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Porous Materials - Something Old, Something New
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Porous Materials - Something Old, Something New

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

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 16989

Special Issue Editor

Prof. Dr. Peizhou Li

E-Mail Website
Guest Editor
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
Interests: metal-organic frameworks; covalent organic frameworks; CO2 fixation; proton conduction; photocatalysts; nanocatalysts

Special Issue Information

Dear Colleagues,

Beside the traditional porous carbons, molecular sieves or zeolites, mesoporous silicas, porous metals or metal oxides, and porous organic polymers, recently, metal-organic frameworks (MOFs) and covalent organic framework (COFs), as well as hydrogen-bond organic frameworks (HOFs), have emerged as novel groups of porous materials. Regardless of whether they are amorphous or crystalline, whether they are microporous, mesoporous, or microporous, owing to their high surface area, low density, diverse structures, and fascinating physical and chemical properties derived from their components, various porous materials have been developed and used as functional materials in a wide range of fundamental research and industrial applications. These include the adsorption and separation of gases or light hydrocarbons, heterogeneous catalysts or catalytic supports, photoresponsive devices or chemical sensors, drug carriers for cancer therapy, photodynamic therapy, and so on. Whether they are inorganic, organic, or organic-inorganic hybrid materials, whether they are old or new, as we celebrate the 25th Anniversary of MDPI, we are launching this Special Issue, “Porous Materials—Something Old, Something New” to collect research on all kinds of porous materials, including their syntheses, structures, morphologies, and applications.

Prof. Dr. Peizhou Li
Guest Editor

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Keywords

  • porous carbons
  • molecular sieves and zeolites
  • mesoporous silicas
  • porous metal and metal oxides
  • porous organic polymers
  • metal-organic frameworks
  • covalent organic frameworks
  • hydrogen-bond organic frameworks

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Published Papers (7 papers)

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Research

14 pages, 5016 KiB  
Article
A Zn(II)–Metal–Organic Framework Based on 4-(4-Carboxy phenoxy) Phthalate Acid as Luminescent Sensor for Detection of Acetone and Tetracycline
by Nairong Wang, Shanshan Li, Zhenhua Li, Yuanyuan Gong and Xia Li
Molecules 2023, 28(3), 999; https://doi.org/10.3390/molecules28030999 - 19 Jan 2023
Cited by 5 | Viewed by 2013
Abstract
As hazardous environmental pollutants, residual tetracycline (TC) and acetone are harmful to the ecosystem. Therefore, it is necessary to detect the presence of these pollutants in the environment. In this work, using Zn (II) salt, 4-(4-carboxy phenoxy) phthalic acid (H3L), and [...] Read more.
As hazardous environmental pollutants, residual tetracycline (TC) and acetone are harmful to the ecosystem. Therefore, it is necessary to detect the presence of these pollutants in the environment. In this work, using Zn (II) salt, 4-(4-carboxy phenoxy) phthalic acid (H3L), and 3,5-bis(1-imidazolyl) pyridine (BMP), a new metal–organic framework (Zn-MOF) known as [Zn3(BMP)2L2(H2O)4]·2H2O was synthesized using a one-pot hydrothermal method. The Zn-MOF has a three-dimensional framework based on the [Zn1N2O2] and [Zn2N2O4] nodes linked by a tridentate bridge BMP ligand and an L ligand with the μ1:η1η0/μ1:η1η0/μ0:η0η0 coordination mode. There were two kinds of left- and right-handed helix chains, Zn1-BMP and Zn1-BMP-Zn1-L. The complex was stable in aqueous solutions with pH values of 4–10. The Zn-MOF exhibited a strong emission band centered at 385 nm owing to the π*→π electron transition of the ligand. It showed high luminescence in some common organic solvents as well as in the aqueous solutions of pH 4–10. Interestingly, TC and acetone effectively quenched the luminescence of the Zn-MOF in aqueous solution and enabled the Zn-MOF to be used as a sensor to detect TC and acetone. The detection limits of TC and acetone were observed to be 3.34 µM and 0.1597%, respectively. Even in acidic (pH = 4) and alkaline (pH = 10) conditions, the Zn-MOF showed a stable luminescence sensing capability to detect TC. Luminescence sensing of the Zn-MOF for TC in urine and aquaculture wastewater systems was not affected by the interfering agent. Furthermore, the mechanism of sensing TC was investigated in this study. Fluorescence resonance energy transfer and photoinduced electron transfer were found to be the possible quenching mechanisms via UV–Vis absorption spectra/the excitation spectra measurements and DFT calculations. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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10 pages, 3528 KiB  
Article
Photodynamic Inactivation of Bacteria and Biofilms with Benzoselenadiazole-Doped Metal-Organic Frameworks
by Liang Luan, Lehan Du, Wenjun Shi, Yunhui Li and Quan Zhang
Molecules 2022, 27(24), 8908; https://doi.org/10.3390/molecules27248908 - 14 Dec 2022
Cited by 6 | Viewed by 1942
Abstract
Bacterial biofilms are difficult to treat due to their resistance to traditional antibiotics. Although photodynamic therapy (PDT) has made significant progress in biomedical applications, most photosensitizers have poor water solubility and can thus aggregate in hydrophilic environments, leading to the quenching of photosensitizing [...] Read more.
Bacterial biofilms are difficult to treat due to their resistance to traditional antibiotics. Although photodynamic therapy (PDT) has made significant progress in biomedical applications, most photosensitizers have poor water solubility and can thus aggregate in hydrophilic environments, leading to the quenching of photosensitizing activity in PDT. Herein, a benzoselenadiazole-containing ligand was designed and synthesized to construct the zirconium (IV)-based benzoselenadiazole-doped metal-organic framework (Se-MOF). Characterizations revealed that Se-MOF is a type of UiO-68 topological framework with regular crystallinity and high porosity. Compared to the MOF without benzoselenadiazole, Se-MOF exhibited a higher 1O2 generation efficacy and could effectively kill Staphylococcus aureus bacteria under visible-light irradiation. Importantly, in vitro biofilm experiments confirmed that Se-MOF could efficiently inhibit the formation of bacteria biofilms upon visible-light exposure. This study provides a promising strategy for developing MOF-based PDT agents, facilitating their transformation into clinical photodynamic antibacterial applications. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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18 pages, 5079 KiB  
Article
Improved Metal Cation Optosensing Membranes through the Incorporation of Sulphated Polysaccharides
by P. R. M. Santos, A. Johny, C. Q. Silva, M. A. Azenha, J. A. Vázquez, J. Valcarcel, C. M. Pereira and A. F. Silva
Molecules 2022, 27(15), 5026; https://doi.org/10.3390/molecules27155026 - 7 Aug 2022
Cited by 2 | Viewed by 1787
Abstract
Optosensing chitosan-based membranes have been applied for the detection of heavy metals, especially in drinking water. The novelty of this study is based on the use of sulphated polysaccharides, in such optosensing membranes, aiming at an improved analytical performance. The sulphated polysaccharides, such [...] Read more.
Optosensing chitosan-based membranes have been applied for the detection of heavy metals, especially in drinking water. The novelty of this study is based on the use of sulphated polysaccharides, in such optosensing membranes, aiming at an improved analytical performance. The sulphated polysaccharides, such as ulvan, fucoidan and chondroitin sulfate, were extracted from by-products and wastes of marine-related activities. The membranes were developed for the analysis of aluminum. The variation in the visible absorbance of the sensor membranes after the contact between the chromophore and the aluminum cation was studied. The membranes containing sulphated polysaccharides showed improved signals when compared to the chitosan-only membrane. As for the detection limits for the membranes containing ulvan, fucoidan and chondroitin sulfate, 0.17 mg L−1, 0.21 mg L−1 and 0.36 mg L−1 were obtained, respectively. The values were much lower than that obtained for the chitosan-only membrane, 0.52 mg L−1, which shows the improvement obtained from the sulphated polysaccharides. The results were obtained with the presence of CTAB in analysis solution, which forms a ternary complex with the aluminum cation and the chromophore. This resulted in an hyperchromic and batochromic shift in the absorption band. When in the presence of this surfactant, the membranes showed lower detection limits and higher selectivity. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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11 pages, 2268 KiB  
Article
Highly Effective Proton-Conduction Matrix-Mixed Membrane Derived from an -SO3H Functionalized Polyamide
by Jamal Afzal, Yaomei Fu, Tian-Xiang Luan, Zhongmin Su and Pei-Zhou Li
Molecules 2022, 27(13), 4110; https://doi.org/10.3390/molecules27134110 - 26 Jun 2022
Cited by 4 | Viewed by 2142
Abstract
Developing a low-cost and effective proton-conductive electrolyte to meet the requirements of the large-scale manufacturing of proton exchange membrane (PEM) fuel cells is of great significance in progressing towards the upcoming “hydrogen economy” society. Herein, utilizing the one-pot acylation polymeric combination of acyl [...] Read more.
Developing a low-cost and effective proton-conductive electrolyte to meet the requirements of the large-scale manufacturing of proton exchange membrane (PEM) fuel cells is of great significance in progressing towards the upcoming “hydrogen economy” society. Herein, utilizing the one-pot acylation polymeric combination of acyl chloride and amine precursors, a polyamide with in-built -SO3H moieties (PA-PhSO3H) was facilely synthesized. Characterization shows that it possesses a porous feature and a high stability at the practical operating conditions of PEM fuel cells. Investigations of electrochemical impedance spectroscopy (EIS) measurements revealed that the fabricated PA-PhSO3H displays a proton conductivity of up to 8.85 × 10−2 S·cm−1 at 353 K under 98% relative humidity (RH), which is more than two orders of magnitude higher than that of its -SO3H-free analogue, PA-Ph (6.30 × 10−4 S·cm−1), under the same conditions. Therefore, matrix-mixed membranes were fabricated by mixing with polyacrylonitrile (PAN) in different ratios, and the EIS analyses revealed that its proton conductivity can reach up to 4.90 × 10−2 S·cm−1 at 353 K and a 98% relative humidity (RH) when the weight ratio of PA-PhSO3H:PAN is 3:1 (labeled as PA-PhSO3H-PAN (3:1)), the value of which is even comparable with those of commercial-available electrolytes being used in PEM fuel cells. Additionally, continuous tests showed that PA-PhSO3H-PAN (3:1) possesses a long-life reusability. This work demonstrates, using the simple acylation reaction with the sulfonated module as precursor, that low-cost and highly effective proton-conductive electrolytes for PEM fuel cells can be facilely achieved. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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17 pages, 4754 KiB  
Article
Experimental Design Optimization of Acrylate—Tannin Photocurable Resins for 3D Printing of Bio-Based Porous Carbon Architectures
by Pauline Blyweert, Vincent Nicolas, Vanessa Fierro and Alain Celzard
Molecules 2022, 27(7), 2091; https://doi.org/10.3390/molecules27072091 - 24 Mar 2022
Cited by 10 | Viewed by 2373
Abstract
In this work, porous carbons were prepared by 3D printing formulations based on acrylate–tannin resins. As the properties of these carbons are highly dependent on the composition of the precursor, it is essential to understand this effect to optimise them for a given [...] Read more.
In this work, porous carbons were prepared by 3D printing formulations based on acrylate–tannin resins. As the properties of these carbons are highly dependent on the composition of the precursor, it is essential to understand this effect to optimise them for a given application. Thus, experimental design was applied, for the first time, to carbon 3D printing. Using a rationalised number of experiments suggested by a Scheffé mixture design, the experimental responses (the carbon yield, compressive strength, and Young’s modulus) were modelled and predicted as a function of the relative proportions of the three main resin ingredients (HDDA, PETA, and CN154CG). The results revealed that formulations containing a low proportion of HDDA and moderate amounts of PETA and CN154CG gave the best properties. Thereby, the optimised carbon structures had a compressive strength of over 5.2 MPa and a Young’s modulus of about 215 MPa. The reliability of the model was successfully validated through optimisation tests, proving the value of experimental design in developing customisable tannin-based porous carbons manufactured by stereolithography. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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11 pages, 1391 KiB  
Article
IR-Spectroscopic Study of Complex Formation of Nitrogen Oxides (NO, N2O) with Cationic Forms of Zeolites and the Reactivity of Adsorbed Species in CO and CH4 Oxidation
by Alexander L. Kustov and Leonid M. Kustov
Molecules 2022, 27(1), 55; https://doi.org/10.3390/molecules27010055 - 22 Dec 2021
Cited by 5 | Viewed by 2933
Abstract
The formation of complexes and disproportionation of nitrogen oxides (NO, N2O) on cationic forms of LTA, FAU, and MOR zeolites was investigated by diffuse-reflectance IR spectroscopy. N2O is adsorbed on the samples under study in the molecular form and [...] Read more.
The formation of complexes and disproportionation of nitrogen oxides (NO, N2O) on cationic forms of LTA, FAU, and MOR zeolites was investigated by diffuse-reflectance IR spectroscopy. N2O is adsorbed on the samples under study in the molecular form and the frequencies of the first overtone of the stretching vibrations ν10–2 and the combination bands of the stretching vibrations with other vibrational modes for N2O complexes with cationic sites in zeolites (ν30–1 + ν10–1, ν10–1 + δ0–2) are more significantly influenced by the nature of the zeolite. The presence of several IR bands in the region of 2400–2600 cm−1 (the ν10–1 + δ0–2 transitions) for different zeolite types was explained by the availability of different localization sites for cations in these zeolites. The frequencies in this region also depend on the nature of the cation (its charge and radius). The data can be explained by the specific geometry of the N2O complex formed, presumably two-point adsorption of N2O on a cation and a neighboring oxygen atom of the framework. Adsorption of CO or CH4 on the samples with preliminarily adsorbed N2O at 20–180 °C does not result in any oxidation of these molecules. NO+ and N2O3 species formed by disproportionation of NO are capable of oxidizing CO and CH4 molecules to CO2, whereas NOx is reduced simultaneously to N2 or N2O. The peculiarities in the behavior of cationic forms of different zeolites with respect to adsorbed nitrogen oxides determined by different density and localization of cations have been established. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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6 pages, 4133 KiB  
Communication
Robust Amino-Functionalized Mesoporous Silica Hollow Spheres Templated by CO2 Bubbles
by Hongjuan Wang, Xuefei Liu, Olena Saliy, Wei Hu and Jingui Wang
Molecules 2022, 27(1), 53; https://doi.org/10.3390/molecules27010053 - 22 Dec 2021
Cited by 16 | Viewed by 3058
Abstract
Hollow-structured mesoporous silica has wide applications in catalysis and drug delivery due to its high surface area, large hollow space, and short diffusion mesochannels. However, the synthesis of hollow structures usually requires sacrificial templates, leading to increased production costs and environmental problems. Here, [...] Read more.
Hollow-structured mesoporous silica has wide applications in catalysis and drug delivery due to its high surface area, large hollow space, and short diffusion mesochannels. However, the synthesis of hollow structures usually requires sacrificial templates, leading to increased production costs and environmental problems. Here, for the first time, amino-functionalized mesoporous silica hollow spheres were synthesized by using CO2 gaseous bubbles as templates. The assembly of anionic surfactants, co-structure directing agents, and inorganic silica precursors around CO2 bubbles formed the mesoporous silica shells. The hollow silica spheres, 200–400 nm in size with 20–30 nm spherical shell thickness, had abundant amine groups on the surface of the mesopores, indicating excellent applications for CO2 capture, Knoevenagel condensation reaction, and the controlled release of Drugs. Full article
(This article belongs to the Special Issue Porous Materials - Something Old, Something New)
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