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Advanced Crystalline Porous Material and Engineering for Separation and Catalysis Application

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

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 25896

Special Issue Editors


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Guest Editor
College of Science, China University of Petroleum (Beijing), Changping District, Beijing 102249, China
Interests: crystal; MOFs; cage; separation; catalysis

E-Mail Website
Guest Editor
College of Science, China University of Petroleum (Beijing), Changping District, Beijing 102249, China
Interests: zeolite; MOFs; catalysis; Olefin polymerization; H2 storage

Special Issue Information

Dear Colleagues,

Crystalline porous materials, as periodic network structures, exhibit excellent properties in separation and catalysis aspects, contributing to their outstanding characteristics such as high specific surface area, flexibility, adjustability, and visual structure, etc. Since the late 1950s, zeolite as a subclass of these materials has aroused extensive research interest in industry and academia, which is widely used in industrial catalysis, separation. Moreover, in the last two decades, other kinds of crystalline porous metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), hydrogen–organic frameworks (HOFs), and Cages have emerged generated interest for their potential use in catalysis and gas separation or storage. At present, the vigorous development of crystalline porous materials is obvious to all, and many groundbreaking and disruptive achievements have been made in both structure-controlled synthesis and function-oriented research. In order to summarize and display the latest research results to further promote the development of crystalline porous materials, this Special Issue aims to collect original high-quality articles that explore the full potential of crystalline porous materials for a wide range of applications related to catalysis and separation. Fundamental and applied research covering multidisciplinary topics as well as review papers with new perspectives will be considered. The scope of the Special Issue includes, but is not limited to, the following topics:

  • Inorganic crystalline porous materials (Zeolite);
  • Organic crystalline porous materials (COFs, HOFs);
  • Organic and inorganic hybrid crystalline porous materials (MOFs);
  • Crystalline porous materials for gas separation and sensor application;
  • Crystalline porous materials for catalysis application;
  • Crystalline porous materials for carbon neutrality;
  • Crystalline porous materials for sustainable water treatment.
  • Simulation and modeling;
  • Novel Crystalline porous materials development;
  • Mathematical modeling, systems analysis, machine learning, and beneficial use of big data;
  • Socio economic, policy, and regulations studies.

Dr. Yun-Lei Peng 
Prof. Dr. Ying Zhang
Guest Editors

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Keywords

  • crystal
  • porous material
  • MOFs
  • COFs
  • HOFs
  • cages
  • separation
  • catalysis

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Published Papers (10 papers)

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Research

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13 pages, 65714 KiB  
Article
Application of a Mixed-Ligand Metal–Organic Framework in Photocatalytic CO2 Reduction, Antibacterial Activity and Dye Adsorption
by Hongwei Jing, Lun Zhao, Guanying Song, Jiayu Li, Ziyun Wang, Yue Han and Zhexin Wang
Molecules 2023, 28(13), 5204; https://doi.org/10.3390/molecules28135204 - 4 Jul 2023
Cited by 7 | Viewed by 1267
Abstract
In this paper, a known mixed-ligand MOF {[Co2(TZMB)2(1,4-bib)0.5(H2O)2]·(H2O)2}n (compound 1) was reproduced, and its potential application potential was explored. It was found that compound 1 had high [...] Read more.
In this paper, a known mixed-ligand MOF {[Co2(TZMB)2(1,4-bib)0.5(H2O)2]·(H2O)2}n (compound 1) was reproduced, and its potential application potential was explored. It was found that compound 1 had high photocatalytic activity for CO2 reduction. After 12 h of illumination, the formation rate of CO, which is the product of CO2 reduction by compound 1, reached 3012.5 μmol/g/h. At the same time, compound 1 has a good antibacterial effect on Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Candida albicans (C. albicans), which has potential research value in the medical field. In addition, compound 1 can effectively remove Congo Red from aqueous solutions and achieve the separation of Congo red from mixed dye solutions. Full article
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9 pages, 2834 KiB  
Communication
A Porous π-Stacked Self-Assembly of Cup-Shaped Palladium Complex for Iodine Capture
by Lin-Lin Li, Min Huang, Ting Chen, Xiao-Feng Xu, Zhu Zhuo, Wei Wang and You-Gui Huang
Molecules 2023, 28(7), 2881; https://doi.org/10.3390/molecules28072881 - 23 Mar 2023
Cited by 5 | Viewed by 1630
Abstract
Acquiring adsorbents capable of effective radioiodine capture is important for nuclear waste treatment; however, it remains a challenge to develop porous materials with high and reversible iodine capture. Herein, we report a porous self-assembly constructed by a cup-shaped PdII complex through intermolecular [...] Read more.
Acquiring adsorbents capable of effective radioiodine capture is important for nuclear waste treatment; however, it remains a challenge to develop porous materials with high and reversible iodine capture. Herein, we report a porous self-assembly constructed by a cup-shaped PdII complex through intermolecular π···π interactions. This self-assembly features a cubic structure with channels along all three Cartesian coordinates, which enables it to efficiently capture iodine with an adsorption capacity of 0.60 g g−1 for dissolved iodine and 1.81 g g−1 for iodine vapor. Furthermore, the iodine adsorbed within the channels can be readily released upon immersing the bound solid in CH2Cl2, which allows the recycling of the adsorbent. This work develops a new porous molecular material promising for practical iodine adsorption. Full article
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11 pages, 2175 KiB  
Article
Customizing Pore System in a Microporous Metal–Organic Framework for Efficient C2H2 Separation from CO2 and C2H4
by Qiang Zhang, Guan-Nan Han, Xin Lian, Shan-Qing Yang and Tong-Liang Hu
Molecules 2022, 27(18), 5929; https://doi.org/10.3390/molecules27185929 - 12 Sep 2022
Cited by 8 | Viewed by 4451
Abstract
Selective-adsorption separation is an energy-efficient technology for the capture of acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4). However, it remains a critical challenge to effectively recognize C2H2 among [...] Read more.
Selective-adsorption separation is an energy-efficient technology for the capture of acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4). However, it remains a critical challenge to effectively recognize C2H2 among CO2 and C2H4, owing to their analogous molecule sizes and physical properties. Herein, we report a new microporous metal–organic framework (NUM-14) possessing a carefully tailored pore system containing moderate pore size and nitro-functionalized channel surface for efficient separation of C2H2 from CO2 and C2H4. The activated NUM-14 (namely NUM-14a) exhibits sufficient pore space to acquire excellent C2H2 loading capacity (4.44 mmol g−1) under ambient conditions. In addition, it possesses dense nitro groups, acting as hydrogen bond acceptors, to selectively identify C2H2 molecules rather than CO2 and C2H4. The breakthrough experiments demonstrate the good actual separation ability of NUM-14a for C2H2/CO2 and C2H2/C2H4 mixtures. Furthermore, Grand Canonical Monte Carlo simulations indicate that the pore surface of the NUM-14a has a stronger affinity to preferentially bind C2H2 over CO2 and C2H4 via stronger C-H···O hydrogen bond interactions. This article provides some insights into customizing pore systems with desirable pore sizes and modifying groups in terms of MOF materials toward the capture of C2H2 from CO2 and C2H4 to promote the development of more MOF materials with excellent properties for gas adsorption and separation. Full article
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19 pages, 7446 KiB  
Article
Synthesis of [B,Al]-EWT-Type Zeolite and Its Catalytic Properties
by Youju Wang, Yongyue Bai, Pohua Chen, Qiang Chen, Yongrui Wang and Xingtian Shu
Molecules 2022, 27(17), 5625; https://doi.org/10.3390/molecules27175625 - 31 Aug 2022
Cited by 1 | Viewed by 2106
Abstract
EWT zeolite belongs to ultra-large pore zeolite with the 10MR and 21MR channels, which has good thermal stability, certain acid strength and good application prospects in petroleum refining and petrochemical reactions. However, EWT zeolite has fewer medium/strong acid sites, especially Brönsted acid sites, [...] Read more.
EWT zeolite belongs to ultra-large pore zeolite with the 10MR and 21MR channels, which has good thermal stability, certain acid strength and good application prospects in petroleum refining and petrochemical reactions. However, EWT zeolite has fewer medium/strong acid sites, especially Brönsted acid sites, which makes it difficult to apply to acid-catalyzed reactions. The regulation of acid amount and distribution was achieved by boron and aluminum substitution into the siliceous framework of EWT. The physico-chemical properties of the samples were characterized by XRD, SEM, N2 adsorption-desorption, XRF, ICP, Py-IR, NH3-TPD and 11B & 27Al & 29Si MAS NMR. The results show that quantities of boron and aluminum elements can occupy the framework of [B,Al]-EWT to increase the density of medium and strong acid centers, with more acidity and Brönsted acid centers than EWT zeolite. In the reaction of glycerol with cyclohexanone, the conversion of the sample (U-90-08-10/U-90-H-HCl) is significantly higher than that of the EWT sample, approaching or exceeding the Beta zeolite. A catalytic activity study revealed a direct correlation between the Brönsted acidic site concentration and the activity of the catalyst. The U-90-08-10-H catalyst was also considerably stable in the catalytic process. This work shows, for the first time, that extra-large pore zeolites can be used in industrial acid-catalytic conversion processes with excellent catalytic performance. Full article
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12 pages, 1923 KiB  
Article
CO2 Capture from High-Humidity Flue Gas Using a Stable Metal–Organic Framework
by Qi Wang, Yang Chen, Puxu Liu, Yi Wang, Jiangfeng Yang, Jinping Li and Libo Li
Molecules 2022, 27(17), 5608; https://doi.org/10.3390/molecules27175608 - 31 Aug 2022
Cited by 13 | Viewed by 2794
Abstract
The flue gas from fossil fuel power plants is a long-term stable and concentrated emission source of CO2, and it is imperative to reduce its emission. Adsorbents have played a pivotal role in reducing CO2 emissions in recent years, but [...] Read more.
The flue gas from fossil fuel power plants is a long-term stable and concentrated emission source of CO2, and it is imperative to reduce its emission. Adsorbents have played a pivotal role in reducing CO2 emissions in recent years, but the presence of water vapor in flue gas poses a challenge to the stability of adsorbents. In this study, ZIF-94, one of the ZIF adsorbents, showed good CO2 uptake (53.30 cm3/g), and the calculated CO2/N2 (15:85, v/v) selectivity was 54.12 at 298 K. Because of its excellent structural and performance stability under humid conditions, the CO2/N2 mixture was still well-separated on ZIF-94 with a separation time of 30.4 min when the relative humidity was as high as 99.2%, which was similar to the separation time of the dry gas experiments (33.2 min). These results pointed to the enormous potential applications of ZIF-94 for CO2/N2 separation under high humidity conditions in industrial settings. Full article
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12 pages, 3057 KiB  
Article
Extraction of Uranium in Nitric Media with Novel Asymmetric Tetra-Alkylcarbamide
by Qi Chen, Baole Li, Junli Wang, Haowei Zhu, Xiwen Chen, Yifu Hu, Jia Zhou, Xiang Li, Weifang Zheng and Taihong Yan
Molecules 2022, 27(17), 5527; https://doi.org/10.3390/molecules27175527 - 27 Aug 2022
Cited by 3 | Viewed by 1649
Abstract
The use of tetra-alkylcarbamides as novel ligands: N,N-butyl-N’,N’-hexylurea (L1: ABHU), and N,N-butyl-N’,N’-pentylurea (L2: ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO3 and NO [...] Read more.
The use of tetra-alkylcarbamides as novel ligands: N,N-butyl-N’,N’-hexylurea (L1: ABHU), and N,N-butyl-N’,N’-pentylurea (L2: ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO3 and NO3 concentrations in the aqueous phase on the distribution ratio of U(VI) were examined. Under 5 mol/L HNO3 concentration, DU reached 5.02 and 4.94 respectively without third-phase formation. During the extraction, slope measurements and IR spectral analysis revealed that the U(VI) complexes are a form of UO2(NO3)2·2L for both ligands. In addition, thermodynamic studies showed that the uranium extraction reaction was a spontaneous exothermic reaction. The deep structural analysis of the complexes was realized with DFT calculation. The bond length, bond properties, and topology of the complexes were discussed in detail to analyze the extraction behavior. This study enriches the coordination chemistry of U(VI) by tetra-alkylcarbamides, which may offer new clues for the design and synthesis of novel ligands for the separation, enrichment, and recovery of uranium in the nuclear fuel cycle. Full article
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15 pages, 3812 KiB  
Article
Facile Fabrication of 1-Methylimidazole/Cu Nanozyme with Enhanced Laccase Activity for Fast Degradation and Sensitive Detection of Phenol Compounds
by Yu Lei, Bin He, Shujun Huang, Xinyan Chen and Jian Sun
Molecules 2022, 27(15), 4712; https://doi.org/10.3390/molecules27154712 - 23 Jul 2022
Cited by 16 | Viewed by 2936
Abstract
Facile construction of functional nanomaterials with laccase-like activity is important in sustainable chemistry since laccase is featured as an efficient and promising catalyst especially for phenolic degradation but still has the challenges of high cost, low activity, poor stability and unsatisfied recyclability. In [...] Read more.
Facile construction of functional nanomaterials with laccase-like activity is important in sustainable chemistry since laccase is featured as an efficient and promising catalyst especially for phenolic degradation but still has the challenges of high cost, low activity, poor stability and unsatisfied recyclability. In this paper, we report a simple method to synthesize nanozymes with enhanced laccase-like activity by the self-assembly of copper ions with various imidazole derivatives. In the case of 1-methylimidazole as the ligand, the as-synthesized nanozyme (denoted as Cu-MIM) has the highest yield and best activity among the nanozymes prepared. Compared to laccase, the Km of Cu-MIM nanozyme to phenol is much lower, and the vmax is 6.8 times higher. In addition, Cu-MIM maintains excellent stability in a variety of harsh environments, such as high pH, high temperature, high salt concentration, organic solvents and long-term storage. Based on the Cu-MIM nanozyme, we established a method for quantitatively detecting phenol concentration through a smartphone, which is believed to have important applications in environmental protection, pollutant detection and other fields. Full article
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13 pages, 3547 KiB  
Article
Highly Effective Removal of Ofloxacin from Water with Copper-Doped ZIF-8
by Xiaowei Wang, Yingjie Zhao, Yiqi Sun and Dahuan Liu
Molecules 2022, 27(13), 4312; https://doi.org/10.3390/molecules27134312 - 5 Jul 2022
Cited by 8 | Viewed by 2785
Abstract
Residual antibiotics in wastewater have gained widespread attention because of their toxicity to humans and the environment. In this work, Cu-doped ZIF-8s (Cu-ZIF-8s) were successfully synthesized by the impregnation of Cu2+ in ZIF-8 and applied in the removal of ofloxacin (OFX) from [...] Read more.
Residual antibiotics in wastewater have gained widespread attention because of their toxicity to humans and the environment. In this work, Cu-doped ZIF-8s (Cu-ZIF-8s) were successfully synthesized by the impregnation of Cu2+ in ZIF-8 and applied in the removal of ofloxacin (OFX) from water. Remarkably, excellent adsorption performance was obtained in Cu-ZIF-8s, especially for Cu-ZIF-8-1, in which the adsorption capacity (599.96 mg·g−1) was 4.2 times higher than that of ZIF-8 and superior to various adsorbents reported previously. The adsorption kinetics and adsorption isotherm follow the pseudo-second-order model and the Langmuir model, respectively. Furthermore, the removal efficiencies of OFX in Cu-ZIF-8-1 reached over 90% at low concentrations. It was revealed that electrostatic interaction and complexation play important roles in the adsorption process. In addition, the material can be regenerated by simple methods. Therefore, the obtained Cu-doped MOFs may have a promising application in the treatment of antibiotic-containing wastewater. Full article
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Review

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24 pages, 9141 KiB  
Review
Advancements of MOFs in the Field of Propane Oxidative Dehydrogenation for Propylene Production
by Shu-Ting Li, Ming Ke, Jie Zhang, Yun-Lei Peng and Guangjin Chen
Molecules 2024, 29(6), 1212; https://doi.org/10.3390/molecules29061212 - 8 Mar 2024
Viewed by 1527
Abstract
Compared to the currently widely used propane dehydrogenation process for propylene production, propane oxidative dehydrogenation (ODHP) offers the advantage of no thermodynamic limitations and lower energy consumption. However, a major challenge in ODHP is the occurrence of undesired over-oxidation reactions of propylene, which [...] Read more.
Compared to the currently widely used propane dehydrogenation process for propylene production, propane oxidative dehydrogenation (ODHP) offers the advantage of no thermodynamic limitations and lower energy consumption. However, a major challenge in ODHP is the occurrence of undesired over-oxidation reactions of propylene, which reduce selectivity and hinder industrialization. MOFs possess a large number of metal sites that can serve as catalytic centers, which facilitates the easier access of reactants to the catalytic centers for reaction. Additionally, their flexible framework structure allows for easier adjustment of their pores compared to metal oxides and molecular sieves, which is advantageous for the diffusion of products within the framework. This property reduces the likelihood of prolonged contact between the generated propylene and the catalytic centers, thus minimizing the possibility of over-oxidation. The research on MOF catalyzed oxidative dehydrogenation of propane (ODHP) mainly focuses on the catalytic properties of MOFs with cobalt oxygen sites and boron oxygen sites. The advantages of cobalt oxygen site MOFs include significantly reduced energy consumption, enabling catalytic reactions at temperatures of 230 °C and below, while boron oxygen site MOFs exhibit high conversion rates and selectivity, albeit requiring higher temperatures. The explicit structure of MOFs facilitates the mechanistic study of these sites, enabling further optimization of catalysts. This paper provides an overview of the recent progress in utilizing MOFs as catalysts for ODHP and explores how they promote progress in ODHP catalysis. Finally, the challenges and future prospects of MOFs in the field of ODHP reactions are discussed. Full article
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33 pages, 6343 KiB  
Review
Recent Progress in Metal Oxide-Based Photocatalysts for CO2 Reduction to Solar Fuels: A Review
by Xuanzhen Li, Jing Xiong, Zhiling Tang, Wenjie He, Yingli Wang, Xiong Wang, Zhen Zhao and Yuechang Wei
Molecules 2023, 28(4), 1653; https://doi.org/10.3390/molecules28041653 - 9 Feb 2023
Cited by 18 | Viewed by 3736
Abstract
One of the challenges in developing practical CO2 photoconversion catalysts is the design of materials with a low cost, high activity and good stability. In this paper, excellent photocatalysts based on TiO2, WO3, ZnO, Cu2O and [...] Read more.
One of the challenges in developing practical CO2 photoconversion catalysts is the design of materials with a low cost, high activity and good stability. In this paper, excellent photocatalysts based on TiO2, WO3, ZnO, Cu2O and CeO2 metal oxide materials, which are cost-effective, long-lasting, and easy to fabricate, are evaluated. The characteristics of the nanohybrid catalysts depend greatly on their architecture and design. Thus, we focus on outstanding materials that offer effective and practical solutions. Strategies to improve CO2 conversion efficiency are summarized, including heterojunction, ion doping, defects, sensitization and morphology control, which can inspire the future improvement in photochemistry. The capacity of CO2 adsorption is also pivotal, which varies with the morphological and electronic structures. Forms of 0D, 1D, 2D and 3DOM (zero/one/two-dimensional- and three-dimensional-ordered macroporous, respectively) are involved. Particularly, the several advantages of the 3DOM material make it an excellent candidate material for CO2 conversion. Hence, we explain its preparation method. Based on the discussion, new insights and prospects for designing high-efficient metallic oxide photocatalysts to reduce CO2 emissions are presented. Full article
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