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Search Results (355)

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Keywords = Covalent-Organic Frameworks

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38 pages, 9212 KiB  
Review
Advanced Materials-Based Nanofiltration Membranes for Efficient Removal of Organic Micropollutants in Water and Wastewater Treatment
by Haochun Wei, Haibiao Nong, Li Chen and Shiyu Zhang
Membranes 2025, 15(8), 236; https://doi.org/10.3390/membranes15080236 - 5 Aug 2025
Abstract
The increasing use of pharmaceutically active compounds (PhACs), endocrine-disrupting compounds (EDCs), and personal care products (PCPs) has led to the widespread presence of organic micropollutants (OMPs) in aquatic environments, posing a significant global challenge for environmental conservation. In recent years, advanced materials-based nanofiltration [...] Read more.
The increasing use of pharmaceutically active compounds (PhACs), endocrine-disrupting compounds (EDCs), and personal care products (PCPs) has led to the widespread presence of organic micropollutants (OMPs) in aquatic environments, posing a significant global challenge for environmental conservation. In recent years, advanced materials-based nanofiltration (NF) technologies have emerged as a promising solution for water and wastewater treatment. This review begins by examining the sources of OMPs, as well as the risk of OMPs. Subsequently, the key criteria of NF membranes for OMPs are discussed, with a focus on the roles of pore size, charge property, molecular interaction, and hydrophilicity in the separation performance. Against that background, this review summarizes and analyzes recent advancements in materials such as metal organic frameworks (MOFs), covalent organic frameworks (COFs), graphene oxide (GO), MXenes, hybrid materials, and environmentally friendly materials. It highlights the porous nature and structural diversity of organic framework materials, the advantage of inorganic layered materials in forming controllable nanochannels through stacking, the synergistic effects of hybrid materials, and the importance of green materials. Finally, the challenges related to the performance optimization, scalable fabrication, environmental sustainability, and complex separation of advanced materials-based membranes for OMP removal are discussed, along with future research directions and potential breakthroughs. Full article
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15 pages, 5007 KiB  
Article
In Situ Construction of Thiazole-Linked Covalent Organic Frameworks on Cu2O for High-Efficiency Photocatalytic Tetracycline Degradation
by Zhifang Jia, Tingxia Wang, Zhaoxia Wu, Shumaila Razzaque, Zhixiang Zhao, Jiaxuan Cai, Wenao Xie, Junli Wang, Qiang Zhao and Kewei Wang
Molecules 2025, 30(15), 3233; https://doi.org/10.3390/molecules30153233 - 1 Aug 2025
Viewed by 155
Abstract
The strategic construction of heterojunctions through a simple and efficient strategy is one of the most effective means to boost the photocatalytic activity of semiconductor materials. Herein, a thiazole-linked covalent organic framework (TZ-COF) with large surface area, well-ordered pore structure, and high stability [...] Read more.
The strategic construction of heterojunctions through a simple and efficient strategy is one of the most effective means to boost the photocatalytic activity of semiconductor materials. Herein, a thiazole-linked covalent organic framework (TZ-COF) with large surface area, well-ordered pore structure, and high stability was developed. To further boost photocatalytic activity, the TZ-COF was synthesized in situ on the surface of Cu2O through a simple multicomponent reaction, yielding an encapsulated composite material (Cu2O@TZ-COF-18). In this composite, the outermost COF endows the material with abundant redox active sites and mass transfer channels, while the innermost Cu2O exhibits unique photoelectric properties. Notably, the synthesized Cu2O@TZ-COF-18 was proven to have the heterojunction structure, which can efficiently restrain the recombination of photogenerated electron–hole pairs, thereby enhancing the photocatalytic performance. The photocatalytic degradation of tetracycline demonstrated that 3-Cu2O@TZ-COF-18 had the highest photocatalytic efficiency, with the removal rate of 96.3% within 70 min under visible light, which is better than that of pristine TZ-COF-18, Cu2O, the physical mixture of Cu2O and TZ-COF-18, and numerous reported COF-based composite materials. 3-Cu2O@TZ-COF-18 retained its original crystallinity and removal efficiency after five cycles in photodegradation reaction, displaying high stability and excellent cycle performance. Full article
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14 pages, 3666 KiB  
Article
A Sensitive Sandwich-Type Electrochemical Immunosensor for Carbohydrate Antigen 19-9 Based on Covalent Organic Frameworks
by Ting Wu, Rongfang Chen, Yaqin Duan, Longfei Miao, Yongmei Zhu and Li Wang
Biosensors 2025, 15(8), 492; https://doi.org/10.3390/bios15080492 - 1 Aug 2025
Viewed by 174
Abstract
Since carbohydrate antigen 19-9 (CA 19-9) is a significant biomarker for the clinical diagnosis and treatment of pancreatic cancer, a sensitive sandwich-type immunosensor was proposed with an epoxy functionalized covalent organic framework (EP-COFTTA-DHTA) as the antibody carrier and an electroactive COF [...] Read more.
Since carbohydrate antigen 19-9 (CA 19-9) is a significant biomarker for the clinical diagnosis and treatment of pancreatic cancer, a sensitive sandwich-type immunosensor was proposed with an epoxy functionalized covalent organic framework (EP-COFTTA-DHTA) as the antibody carrier and an electroactive COFTTA-2,6-NA(OH)2 as the signal amplification probe for the sensitive detection of CA 19-9. The flexible covalent linkage between the epoxy-functionalized EP-COFTTA-DHTA and the antibodies was employed to improve the dynamics of the antigen–antibody interaction significantly. Meanwhile, AuNPs@COFTTA-2,6-NA(OH)2 with abundant electroactive sites enhanced the current response of the immunoreaction significantly. After optimizing the incubation time and concentration of the antibody, CA 19-9 was quantitatively detected by differential pulse voltammetry (DPV) based on the sensitive sandwich-type immunosensor with a low detection limit of 0.0003 U/mL and a wide linear range of 0.0009–100 U/mL. The electrochemical immunosensor exhibits high specificity, stability and repeatability, and it provides a feasible and efficient method for the pathologic analysis and treatment of tumor markers. Full article
(This article belongs to the Special Issue Advances in Biosensors Based on Framework Materials)
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53 pages, 5030 KiB  
Review
Molecular Engineering of Recombinant Protein Hydrogels: Programmable Design and Biomedical Applications
by He Zhang, Jiangning Wang, Jiaona Wei, Xueqi Fu, Junfeng Ma and Jing Chen
Gels 2025, 11(8), 579; https://doi.org/10.3390/gels11080579 - 26 Jul 2025
Viewed by 670
Abstract
Recombinant protein hydrogels have emerged as transformative biomaterials that overcome the bioinertness and unpredictable degradation of traditional synthetic systems by leveraging genetically engineered backbones, such as elastin-like polypeptides, SF, and resilin-like polypeptides, to replicate extracellular matrix (ECM) dynamics and enable programmable functionality. Constructed [...] Read more.
Recombinant protein hydrogels have emerged as transformative biomaterials that overcome the bioinertness and unpredictable degradation of traditional synthetic systems by leveraging genetically engineered backbones, such as elastin-like polypeptides, SF, and resilin-like polypeptides, to replicate extracellular matrix (ECM) dynamics and enable programmable functionality. Constructed through a hierarchical crosslinking strategy, these hydrogels integrate reversible physical interactions with covalent crosslinking approaches, collectively endowing the system with mechanical strength, environmental responsiveness, and controlled degradation behavior. Critically, molecular engineering strategies serve as the cornerstone for functional precision: domain-directed self-assembly exploits coiled-coil or β-sheet motifs to orchestrate hierarchical organization, while modular fusion of bioactive motifs through genetic encoding or site-specific conjugation enables dynamic control over cellular interactions and therapeutic release. Such engineered designs underpin advanced applications, including immunomodulatory scaffolds for diabetic wound regeneration, tumor-microenvironment-responsive drug depots, and shear-thinning bioinks for vascularized bioprinting, by synergizing material properties with biological cues. By uniting synthetic biology with materials science, recombinant hydrogels deliver unprecedented flexibility in tuning physical and biological properties. This review synthesizes emerging crosslinking paradigms and molecular strategies, offering a framework for engineering next-generation, adaptive biomaterials poised to address complex challenges in regenerative medicine and beyond. Full article
(This article belongs to the Special Issue Recent Advances in Protein Gels)
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15 pages, 2190 KiB  
Article
Synthesis and Characterization of Covalent Triazine Frameworks Based on 4,4′-(Phenazine-5,10-diyl)dibenzonitrile and Its Application in CO2/CH4 Separation
by Hanibal Othman, Robert Oestreich, Vivian Küll, Marcus N. A. Fetzer and Christoph Janiak
Molecules 2025, 30(15), 3110; https://doi.org/10.3390/molecules30153110 - 24 Jul 2025
Viewed by 252
Abstract
Covalent triazine frameworks (CTFs) have gained recognition as stable porous organic polymers, for example, for CO2 separation. From the monomer 4,4′-(phenazine-5,10-diyl)dibenzonitrile (pBN), new pBN-CTFs were synthesized using the ionothermal method with a variation in temperature (400 and 550 °C) and the ZnCl [...] Read more.
Covalent triazine frameworks (CTFs) have gained recognition as stable porous organic polymers, for example, for CO2 separation. From the monomer 4,4′-(phenazine-5,10-diyl)dibenzonitrile (pBN), new pBN-CTFs were synthesized using the ionothermal method with a variation in temperature (400 and 550 °C) and the ZnCl2-to-monomer ratio (10 and 20). N2 adsorption yielded BET surface areas up to 1460 m2g −1. The pBN-CTFs are promising CO2 adsorbents and are comparable to other benchmark CTFs such as CTF-1 with a CO2 uptake of pBN-CTF-10-550 at 293 K of up to 54 cm3 g−1 or 96 mg g−1, with a CO2/CH4 IAST selectivity of 22 for a 50% mixture of CO2/CH4. pBN-CTF-10-400 has a very high heat of adsorption of 79 kJ mol−1 for CO2 near zero coverage in comparison to other CTFs, and it also stays well above the liquefaction heat of CO2 due to its high microporosity of 50% of the total pore volume. Full article
(This article belongs to the Section Materials Chemistry)
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32 pages, 10334 KiB  
Review
Advances in Nanozyme Catalysis for Food Safety Detection: A Comprehensive Review on Progress and Challenges
by Renqing Yang, Zeyan Liu, Haili Chen, Xinai Zhang, Qing Sun, Hany S. El-Mesery, Wenjie Lu, Xiaoli Dai and Rongjin Xu
Foods 2025, 14(15), 2580; https://doi.org/10.3390/foods14152580 - 23 Jul 2025
Viewed by 422
Abstract
The prosperity of enzyme-mimicking catalysis has promoted the development of nanozymes with diversified activities, mainly including catalase-like, oxidase-like, peroxidase-like, and superoxide dismutase-like characteristics. Thus far, the reported nanozymes can be roughly divided into five categories, comprising noble metals, metal oxides, carbon-based nanostructures, metal–organic [...] Read more.
The prosperity of enzyme-mimicking catalysis has promoted the development of nanozymes with diversified activities, mainly including catalase-like, oxidase-like, peroxidase-like, and superoxide dismutase-like characteristics. Thus far, the reported nanozymes can be roughly divided into five categories, comprising noble metals, metal oxides, carbon-based nanostructures, metal–organic frameworks, and covalent organic frameworks. This review systematically summarizes the research progress of nanozymes for improving catalytic activity toward sensing applications in food safety monitoring. Specifically, we highlight the unique advantages of nanozymes in enhancing the performance of colorimetric, fluorescence, and electrochemical sensors, which are crucial for detecting various food contaminants. Moreover, this review addresses the challenges faced in food safety detection, such as the need for high sensitivity, selectivity, and stability under complex food matrices. Nanozymes offer promising solutions by providing robust catalytic activity, adjustable enzyme-like properties, and excellent stability, even in harsh environments. However, practical implementation challenges remain, including the need for a deeper understanding of nanozyme catalytic mechanisms, improving substrate selectivity, and ensuring long-term stability and large-scale production. By focusing on these aspects, this review aims to provide a comprehensive overview of the current state of nanozyme-based sensors for food safety detection and to inspire future research directions. Full article
(This article belongs to the Section Food Quality and Safety)
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29 pages, 23821 KiB  
Review
Covalent Organic Frameworks for Immunoassays: A Review
by Suling Yang and Hongmin Liu
Biosensors 2025, 15(7), 469; https://doi.org/10.3390/bios15070469 - 21 Jul 2025
Viewed by 526
Abstract
Immunoassays relying on highly specific antigen–antibody recognition are important tools for effectively measuring the levels of various targets. Efforts have been made in the development of various methods to improve the detection sensitivity and stability of immunoassays. Covalent organic frameworks (COFs), as an [...] Read more.
Immunoassays relying on highly specific antigen–antibody recognition are important tools for effectively measuring the levels of various targets. Efforts have been made in the development of various methods to improve the detection sensitivity and stability of immunoassays. Covalent organic frameworks (COFs), as an emerging class of novel crystalline porous materials, have unique advantages such as flexible designability, high surface area, excellent stability, tunable pore sizes, and multiple functionalities. They have great potential as novel sensory materials. Herein, we summarize the advances of COFs in electrochemical and optical immunoassays serving as electrode modifiers, signal indicators, enzyme or probe carriers, etc. Meanwhile, the design and application of typical COFs-based immunoassays in the determination of different targets are discussed in detail. Finally, challenges and future perspectives are presented. Full article
(This article belongs to the Special Issue Biosensors Based on Self-Assembly and Boronate Affinity Interaction)
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40 pages, 1777 KiB  
Review
Nanomaterials for Direct Air Capture of CO2: Current State of the Art, Challenges and Future Perspectives
by Cataldo Simari
Molecules 2025, 30(14), 3048; https://doi.org/10.3390/molecules30143048 - 21 Jul 2025
Viewed by 396
Abstract
Direct Air Capture (DAC) is emerging as a critical climate change mitigation strategy, offering a pathway to actively remove atmospheric CO2. This comprehensive review synthesizes advancements in DAC technologies, with a particular emphasis on the pivotal role of nanostructured solid sorbent [...] Read more.
Direct Air Capture (DAC) is emerging as a critical climate change mitigation strategy, offering a pathway to actively remove atmospheric CO2. This comprehensive review synthesizes advancements in DAC technologies, with a particular emphasis on the pivotal role of nanostructured solid sorbent materials. The work critically evaluates the characteristics, performance, and limitations of key nanomaterial classes, including metal–organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, amine-functionalized polymers, porous carbons, and layered double hydroxides (LDHs), alongside solid-supported ionic liquids, highlighting their varied CO2 uptake capacities, regeneration energy requirements, and crucial water sensitivities. Beyond traditional temperature/pressure swing adsorption, the review delves into innovative DAC methodologies such as Moisture Swing Adsorption (MSA), Electro Swing Adsorption (ESA), Passive DAC, and CO2-Binding Organic Liquids (CO2 BOLs), detailing their unique mechanisms and potential for reduced energy footprints. Despite significant progress, the widespread deployment of DAC faces formidable challenges, notably high capital and operational costs (currently USD 300–USD 1000/tCO2), substantial energy demands (1500–2400 kWh/tCO2), water interference, scalability hurdles, and sorbent degradation. Furthermore, this review comprehensively examines the burgeoning global DAC market, its diverse applications, and the critical socio-economic barriers to adoption, particularly in developing countries. A comparative analysis of DAC within the broader carbon removal landscape (e.g., CCS, BECCS, afforestation) is also provided, alongside an address to the essential, often overlooked, environmental considerations for the sustainable production, regeneration, and disposal of spent nanomaterials, including insights from Life Cycle Assessments. The nuanced techno-economic landscape has been thoroughly summarized, highlighting that commercial viability is a multi-faceted challenge involving material performance, synthesis cost, regeneration energy, scalability, and long-term stability. It has been reiterated that no single ‘best’ material exists, but rather a portfolio of technologies will be necessary, with the ultimate success dependent on system-level integration and the availability of low-carbon energy. The review paper contributes to a holistic understanding of cutting-edge DAC technologies, bridging material science innovations with real-world implementation challenges and opportunities, thereby identifying critical knowledge gaps and pathways toward a net-zero carbon future. Full article
(This article belongs to the Special Issue Porous Carbon Materials: Preparation and Application)
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34 pages, 3610 KiB  
Review
Metal–Organic Frameworks as Fillers in Porous Organic Polymer-Based Hybrid Materials: Innovations in Composition, Processing, and Applications
by Victor Durán-Egido, Daniel García-Giménez, Juan Carlos Martínez-López, Laura Pérez-Vidal and Javier Carretero-González
Polymers 2025, 17(14), 1941; https://doi.org/10.3390/polym17141941 - 15 Jul 2025
Viewed by 718
Abstract
Hybrid materials based on porous organic polymers (POPs) and metal–organic frameworks (MOFs) are increasing attention for advanced separation processes due to the possibility to combine their properties. POPs provide high surface areas, chemical stability, and tunable porosity, while MOFs contribute a high variety [...] Read more.
Hybrid materials based on porous organic polymers (POPs) and metal–organic frameworks (MOFs) are increasing attention for advanced separation processes due to the possibility to combine their properties. POPs provide high surface areas, chemical stability, and tunable porosity, while MOFs contribute a high variety of defined crystalline structures and enhanced separation characteristics. The combination (or hybridization) with PIMs gives rise to mixed-matrix membranes (MMMs) with improved permeability, selectivity, and long-term stability. However, interfacial compatibility remains a key limitation, often addressed through polymer functionalization or controlled dispersion of the MOF phase. MOF/COF hybrids are more used as biochemical sensors with elevated sensitivity, catalytic applications, and wastewater remediation. They are also very well known in the gas sorption and separation field, due to their tunable porosity and high electrical conductivity, which also makes them feasible for energy storage applications. Last but not less important, hybrids with other POPs, such as hyper-crosslinked polymers (HCPs), covalent triazine frameworks (CTFs), or conjugated microporous polymers (CMPs), offer enhanced functionality. MOF/HCP hybrids combine ease of synthesis and chemical robustness with tunable porosity. MOF/CTF hybrids provide superior thermal and chemical stability under harsh conditions, while MOF/CMP hybrids introduce π-conjugation for enhanced conductivity and photocatalytic activity. These and other findings confirm the potential of MOF-POP hybrids as next-generation materials for gas separation and carbon capture applications. Full article
(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials, 4th Edition)
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21 pages, 4609 KiB  
Review
Covalent Organic Framework Membranes for Ion Separation: A Review
by Yutong Lou, Zhanyong Wang, Wanbei Yang, Shuchen Lang, Jiaxing Fan, Qiaomei Ke, Rui Wang, Zhen Zhang, Wentao Chen and Jian Xue
Membranes 2025, 15(7), 211; https://doi.org/10.3390/membranes15070211 - 15 Jul 2025
Viewed by 636
Abstract
Covalent organic framework (COF) membranes have garnered significant attention in ion separation due to their high surface area, tunable pore size, excellent stability, and diverse functional groups. Over the past decade, various synthesis methods, such as solvothermal synthesis, interfacial synthesis, microwave-assisted solvothermal synthesis, [...] Read more.
Covalent organic framework (COF) membranes have garnered significant attention in ion separation due to their high surface area, tunable pore size, excellent stability, and diverse functional groups. Over the past decade, various synthesis methods, such as solvothermal synthesis, interfacial synthesis, microwave-assisted solvothermal synthesis, and in situ growth, have been developed to fabricate COF membranes. COF membranes have demonstrated remarkable ion separation performance in different separation processes driven by pressure, electric field, and vapor pressure difference, showing great potential in a wide range of applications. Nevertheless, challenges in the synthesis and application of COF membranes still remain, requiring further research to fully realize their potential in ion separation. This review critically examines the development of COF membranes, from synthesis methods to ion separation applications. We evaluate the advantages and limitations of various synthesis techniques and systematically summarize COF membrane performance based on separation driving forces. Finally, we present a critical analysis of current challenges and offer perspectives on promising future research directions for advancing COF membrane technology in separation. Full article
(This article belongs to the Section Membrane Applications for Water Treatment)
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24 pages, 7899 KiB  
Review
Catalyst-Driven Improvements in Conventional Methods for Imine-Linked Covalent Organic Frameworks
by Maziar Jafari, Zhiyuan Peng, Ali Samie, Faezeh Taghavi, Amir Khojastehnezhad and Mohamed Siaj
Molecules 2025, 30(14), 2969; https://doi.org/10.3390/molecules30142969 - 15 Jul 2025
Viewed by 404
Abstract
Imine-linked covalent organic frameworks (COFs) have attracted considerable interest in recent years because they can form strong and reversible covalent bonds, enabling the development of highly ordered crystalline structures. This reversibility is crucial in correcting structural defects during the crystallization process, which requires [...] Read more.
Imine-linked covalent organic frameworks (COFs) have attracted considerable interest in recent years because they can form strong and reversible covalent bonds, enabling the development of highly ordered crystalline structures. This reversibility is crucial in correcting structural defects during the crystallization process, which requires sufficient time to proceed. This review critically examines the advancements in synthetic strategies for these valuable materials, focusing on catalytic versus conventional approaches. Traditional methods for synthesizing imine-linked COFs often involve harsh reaction conditions and prolonged reaction times, which can limit the scalability and environmental sustainability of these frameworks. In contrast, catalytic approaches offer more efficient pathways, enabling shorter reaction times, milder reaction conditions, and higher yields. This article elucidates the key differences between these methodologies and examines the impact of reduced reaction times and milder conditions on the crystallinity and porosity of COFs. By comparing the catalytic and conventional synthesis routes, this review aims to provide a comprehensive understanding of the advantages and limitations of each approach, offering insights into the optimal strategies for the development of high-performance COFs. Full article
(This article belongs to the Special Issue Feature Papers in Applied Chemistry: 4th Edition)
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18 pages, 4672 KiB  
Article
Tailoring Porosity and CO2 Capture Performance of Covalent Organic Frameworks Through Hybridization with Two-Dimensional Nanomaterials
by Hani Nasser Abdelhamid
Inorganics 2025, 13(7), 237; https://doi.org/10.3390/inorganics13070237 - 11 Jul 2025
Viewed by 404
Abstract
This study reported covalent organic frameworks (COFs) and their hybrid composites with two-dimensional materials, graphene oxide (GO), graphitic carbon nitride (g-C3N4), and boron nitride (BN), to examine their structural, textural, and gas adsorption properties. Material characterization confirmed the crystallinity [...] Read more.
This study reported covalent organic frameworks (COFs) and their hybrid composites with two-dimensional materials, graphene oxide (GO), graphitic carbon nitride (g-C3N4), and boron nitride (BN), to examine their structural, textural, and gas adsorption properties. Material characterization confirmed the crystallinity of COF-1 and the preservation of framework integrity after integrating the 2D nanomaterials. FT-IR spectra exhibited pronounced vibrational fingerprints of imine linkages and validated the functional groups from the COF and the integrated nanomaterials. TEM images revealed the integration of the two components, porous, layered structures with indications of interfacial interactions between COF and 2D nanosheets. Nitrogen adsorption–desorption isotherms revealed the microporous characteristics of the COFs, with hysteresis loops evident, indicating the development of supplementary mesopores at the interface between COF-1 and the 2D materials. The BET surface area of pristine COF-1 was maximal at 437 m2/g, accompanied by significant micropore and Langmuir surface areas of 348 and 1290 m2/g, respectively, offering enhanced average pore widths and hierarchical porous strcuture. CO2 adsorption tests were investigated showing maximum adsorption capacitiy of 1.47 mmol/g, for COF-1, closely followed by COF@BN at 1.40 mmol/g, underscoring the preserved sorption capabilities of these materials. These findings demonstrate the promise of designed COF-based hybrids for gas capture, separation, and environmental remediation applications. Full article
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6 pages, 2223 KiB  
Proceeding Paper
Photocatalytic Degradation of Dyes Using TpPa-COF-Cl2 Membrane
by Mayu Kawaguchi, Hideyuki Katsumata, Ikki Tateishi, Mai Furukawa and Satoshi Kaneco
Chem. Proc. 2025, 17(1), 1; https://doi.org/10.3390/chemproc2025017001 - 4 Jul 2025
Viewed by 345
Abstract
Covalent organic frameworks (COFs) are photocatalysts composed of covalent bonds of light elements and free of toxic metals. COFs are highly active against dyes. Furthermore, we aimed to improve the utility of COFs by making them into membranes. In this study, by utilizing [...] Read more.
Covalent organic frameworks (COFs) are photocatalysts composed of covalent bonds of light elements and free of toxic metals. COFs are highly active against dyes. Furthermore, we aimed to improve the utility of COFs by making them into membranes. In this study, by utilizing the cross-linked structure of calcium alginate, we succeeded in forming the photocatalyst TpPa-COF-Cl2 into a membrane without destroying its structure. This was confirmed by characterization such as FT-IR. In addition, methyl orange was decolorized at 450 nm, confirming the photocatalytic activity of the membrane. Full article
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15 pages, 1943 KiB  
Article
Theoretical Study on the Influence of Building Blocks in Benzotrithiophene-Based Covalent Organic Frameworks for Optoelectronic Properties
by Xu Li, Yue Niu, Kexin Ma, Xin Huang, Qingji Wang and Zhiqiang Liang
Catalysts 2025, 15(7), 647; https://doi.org/10.3390/catal15070647 - 2 Jul 2025
Viewed by 419
Abstract
Covalent organic frameworks (COFs) have emerged as unique catalysts for photocatalysis; however, the relationship between their building block units and optoelectronic properties remains elusive. Herein, we explored the influence of building blocks on the optoelectronic properties of benzotrithiophene-based COFs (BTT-COFs) using density functional [...] Read more.
Covalent organic frameworks (COFs) have emerged as unique catalysts for photocatalysis; however, the relationship between their building block units and optoelectronic properties remains elusive. Herein, we explored the influence of building blocks on the optoelectronic properties of benzotrithiophene-based COFs (BTT-COFs) using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The calculation results suggested that three critical factors—the conjugated structure, planarity, and the introduction of nitrogen heteroatoms—significantly influenced charge separation and transfer within BTT-COFs. Structure–property relationships were established through several critical quantitative parameters, such as Sr, t, and CT. Among seven BTT-COFs, BTT-Tpa (Tpa: 4,4′,4″-triaminotriphenylamine) exhibited the most efficient charge separation and the highest charge transfer capability due to the electronegativity of triphenylamine, the delocalization of its lone pair electrons, and its unique star-shaped configuration. These theoretical results will provide an essential foundation for selecting donor–acceptor units in the design of novel COF materials for photocatalytic reaction applications. Full article
(This article belongs to the Section Computational Catalysis)
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15 pages, 5017 KiB  
Article
Constructing Hydrazone-Linked Chiral Covalent Organic Frameworks with Different Pore Sizes for Asymmetric Catalysis
by Haichen Huang, Kai Zhang, Yuexin Zheng, Hong Chen, Dexuan Cai, Shengrun Zheng, Jun Fan and Songliang Cai
Catalysts 2025, 15(7), 640; https://doi.org/10.3390/catal15070640 - 30 Jun 2025
Viewed by 332
Abstract
Chiral covalent organic frameworks (COFs) hold great promise in heterogeneous asymmetric catalysis due to their designable structures and well-defined chiral microenvironments. However, precise control over the pore size of chiral COFs to optimize asymmetric catalytic performance remains challenging. Herein, we designed a proline-derived [...] Read more.
Chiral covalent organic frameworks (COFs) hold great promise in heterogeneous asymmetric catalysis due to their designable structures and well-defined chiral microenvironments. However, precise control over the pore size of chiral COFs to optimize asymmetric catalytic performance remains challenging. Herein, we designed a proline-derived dihydrazide chiral monomer (L-DBP-Boc), which was subjected to Schiff-base reactions with two aromatic aldehydes of different lengths, 1,3,5-triformyl phloroglucinol (BTA) and 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (TZ), to construct two hydrazone-linked chiral COFs with distinct pore sizes (L-DBP-BTA COF and L-DBP-TZ COF). Interestingly, the Boc protecting groups were removed in situ during COF synthesis. We systematically investigated the catalytic performance of these two chiral COFs in asymmetric aldol reactions and found that their pore sizes significantly influenced both catalytic activity and enantioselectivity. The large-pore L-DBP-TZ COF (pore size: 3.5 nm) exhibited superior catalytic performance under aqueous conditions at room temperature, achieving a yield of 98% and an enantiomeric excess (ee) value of 78%. In contrast, the small-pore L-DBP-BTA COF (pore size: 2.0 nm) showed poor catalytic performance. Compared to L-DBP-BTA COF, L-DBP-TZ COF demonstrated a 1.69-fold increase in yield and a 1.56-fold enhancement in enantioselectivity, possibly attributed to the facilitated diffusion and transport of substrates and products within the larger pore, thus improving the accessibility of active sites. This study presents a facile synthesis of pyrrolidine-functionalized chiral COFs and establishes the possible structure–activity relationship in their asymmetric catalysis, offering new insights for the design of efficient chiral COF catalysts. Full article
(This article belongs to the Special Issue Asymmetric Catalysis: Recent Progress and Future Perspective)
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