/TiO2 nanoheterostructure films at an atomic ratio of 1:1 showed the highest photocatalytic performance, which improved the degradation rate up to 24% compared to pure TiO2 film. It is believed that the formed nanoheterostructure and greater portion of V4+ ions are reflected by this ratio. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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Review

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38 pages, 6889 KiB  
Review
A Comprehensive Review on Adsorption, Photocatalytic and Chemical Degradation of Dyes and Nitro-Compounds over Different Kinds of Porous and Composite Materials
by Abdul Haleem, Anum Shafiq, Sheng-Qi Chen and Mudasir Nazar
Molecules 2023, 28(3), 1081; https://doi.org/10.3390/molecules28031081 - 21 Jan 2023
Cited by 160 | Viewed by 11226
Abstract
Dye and nitro-compound pollution has become a significant issue worldwide. The adsorption and degradation of dyes and nitro-compounds have recently become important areas of study. Different methods, such as precipitation, flocculation, ultra-filtration, ion exchange, coagulation, and electro-catalytic degradation have been adopted for the [...] Read more.
Dye and nitro-compound pollution has become a significant issue worldwide. The adsorption and degradation of dyes and nitro-compounds have recently become important areas of study. Different methods, such as precipitation, flocculation, ultra-filtration, ion exchange, coagulation, and electro-catalytic degradation have been adopted for the adsorption and degradation of these organic pollutants. Apart from these methods, adsorption, photocatalytic degradation, and chemical degradation are considered the most economical and efficient to control water pollution from dyes and nitro-compounds. In this review, different kinds of dyes and nitro-compounds, and their adverse effects on aquatic organisms and human beings, were summarized in depth. This review article covers the comprehensive analysis of the adsorption of dyes over different materials (porous polymer, carbon-based materials, clay-based materials, layer double hydroxides, metal-organic frameworks, and biosorbents). The mechanism and kinetics of dye adsorption were the central parts of this study. The structures of all the materials mentioned above were discussed, along with their main functional groups responsible for dye adsorption. Removal and degradation methods, such as adsorption, photocatalytic degradation, and chemical degradation of dyes and nitro-compounds were also the main aim of this review article, as well as the materials used for such degradation. The mechanisms of photocatalytic and chemical degradation were also explained comprehensively. Different factors responsible for adsorption, photocatalytic degradation, and chemical degradation were also highlighted. Advantages and disadvantages, as well as economic cost, were also discussed briefly. This review will be beneficial for the reader as it covers all aspects of dye adsorption and the degradation of dyes and nitro-compounds. Future aspects and shortcomings were also part of this review article. There are several review articles on all these topics, but such a comprehensive study has not been performed so far in the literature. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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34 pages, 3881 KiB  
Review
Template Synthesis of Porous Ceria-Based Catalysts for Environmental Application
by Igor Yu. Kaplin, Ekaterina S. Lokteva, Elena V. Golubina and Valery V. Lunin
Molecules 2020, 25(18), 4242; https://doi.org/10.3390/molecules25184242 - 16 Sep 2020
Cited by 44 | Viewed by 7077
Abstract
Porous oxide materials are widely used in environmental catalysis owing to their outstanding properties such as high specific surface area, enhanced mass transport and diffusion, and accessibility of active sites. Oxides of metals with variable oxidation state such as ceria and double oxides [...] Read more.
Porous oxide materials are widely used in environmental catalysis owing to their outstanding properties such as high specific surface area, enhanced mass transport and diffusion, and accessibility of active sites. Oxides of metals with variable oxidation state such as ceria and double oxides based on ceria also provide high oxygen storage capacity which is important in a huge number of oxidation processes. The outstanding progress in the development of hierarchically organized porous oxide catalysts relates to the use of template synthetic methods. Single and mixed oxides with enhanced porous structure can serve both as supports for the catalysts of different nature and active components for catalytic oxidation of volatile organic compounds, soot particles and other environmentally dangerous components of exhaust gases, in hydrocarbons reforming, water gas shift reaction and photocatalytic transformations. This review highlights the recent progress in synthetic strategies using different types of templates (artificial and biological, hard and soft), including combined ones, in the preparation of single and mixed oxide catalysts based on ceria, and provides examples of their application in the main areas of environmental catalysis. Full article
(This article belongs to the Special Issue Development of Novel Porous Materials)
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