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MATERIALS RESEARCH BULLETIN · 2024 · IF 5.3

The structure-activity relationship for the electron-donating functional groups in hydrazone-linked COFs and their photocatalytic H2O2 production

Changlai Li,Haoran Xie,Shijian Zhou,Hao Hu,Guangyuan Chen,Zheng Wei,Jingjing Jiang,Jinping Qin,Zewu Zhang,Yan Kong

Electron-donating group modification on covalent organic frameworks (COFs) would reasonably stimulate photocatalytic activity. However, the structure-activity relationship between the electron-donating capacity and the photocatalytic activity of electron-donating functional COFs remains greatly obscure. Herein, a series of functionalized hydrazone-linked COFs containing different electron-donating capacity groups (R-COF, R = H, Me, MeO, OH) were constructed. The results suggest that the existence of substituents with strong electron-donating capacity in R-COFs can enhance the conjugation effect and thereby accelerate the separation and transfer of photogenerated electron-hole pairs. And the stronger electron-donating capacity of groups are more favorable for the electron push-pull effect, which is beneficial for photocatalytic H 2 O 2 production. Among them, MeO-COF had the highest H 2 O 2 generation performance without sacrificial agents under air (847.9 μmol g −1  h −1 ), which is 4.95 times higher than that of H-COF. This work provides insights for the design of functionalized COFs to achieve efficient photocatalytic H 2 O 2 production.

研究领域: 材料科学 · 光化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Efficient separation of dyes/salts using ionic liquid-modified covalent organic framework THPC-PEI/COFs-NH2PES composite nanofiltration membrane

Li Nan Xu,Yu Xiang Liu,Ya Yuan Zhang,Na Qin,Peng Xiang,Xiong Huang,Jian Hua Chen,Qian Yang

Covalent Organic Frameworks (COFs), with their high porosity, low mass density, excellent thermal stability, and tunable structures, exhibit immense potential in the field of membrane separation. However, the porous structure of COFs and their negatively charged nature result in suboptimal performance in dye/salt separation. Tetrakis(hydroxymethyl)phosphonium chloride (THPC), a zwitterionic liquid, contains a central phosphorus atom and numerous hydroxyl groups, offering the dual optimization characteristics of balancing membrane surface charge and optimizing membrane pore structure. In this study, we first modified polyethersulfone (PES) with p-phenylenediamine to prepare an amino-functionalized NH 2 PES support membrane. Subsequently, we synthesized the COFs selective layer on the NH 2 PES surface via interfacial polymerization to obtain the COFs-NH 2 PES composite membrane. Then, we employed polyethyleneimine (PEI) to modify the COFs-NH 2 PES membrane surface through a polyelectrolyte-mediated assembly strategy, forming the PEI/COFs-NH 2 PES composite membrane. Finally, we conducted THPC modification to prepare the THPC-PEI/COFs-NH 2 PES composite nanofiltration membrane. Zeta potential analysis indicated that the surface charge of the THPC-PEI/COFs-NH 2 PES composite nanofiltration membrane was essentially neutral, favoring dye/salt separation. Dye/salt separation experiments demonstrated that the THPC-PEI/COFs-NH 2 PES composite nanofiltration membrane exhibited excellent separation performance, with a CR rejection rate and dye/salt separation factor reaching up to 99.5 % and 181.2, respectively, and a flux of 211.36 L m −2 bar -1 h −1 . Additionally, by adding THPC, the membrane surface was exposed to a greater number of hydroxyl functional groups, which improved the anti-fouling and stability of the THPC-PEI/COFs-NH 2 PES composite nanofiltration membrane over time.

研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Boosting photocatalytic nitrogen fixation performance by adjusting the intramolecular D-A structure and band gap of thiophene-based COFs

Yunchao Ma,Yuxin Yao,Shengnan Qi,Chuanxue You,Yuanyuan Wu,Chunbo Liu,Bo Hu,Keyu Cui

Herein, we successfully synthesized two photoactive donor–acceptor (D-A) covalent organic frameworks by incorporating electric-deficient triazine and electric-rich benzotrithiophene moieties into the framework. The introduction of sulfur atom and triazine unit significantly change the intrinsic band gap of JLNU-COFs, this leads to an expanded range of light absorption, encompassing wavelengths from ultraviolet to visible. The narrow band gap of JLNU-311 allows for efficient utilization of visible light while maintaining the thermodynamic activity required for nitrogen reduction within appropriate energy bands. JLNU-311 modified with strong electron absorbing groups has higher activity to NH 3 production without co-catalyst or sacrificial agent, and yield can reach 325.6 µmol/g/h. Theoretical calculation further confirm that acceptor structure can effectively regulate the band gap width, promote the adsorption, dissociation and protonation of N 2 molecules on JLNU-COFs, and thus reduce the energy barrier of photocatalytic nitrogen reduction reaction (PNRR). Therefore, this study provides an effective strategy for design of active nitrogen fixing photocatalysts.

研究领域: 材料科学 · 催化化学 · 环境科学
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JOURNAL OF MEMBRANE SCIENCE · 2018 · IF 6.578

Embedding Ag+@COFs within Pebax membrane to confer mass transport channels and facilitated transport sites for elevated desulfurization performance

Fusheng Pan,Meidi Wang,He Ding,Yimeng Song,Weidong Li,Hong Wu,Zhongyi Jiang,Baoyi Wang,Xingzhong Cao

In this study, covalent organic frameworks (COFs) are utilized as carriers to immobilize metal ions in facilitated transport membranes for organic solvent separation for the first time. SNW-1, a kind of COFs with high amount of amino groups, were loaded with Ag + ions and then incorporated into Pebax matrix to prepare hybrid membranes. Under optimal conditions, 48.11 wt% of Ag + was loaded onto SNW-1 through a facile approach, which greatly intensified the mass transfer of unsaturated penetrant molecules (thiophene) by π-complexation. The channels within SNW-1 decreased the mass transport resistance and imparted the molecular sieving ability. The organic nature of SNW-1 optimized the interfacial affinity between filler and polymer, and rendered appropriate free volume properties. The membranes displayed simultaneously enhanced permeation flux and selectivity in pervaporation gasoline desulfurization. Especially, when the content of Ag + @SNW-1 was 9 wt%, the optimum performance towards thiophene concentration of 1312 ppm under 60 °C, was achieved with permeation flux of 16.35 kg/(m 2 h) and enrichment factor of 6.8, which was increased by 78.5% and 30.0%, respectively, compared with pure Pebax membranes. In addition, the anti-swelling property of the membranes was improved and the membranes possessed superior long-term stability. This study demonstrates that COFs are superior carriers to immobilize metal ions within facilitated transport membrane for efficient liquid separation.

研究领域: 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2026 · IF 8.8

Fabrication of photocatalytic antifouling 3D COFs/MXene membrane via oil–oil–water ternary strategy for efficient oil–water separation

Yanqing Qu,Jiahao Li,Xiaoyu Du,Hongge Jia,Jingyu Xu

With the acceleration of industrialization, oily wastewater poses a serious threat to the ecological environment. Membrane separation technology has emerged as a research hotspot due to its advantages of high efficiency and energy savings; however, membrane fouling significantly restricts its long term stable operation. This study introduces a 3D COFs/MXene composite membrane with photocatalytic self–cleaning capability for highly efficient oil–water separation. A well dispersed 3D COFs colloidal dispersion was prepared via oil–oil–water three phase interfacial polymerization, effectively overcoming the dispersion challenges of COFs materials. Ti 3 C 2 T x MXene nanosheets were synthesized using the LiF/HCl etching method. Using intermolecular hydrogen bonding, the two components were ultrasonically assembled, and a COFs/MXene composite membrane was fabricated via vacuum assisted filtration. The membrane exhibits excellent hydrophilicity (water contact angle as low as 54.3°) and underwater oleophobicity (underwater oil contact angle up to 144.9°). Under visible light irradiation, the MXene component generates reactive oxygen species (·O 2 − and ·OH), enabling photocatalytic degradation of oil contaminants adsorbed on the membrane surface and thereby imparting self–cleaning functionality. Separation performance tests reveal that the composite membrane achieves efficient separation of various oil–in–water emulsions, with a maximum water flux of 1918.9 L m −2 h −1 bar −1 . The flux for n –hexane emulsion increased to 2.1 times that of pure MXene membrane, while maintaining a rejection rate above 98.8%. Moreover, the membrane demonstrates excellent cycling stability and photocatalytic antifouling performance. This research offers a novel strategy for developing self–cleaning separation membranes and holds promising potential for application in oily wastewater treatment.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2026 · IF 3.9

Magnetic Rod-Shaped Covalently Connected MOFs@COFs Imprinted Adsorbents with Ultrahigh Adsorption Capacity for Highly Specific Adsorption of Flavonoids

Shucheng Liu,Bo Wang,Ruiheng Lu,Hongxiang Ou,Xuan Zhang

Naringin (NRG) is a bioactive substance with important pharmaceutical and industrial value. However, the major challenges in the separation of NRG arise from the complexity and low concentration of crude extracts. In this work, by integrating the advantages of magnetic separation, MOFs@COFs composite materials, and surface molecular imprinting strategy, a new kind of magnetic MOF@COF-based boronate-affinity molecular imprinted adsorbent (NH2-MIL-68-Fe3O4@COFs@BA-MIPs) was constructed. Magnetic NH2-MIL-68 substrates were prepared by the solvothermal method, aldehyde-functionalized by surface modification with 2,4,6-triformylphloroglucinol (Tp). Then, a covalent organic framework shell was grown on the surface of substrates via the Schiff base reaction. Finally, a boronate-affinity imprinted polymer was prepared via surface-initiated atom transfer radical polymerization (SI-ATRP). The as-prepared adsorbent features rapid magnetic separation. In addition, the high-density boronate-imprinted recognition sites and porous structure endow the material with a fast adsorption rate (reaching equilibrium about 60 min), a high adsorption capacity (57.29 μmol g–1), and good retention performance (92.79%) after six adsorption–desorption cycles at 308 K under pH 8.0. Moreover, the extraction rate of crude NRG by NH2-MIL-68-Fe3O4@COFs@BA-MIPs reached 93.61%. This study provides a design strategy for constructing NRG adsorbents with rapid magnetic response and has important application value in the specific separation and purification of flavonoids.

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Journal of Materials Chemistry A · 2026 · IF 9.2

Modulating Exciton Dissociation and Charge Transfer by Extending π-conjugation in Thiazole-based COFs to Boost Photocatalytic Hydrogen Evolution

Jianing Tang,Jinfeng Wang,Ziang Song,Man Wang,Haitao Song,Yujun Xie,Zhen Li

Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalytic hydrogen evolution due to their designable structures and tunable optoelectronic properties. Recently, while significant research efforts have focused on developing high-performance COF photocatalysts, the rational modulation of charge carrier dynamics through precise molecular structure regulation remains challenge. In this study, we addressed this by systemically tuning π-conjugation extension employing bithiazole, benzobisthiazole and naphthobisthiazole as building blocks. Theoretical calculation and experimental characterization revealed that extending the π-conjugation significantly enhances light absorption, facilitates the separation and transport of photogenerated charge carriers. As the result, the naphthothiazole based COF (NTz-TP-COF) exhibited the most efficient photocatalytic performance, achieving a superior hydrogen evolution rate of 92.3 mmol g -1 h -1 under visible light irradiation, substantially higher than its bithiazole (Tz-TP-COF, 4.7 mmol g -1 h-1 and benzobisthiazole (BTz-TP-COF, 29.15 mmol g -1 h -1 ) counterparts, as well as most previously reported thiazole-based COFs. Moreover, platinum photodeposited on NTz-TP-COF was found to exist predominantly in the metallic Pt 0 state and exhibits uniform particle size distribution, confirming the presence of abundant active sites for hydrogen evolution. These findings highlight the critical role of π-conjugation engineering in optimizing photocatalytic performance and provide a rational design strategy for highly efficient COF photocatalysts.

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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Constructing compressed hexagonal COFs via “Debus-Radziszewski” multicomponent reaction based on “two-in-one” monomers for Ba2+/Pb2+ separation

Jingyang Zhou,Ningning He,Pan He,Yang Li,Lijian Ma

The “two-in-one” strategy has been widely adopted for constructing diverse covalent organic frameworks (COFs) due to its excellent solvent adaptability. However, its reliance on simple single component reactions limits access to COFs with higher complexity and functionality. Herein, we integrated multicomponent reactions (MCRs) with the “two-in-one” strategy for the first time, fabricating three dual-linkage COFs (TAPQ-COF, 2,3-DHTAPQ-COF, and 2,5-DHTAPQ-COF) featuring compressed hexagonal pore structures. The concurrent presence of imine and imidazole linkages in the COF skeletons induced distinct crystallization pathways compared to counterparts with single linkage. Crucially, hydrogen bonding was found to modulate final crystallinity by influencing crystallization pathways. When applied to Ba 2+ /Pb 2+ separation—simulating the isolation of medical radionuclide 212 Pb from 224 Ra/ 212 Pb or 228 Ra/ 212 Pb generators—the isomeric 2,3-DHTAPQ-COF significantly outperformed 2,5-DHTAPQ-COF in adsorption performance. 2,3-DHTAPQ-COF exhibited exceptional selectivity for Pb 2+ (separation coefficient β Pb/Ba up to 54.2). Experimental and theoretical evidence revealed that the enhanced selectivity originates from the enhanced coordination ability of ortho-hydroxyl groups. This work ingeniously merges MCRs with the “two-in-one” strategy, expanding the structural diversity of COFs accessible through simplified synthesis and broadening the scope of MCR applications. The superior Ba 2+ /Pb 2+ separation capability of 2,3-DHTAPQ-COF provides new insights for designing COFs targeting medical radionuclide purification.

CAS / MDL: 10022-31-8 10099-74-8
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

3D Interwoven COFs nano-network: Synergistic integration of CO2-philic and low-resistance transport through continuous electrospun-based pathways

Ziheng Li,Fengting Yao,Wenji Zheng,Xuehua Ruan,Yan Dai,Xiaobin Jiang,Xuemei Wu,Gaohong He

The performance upper bound of mixed-matrix membranes (MMMs) stems from discontinuous filler dispersion and impaired transfer kinetics. Herein, we propose to construct 3D interpenetrating covalent organic frameworks (COFs) architecture synergizing physisorption and rapid gas molecular transport to enhance CO 2 separation. Electrospun polyacrylonitrile (PAN) nanofibers induce the heterogeneous epitaxial growth of functionalized TpPa-1/TpPa-SO 3 H to create a bi-continuous transport highway with (i) 3D-interconnected micropores (∼1.8 nm) for low-resistance diffusion and physical adsorption and (ii) multi-channel chemisorption via CO 2 -philic groups (such as amino, hydroxyl, and sulfonic acid). Resultantly, the CO 2 permeability and CO 2 /N 2 selectivity of the prepared PEO/HPAN@TpPa-SO 3 H 3 MMM were improved by 32.02 % and 62.18 %, respectively, compared with the direct-blending PEO/TpPa–SO 3 H–14.90 wt% membrane. The electrospun-based nano-network assembly establishes a material paradigm for overcoming the physico-chemical adsorption-diffusion trade-off in gas separation membranes.

研究领域: 材料科学 · 化学工程 · 纳米技术 · 环境科学
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ANALYTICA CHIMICA ACTA · 2026 · IF 6.1

Signal on–off ratiometric electrochemical immunosensor based on Au@C-COFs and Thi@aCOFs for ultrasensitive IGF-1 detection

Zimiao Wen,Xinhua Lian,Zihan Zhang,Haiyan Zhao,Na Li,Min Cui,Cong Zhang

Insulin-like growth factor-1 (IGF-1) is a critical biomarker linked to various human diseases, necessitating sensitive and reliable detection methods. Herein, we report a novel sandwich-type ratiometric electrochemical immunosensor with signal on–off capability for the ultrasensitive measurement of IGF-1. The sensor was constructed using gold nanoparticle-engineered carbonized covalent organic frameworks (Au@C-COFs) as the sensing platform and thionine-enriched alkynyl COFs (Thi@aCOFs) as the signal amplification probe. Au@C-COFs exhibited excellent electrocatalytic activity toward hydroquinone (HQ) oxidation, providing a stable internal reference signal, while Thi@aCOFs generated a concentration-dependent reporter signal upon specific recognition of IGF-1 via the immobilized aptamer. The ratiometric strategy effectively eliminated external interferences, significantly enhancing accuracy and reliability. Under optimal conditions, the biosensor displayed a wide linear range from 10 fM to 1 nM, a low detection limit of 0.45 fM (S/N = 3), good specificity, stability, and satisfactory reproducibility. Furthermore, the sensor performed well for measuring IGF-1 in diluted human serum, achieving satisfactory recoveries. This work presents a robust and adaptable platform toward ratiometric electrochemical biosensing, holding great promise to achieve clinical diagnosis and management treatment of IGF-1-related disorders.

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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

The construction of COFs functionalized CRISPR electrochemical sensor for ultrasensitive detection of bacteria by hyper-branched rolling circle amplification

Jialin Zhang,Ming Zhou,Biyao Mao,Bin Huang,Herui Wen,Jiali Ren

Rapid, sensitive, and low-cost foodborne pathogens detection is crucial for dealing with foodborne diseases caused by bacteria. In this work, we designed a new CRISPR/Cas9-mediated electrochemical biosensor for ultrasensitive detection of Escherichia coli ( E. coli ) based on multifunctional covalent organic framework-based nanocomposite (GOx-AuNPs-COF-H2) and hyperbranched rolling circle amplification (HB-RCA) reaction. When specific DNA targets were present in the system, the targets could be recognized and cleaved by CRISPR-Cas9 system, which triggered strand displacement reaction (SDR) and HB-RCA reaction. By introducing GOx-AuNPs-COF-H2 nanocomposite, H2 probe could hybridize with RCA products to bind to the electrode surface. After added glucose solution, GOx could catalyze it in the detection system and thus offered significant current signals for bacteria detection. This approach showed high analytical performance for assay of E. coli with the detection limit (LOD) of 10 CFU/mL. Furthermore, real samples were detected by this approach, demonstrating its promising potential for foodborne pathogens detection in food monitoring and clinical diagnosis.

研究领域: 生物传感器 · 分子生物学 · 分析化学 · 食品安全
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JOURNAL OF MEMBRANE SCIENCE · 2021 · IF 8.742

Sulfonated covalent organic frameworks (COFs) incorporated cellulose triacetate/cellulose acetate (CTA/CA)-based mixed matrix membranes for forward osmosis

Xiaogeng Lin,Yasan He,Yuting Zhang,Wanyin Yu,Tao Lian

The comparably low performance hinders the application of CTA based forward osmosis (FO) membranes. Herein, sulfonated-COFs incorporated CTA/CA membranes were designed to enhance the FO performance, taking advantages of the sulfonated COFs with high hydrophilicity, size exclusion and electrostatic repulsion to salt. Two COFs with different pore size were synthesized and sulfonated to prepare hydrophilic COF-SO 3 H. The COF-SO 3 H with different loading was then added into CTA/CA casting solution to fabricate incorporated membranes. Characterizations and FO tests revealed that an appropriate amount of COF-SO 3 H in the membrane matrix could increase membrane porosity, reduce structural parameter (S), bring more negative charges and improve hydrophilicity, leading to enhanced permeability, higher selectivity and suppressed internal concentration polarization. One of the synthesized COF-SO 3 H, named TATP-SO 3 H, had a pore size of 0.84 nm, ideal for both easy passthrough of water and high rejection to salt. The XPS results verified the existence of H-bonding between TATP-SO 3 H and CTA/CA. The membrane with 0.2 wt% TATP-SO 3 H loading had the best porosity and S, and achieved high flux (13.34 LMH) and selectivity ( J w /J s 6.26 L/g) in FO mode, both of which were 2–3 times of those of the neat CTA/CA membrane and the unfunctionalized-COFs incorporated membrane.

研究领域: 材料科学 · 环境工程
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