ACS Applied Materials & Interfaces
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2022
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IF 10.383
Yiming Wang,Haimeng Tian,Hong Li,Xinchen Deng,Qiao Zhang,Yongjian Ai,Zejun Sun,Yu Wang,Lei Liu,Ze-Nan Hu,Xinyue Zhang,Rongxiu Guo,Wenjuan Xu,Qionglin Liang,Hong-bin Sun
Cascade reactions take advantage of step-saving and facile operation for obtaining chemicals. Herein, catalytic hydrogenation of nitroarene coupled condensation with β-diketone to afford β-ketoenamines is achieved by an integrated nanocatalyst, Pd-e@UiO-66. The catalyst has the structure of an acid-rich metal–organic framework (MOF), UiO-66-encapsulated electron-rich Pd nanoparticles, and it reconciles the electron-effect contradiction of cascade catalytic reactions: catalytic hydrogenation requires an electron-rich catalyst, while condensation requires electron-deficient Lewis acid sites. The catalyst showed good activity, high chemoselectivity, and universal applicability for the synthesis of β-ketoenamines using nitroarenes. More than 30 β-ketoenamines have been successfully prepared with up to 99% yield via the methodology of relay catalysis. The catalyst exhibited excellent stability to maintain its catalytic performance for more than five cycles. Furthermore, we conducted an in-depth exploration of the reaction mechanism with theoretical calculations.
研究领域:
化学
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催化材料科学
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DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
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2022
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IF 8.047
Hong Li,Yiming Wang,Rongxiu Guo,Jianwei Zheng,Zejun Sun,Xinyue Zhang,Ying Guo,Hongna Jia,Qionglin Liang,Hong-bin Sun
The heterogeneously tandem catalytic synthesis is a step-economic and work-up-saving strategy for producing chemicals, but it usually requires a special catalyst to achieve the sequential catalytic reactions . The development of metal organic frameworks provides an opportunity to fabricate multifunctional catalysts. In this work, a MOF-based sandwich-nanostructure catalyst UiO-66-NH 2 @Pt@PCN-222 is fabricated, which is made of the UiO-66-NH 2 as the core, Pt nanoparticles as the interlayer, and the defective PCN-222 as the shell. The developed catalyst shows outstanding performance for the tandem catalytic synthesis, which is the hydrogenation of nitroarenes cascaded with β-dicarbonyl compounds to form β-ketoenamines. The selectivity of β-ketoenamines reached 98% upon the completed hydrogenation of p-nitrotoluene. The stable PCN-222 shell can be regarded as an active armor, which not only protects the Pt particles from leaching or agglomerating, but also has plenty of acid sites that are conducive to the second-step condensation. At the same time, the kinetic studies show that the armor layer also affects the activity of hydrogenation, so that the hydrogenation and condensation reactions can proceed simultaneously to give the best selectivity. Various substituted dicarbonyl compounds and structurally different nitroarenes completed the conversion with excellent conversion (90–99%) and selectivity (87–98%), and this nanocatalyst can be recycled for up to six cycles without the expense of activity.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Ziqi Zhao,Shaokun Liang,Chengjun Kang,Zhaoqiang Zhang,Liqin Zhou,Zhenxia Zhao,Xingzhen Qin,Yushan Pang,Hongbing Ji,Kungang Chai
Adsorption is considered as a promising method to purify the mixed acetophenone (AP) and 1-phenylethanol (1-PE) that are generally difficult to separate. Many efforts have been made to improve the preferential uptake of AP over 1-PE in aqueous phase, but there exists a practical bottleneck associated with their limited aqueous solubility. Herein, we demonstrate unprecedented reversal of selectivity in the organic medium enabled by β-ketoenamine-linked covalent organic frameworks (COFs), which were fabricated successfully by polycondensation between 1,3,5-triformylphloroglucinol (Tp) and diamines. The dependence of selective adsorption ability toward 1-PE on pore size was firstly investigated experimentally, indicating that TpBZ-COF with moderate pore size outperformed other analogues. The adsorption behaviors of 1-PE and AP onto TpBZ-COF were examined systematically. The evaluation results revealed a strong affinity toward 1-PE versus AP as well as excellent stability in recycling experiments. Further, the dynamic breakthrough experiments confirmed the practical application potential and remarkable recyclability. To probe the mechanism and structure–activity relationship, an imine-linked COF possessing similar porous structure was used as a reference for comparison of separation performance both experimentally and theoretically. The occurrence of hydrogen bonding between the hydroxyl of 1-PE and β-ketoenamine-linkage as H-bond acceptor in suitable pore spaces endows TpBZ-COF a fantastic candidate for purifying 1-PE and AP from petrochemical by-products.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2025
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IF 9
Zhihong Dong,Ying Zhu,Xuexi Zhang,Xinliang Zhang,Xueting Zhao,Jiefeng Pan
Covalent organic frameworks (COFs) are ideal materials for engineering molecular sieves membranes. Colloidal COFs play an important role in the preparation of defect-free COF membranes. Herein, we present the alkali-mediated approach to synthesize uncharged β -ketoenamine-linked COFs with high colloidal dispersibility that can serve as preferred membrane-forming materials. The colloidal β -ketoenamine-linked COFs are synthesized in the single solution-phase system and alkali is employed to regulate the reversible dynamic amine-aldehyde condensation process by directing the weak hydrogen bond networks. The colloidal COFs obtained from alkali-mediated synthesis exhibit promoted crystallinity and outstanding dispersity for membrane construction. Furthermore, the alkali-mediated synthesis approach is universal and suitable for synthesizing a series of colloidal β -ketoenamine-linked COFs without the limitations of charged monomers or frameworks. The colloidal COFs are further assembled into COF membranes by vacuum-assisted assembly. Thanks to the intrinsic regular pore structure of COFs, the COF membranes exhibit high permeability (58 L m −2 h −1 ·bar −1 ) and can achieve accurate screening of dye molecules. This work provides a facile and scalable synthesis strategy for uncharged colloidal COFs, and can be employed to develop COF membranes for on-demand molecule separation.
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产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2025
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IF 9
Xuan Wang,Jiaojiao Duan,Weiliang Li,Xiaoli Wu,Yong Wang,Mingjie Wei,Yifan Li,Runnan Zhang,Jingtao Wang
Covalent organic framework (COF) materials hold significant promise for membrane technology due to their precisely defined porous structures and tunable functionalities. However, the stability of COF membranes in organic solvents, critical for long-term operation, has seldom been studied and remains unclear. This study synthesizes three β-ketoenamine type COF membranes with different amounts of sulfonate groups via vacuum-assisted assembly and systematically evaluates their stability in four typical organic solvents (alcohol, ketone, ester, and alkane), respectively. We investigated the time-dependent membrane morphologies, thickness swelling, and long-term organic solvent nanofiltration (OSN) performance within a period of up to 180 days. Although the COF membranes suffer from a certain degree of structural change and permeance decline during the initial testing period, they can finally achieve quite stable separation performance. The effects of solvent type and the number of –SO 3 H groups on membrane stability are systematically discussed. Based on the evaluation methods adopted in this study, the prospects of COF membranes for long-time application in organic solvent can be highlighted, but some critical problems are also raised. We also investigate the swelling behavior under harsh conditions (e.g. elevated temperature, strong acids, and alkalis) to accelerate the swelling process, which is found to enable fast and effective evaluation of the long-term stability.
研究领域:
材料科学
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化学工程
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产品关联
DOI
高影响因子
JOURNAL OF SEPARATION SCIENCE
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2022
·Vol. 45
·期 9
·1493-1501
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IF 3.614
Chengjiang Zhang,Hongmei Yuan,Zeyi Lu,Yuhuang Li,Lirong Zhao,Zhuomin Zhang,Gongke Li
Covalent organic frameworks with tunable porous crystallinity and outstanding stability have exhibited fascinating pretreatment performance as ideal extraction media. Herein, the β-ketoenamine-linked TpPa-1 synthesized by 1,3,5-triformylphloroglucinol and paraphenylenediamine was employed as the absorbent for online micro-solid phase extraction of trace bisphenols combined with high-performance liquid chromatography detection. A series of characterizations indicated that the TpPa-1 possessed large surface areas, high stability, and hydrophobicity. The main experimental parameters affecting the extraction efficiency were optimized in detail. Compared with four commercial sorbents, the TpPa-1 exhibited superior enrichment capacity for extracting bisphenols. Under the optimum conditions, the established method demonstrated a wide linear range and high sensitivity with the limit of detection ranging from 0.05–0.06 μg/L. Furthermore, the developed method was successfully applied to determine bisphenols in plastic samples. Bisphenol A was actually detected in a transparent box with a concentration of 0.31 μg/g, and the recoveries of the four bisphenols in the plastic samples were 80.5–116% with the relative standard deviation less than 9.2%. Such performance was attributed to recognition affinity, including the π-π affinity, hydrophobic effect, and hydrogen bond. These results demonstrated that TpPa-1 possessed great potential to be an excellent pretreatment medium for online separation and analysis of trace analytes in complex samples.
研究领域:
分析化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
TALANTA
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2022
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IF 6.556
Qidong Yu,Yaping Wu,Wenmin Zhang,Wende Ma,Juan Wang,Hui Chen,Qingqing Ding,Lan Zhang
Rapid and convenient preparation of covalent organic framework (COF) coated fibers is of great significance to solid-phase microextraction (SPME) technology. In this work, a novel chemical preparation strategy was established for rapid fabrication of β -ketoenamine-linked COF coatings, in which clay-like starting materials of COFs were first wrapped on the fiber surface through self-viscosity and further fixed on the fiber in an oven via chemical bonding. Based on this strategy, four different COF (TpTph, TpPa-1, TpBD and TpTpb) coated fibers was fabricated within 1 h, which is very rapid compared to the recently reported research. Moreover, the strategy also demonstrates the good general applicability for COF fiber preparation. Subsequently, the TpTph coated fiber was used to develop a new SPME method for gas chromatography-tandem mass spectrometry (GC-MS/MS) of trace phthalic acid esters (PAEs) in environmental water. The developed analytical method compared to the previous SPME methods for PAEs based on other sorbents possesses low limits of detection (LODs, 0.02–0.08 ng L −1 ), and better or comparable precision (RSD ≤9.4%, n = 6), and relatively short extraction time. Furthermore, the trace PAEs (0.27–11.62 ng L −1 ) in the real water samples were successfully detected with recoveries of 82.2–117.5%. The above results indicates that the proposed fiber preparation strategy is reliable and opens a potential avenue for rapid and facile fabrication of COF coated fibers.
研究领域:
分析化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
ANALYTICA CHIMICA ACTA
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2022
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IF 6.911
Yalan Hu,Yueru Shi,Yuefan Liu,Yixin Kuang,Suxin Zhou,Luyi Chen,Sai Ouyang,Ningbo Zhou,Juan Zheng,Gangfeng Ouyang
Aromatic esters have been widely used in daily life with non-ignorable dangers, such as plasticizer , flavor , and preservative. Their wide applications and corresponding hazards caused by overuse have promoted the rapid development of sensitively analytical method for effective regulation. However, the variety makes it challenging for broad-spectrum and simultaneous extraction of diverse aromatic esters from the highly complex cosmetic samples. To our delight, a covalent organic framework, named DaTp (1, 3, 5-triformylphloroglucinol-2, 6-diaminoanthracene), possessing high specific surface, excellently thermochemical stability, and abundant electron-rich heteroatoms , has been synthesized and fabricated as a competitive solid phase microextraction coating for extracting the trace analytes with diverse polarity, through the hydrophobic interaction, π-π conjugation and hydrogen bond . Herein, this self-made SPME fiber has been further coupled with gas chromatography-tandem mass spectrometry (GC-MS) to determine the multi-polar aromatic esters in cosmetics packaged with plastic. This developed analytical method showed wide liner ranges, low limits of detection, good repeatability and reproducibility. Finally, the aromatic esters in four cosmetic samples were quantified precisely with satisfactory recoveries (80.7%–118%).
研究领域:
分析化学
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材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Liying Yin,Yingnan Zhao,Yanmei Xing,Huaqiao Tan,Zhongling Lang,Wingkei Ho,Yonghui Wang,Yangguang Li
Covalent organic frameworks (COFs), as new promising photocatalysts, have aroused great interests, but the systematic study on the structure–property relationship of COF-photocatalysts is scarcely reported. Herein, six β-keto-enamine-based COFs with different backbones and substituents have been prepared. Through systematic experiments and DFT calculation, the structure–property relationships of the composition, structure and substituents of COFs on their spectra, specific surface area, hydrophobicity, electronic structures, carrier separation and photocatalytic hydrogen production have been studied. We explore that the backbone of COFs has important influence on their band gap, spectral absorption and carrier separation. While the substituents affect the band positions, surface area and hydrophobicity of COFs. Comprehensively, TpPa-Cl 2 (constructed by 1,3,5-triformylphloroglucinol and 2,5-dichloro-1,4-phenylenediamine) exhibits the best area-normalised photocatalytic performance for hydrogen production, which is about 11.73 µmol·m −2 ·h −1 (0.01 g catalysts) with apparent quantum efficiency of 17% at 400 nm. This work provides a new perspective for the rational design and construction of efficient COF-photocatalysts.
研究领域:
材料科学
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光催化
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化学
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理论化学
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产品关联
DOI
高影响因子
Analytical Methods
·
2020
·Vol. 12
·期 19
·2434-2442
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IF 2.596
Lian Wen,Peng Wu,Lei-Lei Wang,Li-Zong Chen,Ming-Lin Wang,Xia Wang,Jin-Ming Lin,Ru-Song Zhao
Covalent organic frameworks with tunable porous crystallinity and outstanding stability have recently exhibited fascinating pretreatment performance as solid-phase microextraction coatings. In this report, a β-ketoenamine-linked covalent organic framework (TpPa-1) was successfully constructed through a Schiff-base-type reaction between 1,3,5-triformylphloroglucinol (Tp) and para-phenylenediamine (Pa-1). A TpPa-1 coating was then fabricated on a stainless-steel fiber for capturing trace synthetic musks. This TpPa-1 coating exhibited strong interaction with synthetic musks because of its hydrophobicity and π–π affinity. This TpPa-1-based solid-phase microextraction methodology, coupled with gas chromatography-tandem mass spectrometry, provided high enrichment factors (1214–12 487), wide linearity (0.5–1000 ng L−1), low limits of detection (0.04–0.31 ng L−1), and acceptable reproducibility (relative standard deviation, <10%) for nine synthetic musks. Recoveries at three spiked levels in three types of water samples were between 76.2% and 118.7%. These results indicated the promising applicability of the TpPa-1 as a solid-phase microextraction fiber coating for reliably detecting trace concentrations of synthetic musks in the environment.
研究领域:
分析化学
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
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IF 19
Ying Bao,Ziwen Gao,Yuting Yan,Yujie Duan,Yao Zhao,Hao Wang,Chunsheng Xiao,Xuesi Chen
Bioorthogonal Raman probes offer significant advantages for multiplexed, background-free biological imaging due to their unique vibrational fingerprints and photostability. However, their widespread application is limited by the inherently weak Raman scattering signal, which creates a pressing need for high-sensitivity Raman probes. Here, chemically stable diacetylene (─C≡C─C≡C─) functionalized β-ketoenamine covalent organic frameworks (BDDA COFs) are synthesized as Raman probes for in vivo imaging of bone cracks. The BDDA COFs exhibited significantly enhanced Raman intensity at 2205 cm −1 (up to ≈10 5 fold vs 5-ethynyl-2′-deoxyuridine) compared to conventional alkyne-based probes. Moreover, polydopamine (PDA)-coated COFs (BDDA@PDA COFs) are prepared by utilizing the high affinity of PDA for calcium ions exposed at bone injury sites, thereby enabling highly sensitive and specific ex vivo and in vivo Raman imaging of bone cracks. The development of COFs containing alkyne groups as strong Raman imaging probes in the silent region provides a new paradigm for in vivo Raman imaging materials and also establishes a technical foundation for future applications in disease diagnosis and precision medicine.
研究领域:
材料科学
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生物医学成像
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纳米技术
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分子探针
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骨科
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
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2022
·Vol. 40
·期 4
·338-344
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IF 3.815
Yang Guang-Hui,Zhang Zhe,Yin Cong-Cong,Shi Xian-Song,Wang Yong
Two-dimensional covalent organic frameworks (COFs) with specific morphologies including nanofibers and nanoplates are highly desired in both nanoscience research and practical applications. Thus far, however, morphology engineering for COFs remains challenging because the mechanism underlying the morphology formation and evolution of COFs is not well understood. Herein, we propose a strategy of surfactant mediation coupled with acid adjustment to engineer the morphology of a β -ketoenamine-linked COF, TpPa, during solvothermal synthesis. The surfactants function as stabilizers that can encapsulate monomers and prepolymers to create micelles, enabling the formation of fiber-like and plate-like morphologies of TpPa rather than irregularly shaped aggregates. It is also found that acetic acid is important in regulating such morphologies, as the amino groups inside the prepolymers can be precisely protonated by acid adjustment, leading to an inhibited ripening process for the creation of specific morphologies. Benefitting from the synergistic enhancement of surfactant mediation and acid adjustment, TpPa nanofibers with a diameter down to ∼20 nm along with a length of up to a few microns and TpPa nanoplates with a thickness of ∼18 nm are created. Our work sheds light on the mechanism underlying the morphology formation and evolution of TpPa, providing some guidance for exquisite control over the growth of COFs, which is of great significance for their practical applications.
研究领域:
材料科学
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纳米技术
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化学工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）