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Porous Organic Polymers: Synthesis, Characterization and Applications
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Porous Organic Polymers: Synthesis, Characterization and Applications

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

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 24706

Special Issue Editor

Dr. Himanshu Jena

E-Mail Website
Guest Editor
Department of Chemistry, Ghent University, 9000 Ghent, Belgium
Interests: porous materials; metal-organic frameworks; COF; nanoparticles; catalysis; gas adsorptions and separation; sensor; lanthanides; quantum dots
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Porous organic materials have recently emerged as smart materials for carbon capture, storage, separation, catalysis, dye adsorption and degradation, luminescence and electrochemical and photochemical reactions. This set of materials includes porous organic polymers (POPs), covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and porous aromatic frameworks (PAFs). In addition, the properties of these materials are comparable with those of metal–organic frameworks (MOFs) in most cases. These materials have gained significant interest in the scientific communities due to their low density, high stability and large surface area, along with the possibility to customize their pore volume, size and modifications. Using such materials, several parameters can be tuned towards achieving enhanced properties. They have also gained significant attention in catalysis, as this sort of catalyst bridges the gap between homogenous and heterogeneous catalysis. Due to pore confinements and high surface area, these materials have shown interesting and selective dye adsorption and even degradation. Lanthanide-functionalized materials have shown outstanding luminescence properties as white-light-emitting materials. Noble and transition metal nanoparticle loaded porous organic materials have shown potential in electrochemical and photochemical reactions, including organic transformation, CO2 reduction, hydrogen evolution, oxygen reduction and oxygen evolution reactions.

Within this context, the aim of this Special Issue is to collect articles describing porous organic materials for different potential applications. From the perspective of materials, amorphous as well as crystalline porous materials will be considered. Regarding applications, the scope of the Special Issue will be extended to all sorts of potential applications reported using POPs, COFs, PAFs and MOFs.

Dr. Himanshu Sekhar Jena
Guest Editor

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

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 organic polymers
  • Covalent organic frameworks
  • Porous aromatic frameworks
  • Metal–organic frameworks
  • Catalysis
  • Luminescence
  • Dye adsorption and degradation
  • Electrocatalysis
  • Photocatalysis
  • CO2 storage, separation and utilization
  • Hydrogen evolution
  • Oxygen evolution
  • Oxygen reduction
  • Supercapacitors
  • Li batteries

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Published Papers (7 papers)

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Research

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10 pages, 3020 KiB  
Article
Co3Gd4 Cage as Magnetic Refrigerant and Co3Dy3 Cage Showing Slow Relaxation of Magnetisation
by Javeed Ahmad Sheikh, Himanshu Sekhar Jena and Sanjit Konar
Molecules 2022, 27(3), 1130; https://doi.org/10.3390/molecules27031130 - 8 Feb 2022
Cited by 6 | Viewed by 2042
Abstract
Two structurally dissimilar 3d-4f cages having the formulae [(CoIII)3Gd4(μ3-OH)2(CO3) (O2CtBu)11(teaH)3]·5H2O (1) and [(CoIII)3Dy3(μ [...] Read more.
Two structurally dissimilar 3d-4f cages having the formulae [(CoIII)3Gd4(μ3-OH)2(CO3) (O2CtBu)11(teaH)3]·5H2O (1) and [(CoIII)3Dy3(μ3-OH)4(O2CtBu)6(teaH)3]·(NO3)2·H2O (2) have been isolated under similar reaction conditions and stoichiometry of the reactants. The most important factor for structural diversity seems to be the incorporation of one μ3-carbonate anion in 1 and not in 2. Co atoms are in a +3 oxidation state in both complexes, as shown by the Bond Valence Sum (BVS) calculations and bond lengths, and as further supported by magnetic measurements. Co3Gd4 displays a significant magnetocaloric effect (−∆Sm = 25.67 J kg−1 K−1), and Co3Dy3 shows a single molecule magnet (SMM) behavior. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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8 pages, 1131 KiB  
Communication
Rigid Nanoporous Urea-Based Covalent Triazine Frameworks for C2/C1 and CO2/CH4 Gas Separation
by Chidharth Krishnaraj, Himanshu Sekhar Jena, Florence Lecoeuvre, Karen Leus and Pascal Van Der Voort
Molecules 2021, 26(12), 3670; https://doi.org/10.3390/molecules26123670 - 16 Jun 2021
Cited by 5 | Viewed by 2590
Abstract
C2/C1 hydrocarbon separation is an important industrial process that relies on energy-intensive cryogenic distillation methods. The use of porous adsorbents to selectively separate these gases is a viable alternative. Highly stable covalent triazine frameworks (urea-CTFs) have been synthesized using 1,3-bis(4-cyanophenyl)urea. Urea-CTFs exhibited gas [...] Read more.
C2/C1 hydrocarbon separation is an important industrial process that relies on energy-intensive cryogenic distillation methods. The use of porous adsorbents to selectively separate these gases is a viable alternative. Highly stable covalent triazine frameworks (urea-CTFs) have been synthesized using 1,3-bis(4-cyanophenyl)urea. Urea-CTFs exhibited gas uptakes of C2H2 (3.86 mmol/g) and C2H4 (2.92 mmol/g) at 273 K and 1 bar and is selective over CH4. Breakthrough simulations show the potential of urea-CTFs for C2/C1 separation. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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10 pages, 409 KiB  
Article
Pyrolysis of Porous Organic Polymers under a Chlorine Atmosphere to Produce Heteroatom-Doped Microporous Carbons
by Wojciech Kiciński, Sławomir Dyjak and Mateusz Gratzke
Molecules 2021, 26(12), 3656; https://doi.org/10.3390/molecules26123656 - 15 Jun 2021
Cited by 3 | Viewed by 2077
Abstract
Three types of cross-linked porous organic polymers (either oxygen-, nitrogen-, or sulfur-doped) were carbonized under a chlorine atmosphere to obtain chars in the form of microporous heteroatom-doped carbons. The studied organic polymers constitute thermosetting resins obtained via sol-gel polycondensation of resorcinol and five-membered [...] Read more.
Three types of cross-linked porous organic polymers (either oxygen-, nitrogen-, or sulfur-doped) were carbonized under a chlorine atmosphere to obtain chars in the form of microporous heteroatom-doped carbons. The studied organic polymers constitute thermosetting resins obtained via sol-gel polycondensation of resorcinol and five-membered heterocyclic aldehydes (either furan, pyrrole, or thiophene). Carbonization under highly oxidative chlorine (concentrated and diluted Cl2 atmosphere) was compared with pyrolysis under an inert helium atmosphere. All pyrolyzed samples were additionally annealed under NH3. The influence of pyrolysis and additional annealing conditions on the carbon materials’ porosity and chemical composition was elucidated. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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13 pages, 4815 KiB  
Article
Mesoporous Porphyrin-Silica Nanocomposite as Solid Acid Catalyst for High Yield Synthesis of HMF in Water
by Arindam Modak, Akshay R. Mankar, Kamal Kishore Pant and Asim Bhaumik
Molecules 2021, 26(9), 2519; https://doi.org/10.3390/molecules26092519 - 26 Apr 2021
Cited by 24 | Viewed by 3280
Abstract
Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, [...] Read more.
Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N2 sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m2/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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11 pages, 5328 KiB  
Article
Nitrogen-Doped Carbons Derived from Imidazole-Based Cross-Linked Porous Organic Polymers
by Wojciech Kiciński and Sławomir Dyjak
Molecules 2021, 26(3), 668; https://doi.org/10.3390/molecules26030668 - 27 Jan 2021
Cited by 13 | Viewed by 5636
Abstract
Nitrogen-doped and heteroatom multi-doped carbon materials are considered excellent metal-free catalysts, superior catalyst supports for transition metal particles and single metal atoms (single-atom catalysts), as well as efficient sorbents for gas- and liquid-phase substances. Acid-catalyzed sol–gel polycondensation of hydroxybenzenes with heterocyclic aldehydes yields [...] Read more.
Nitrogen-doped and heteroatom multi-doped carbon materials are considered excellent metal-free catalysts, superior catalyst supports for transition metal particles and single metal atoms (single-atom catalysts), as well as efficient sorbents for gas- and liquid-phase substances. Acid-catalyzed sol–gel polycondensation of hydroxybenzenes with heterocyclic aldehydes yields cross-linked thermosetting resins in the form of porous organic polymers (i.e., organic gels). Depending on the utilized hydroxybenzene (e.g., phenol, resorcinol, phloroglucinol, etc.) and heterocyclic aldehyde variety of heteroatom-doped organic polymers can be produced. Upon pyrolysis, highly porous and heteroatom-doped carbons are obtained. Herein, polycondensation of phloroglucinol with imidazole-2-carboxaldehyde (and other, similar heterocyclic aldehydes with two heteroatoms in the aromatic ring) is utilized to obtain porous, N-doped organic and carbon gels with N-content of up to 16.5 and 12 wt.%, respectively. Utilization of a heterocyclic aldehyde with two different heteroatoms yields dually-doped carbon materials. Upon pyrolysis, the porous polymers yield ultramicroporous N-doped and N,S co-doped carbons with specific surface areas of up to 800 m2g−1. The influence of the initial composition of reactants and the pyrolysis temperature on the structure and chemical composition of the final doped organic and carbon materials is studied in detail. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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Review

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19 pages, 4021 KiB  
Review
Redesigning Nature: Ruthenium Flavonoid Complexes with Antitumour, Antimicrobial and Cardioprotective Activities
by Nádia E. Santos and Susana Santos Braga
Molecules 2021, 26(15), 4544; https://doi.org/10.3390/molecules26154544 - 27 Jul 2021
Cited by 11 | Viewed by 2677
Abstract
Flavonoids are a class of natural polyphenolic compounds sharing a common 2-phenyl-3,4-dihydro-2H-1-benzopyran (flavan) backbone. Typically known for their antioxidant activity, flavonoids are also being investigated regarding antitumour and antimicrobial properties. In this review, we report on the complexation of both natural [...] Read more.
Flavonoids are a class of natural polyphenolic compounds sharing a common 2-phenyl-3,4-dihydro-2H-1-benzopyran (flavan) backbone. Typically known for their antioxidant activity, flavonoids are also being investigated regarding antitumour and antimicrobial properties. In this review, we report on the complexation of both natural and synthetic flavonoids with ruthenium as a strategy to modulate the biological activity. The ruthenoflavonoid complexes are divided into three subclasses, according to their most prominent bioactivity: antitumour, antimicrobial, and protection of the cardiovascular system. Whenever possible the activity of the ruthenoflavonoids is compared with that of commercial drugs for a critical assessment of the feasibility of using them in future clinical applications. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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27 pages, 18820 KiB  
Review
Rational Design and Application of Covalent Organic Frameworks for Solar Fuel Production
by Priyanka Verma, Joshua J.M. Le Brocq and Robert Raja
Molecules 2021, 26(14), 4181; https://doi.org/10.3390/molecules26144181 - 9 Jul 2021
Cited by 8 | Viewed by 4871
Abstract
Harnessing solar energy and converting it into renewable fuels by chemical processes, such as water splitting and carbon dioxide (CO2) reduction, is a highly promising yet challenging strategy to mitigate the effects arising from the global energy crisis and serious environmental [...] Read more.
Harnessing solar energy and converting it into renewable fuels by chemical processes, such as water splitting and carbon dioxide (CO2) reduction, is a highly promising yet challenging strategy to mitigate the effects arising from the global energy crisis and serious environmental concerns. In recent years, covalent organic framework (COF)-based materials have gained substantial research interest because of their diversified architecture, tunable composition, large surface area, and high thermal and chemical stability. Their tunable band structure and significant light absorption with higher charge separation efficiency of photoinduced carriers make them suitable candidates for photocatalytic applications in hydrogen (H2) generation, CO2 conversion, and various organic transformation reactions. In this article, we describe the recent progress in the topology design and synthesis method of COF-based nanomaterials by elucidating the structure-property correlations for photocatalytic hydrogen generation and CO2 reduction applications. The effect of using various kinds of 2D and 3D COFs and strategies to control the morphology and enhance the photocatalytic activity is also summarized. Finally, the key challenges and perspectives in the field are highlighted for the future development of highly efficient COF-based photocatalysts. Full article
(This article belongs to the Special Issue Porous Organic Polymers: Synthesis, Characterization and Applications)
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