RSC Advances
·
2024
·Vol. 14
·期 38
·28148-28159
·
IF 3.9
Lidi Gao,Xinran Qu,Shuang Meng,Mo Chen,Yuxin He,Fuquan Zhao,Hongtao Chu,Shili Qin,Fenglong Jin
The excellent stability of covalent organic frameworks (COFs) and the diversity of metal organic frameworks (MOFs) make MOF/COF hybrid materials promising candidates for chromatographic stationary phases. In this paper, a TpBD/UiO-66-NH2 hybrid material was synthesized through a Schiff-base reaction between TpBD COFs and UiO-66-NH2 MOFs; characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy; and bonded to a capillary to prepare a TpBD/UiO-66-NH2-bonded open tubular capillary electrochromatography (OT-CEC) column. Results suggested that the hybrid material had the crystal morphology of a single COF and MOF, a micro–mesoporous structure, and good thermal stability. The inner surface of the OT-CEC column was tightly and uniformly distributed with the stationary phase (∼1.5 μm). The baseline separation of 13 amino acids and three families (4 acidic antibiotics, 4 preservatives and 6 sulfonamides) of emerging pollutant mixtures was achieved due to the synergistic effect of TpBD and UiO-66-NH2 in the stationary phase. The OT-CEC column showed good reproducibility and stability with relative standard deviations of migration time and resolutions in the range of 1.17–3.93% and 1.79–4.31%, respectively.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2024
·
IF 4.9
Qin Cheng,Jinping Gan,Kai Cai,Ming Xia,Yi Wu,Shanshan He,Pan Cheng,Qihao Guo,Ke Liu,Dong Wang
High-quality polyamide (PA) nanofiltration (NF) membrane with excellent selectivity and permeability is of great research significant because of their high practical application value, especially for the precise separation of divalent and monovalent ions, such as Mg 2+ and Li + . Herein, UiO-66-NH 2 nanoparticles (NPs) decorated ethylene vinyl alcohol copolymer (EVOH) nanofiber substrate (M-NFM) was utilized to construct high-quality Janus NF membrane through interfacial polymerization (IP) reaction using polyethyleneimine (PEI) and piperazine (PIP) as aqueous phase monomers and trimesoyl chloride (TMC) as organic phase monomers. The incorporation of UiO-66-NH 2 NPs significantly influenced the hydrophilicity, surface morphology, and pore structure of the substrate, thereby enhancing the properties of the resulting NF. Optimally prepared membranes demonstrated improved separation performance, permeability, stability, and antifouling characteristics compared to the unmodified substrate. Notably, at a Mg 2+ /Li + ratio of 30, the resultant NF membrane achieved a separation factor (S Mg 2+ /Li + ) of 28.4 and a salt permeation flux of 156.8 L·m -2 ·h -1 ·MPa -1 . Additionally, the membrane exhibited over 98% rejection rates for FeCl 3 , CuSO 4 , CaCl 2 , MgSO 4 , MgCl 2 and Na 2 SO 4 with fluxes exceeding 150 L·m -2 ·h -1 ·MPa -1 , highlighting its effectiveness in rejecting multivalent ions. This research presents a simpler and more reliable approach to the fabrication of high-quality Janus PA NF membrane, offering promising potential for industrial-scale applications.
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CHEMICAL PAPERS
·
2026
·
IF 2.7
Zhong Xiangyan,He Xinye,Long Ruiqing,Qi Linfeng,Zhao Qiang
Efficient utilization of long-wavelength visible light remains a key challenge in developing metal-organic-framework-based photocatalysts for solar-driven pollutant removal. To address this issue, carbon quantum dot (CQD)-modified UiO-66-NH 2 hybrid materials with different nominal CQD loadings were constructed through induced loading and secondary thermal fixation to combine spectral conversion with interfacial photophysical regulation. Structural and textural characterizations showed that CQD incorporation preserved the crystalline and porous framework of UiO-66-NH 2 while modifying its surface composition, pore characteristics, and optical response. The CQDs displayed visible-to-ultraviolet anti-Stokes emission centered at approximately 340 nm under 600 nm excitation. CQD incorporation also enhanced visible-light absorption and induced photoluminescence quenching consistent with interfacial photophysical coupling. Transient-current measurements showed reproducible light-switching responses, while EIS revealed a lower impedance response for CU-3 under illumination; together, these results are consistent with facilitated interfacial charge migration. Under visible-light irradiation in the presence of FeCl 3 as an electron scavenger, CU-3, containing 3 wt% CQDs, achieved a background-corrected net methyl orange removal of 67% within 90 min. Its apparent rate constant was 1.203 × 10 − 2 min − 1 , approximately 6.6 times that of pristine UiO-66-NH 2 . Tert-butanol inhibition and DMPO spin-trapping ESR measurements jointly supported the involvement of hydroxyl radicals, with CU-3 exhibiting a stronger light-induced DMPO–·OH signal than pristine UiO-66-NH 2 . The effect of EDTA-2Na could not be assigned exclusively to photogenerated holes because of its complexation with Fe 3+ . These findings demonstrate the importance of optimizing CQD loading and suggest that spectral conversion and interfacial photophysical coupling contribute to the enhanced apparent visible-light activity.
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BIOSENSORS & BIOELECTRONICS
·
2026
·
IF 11.8
Jixiang Li,Genyun Zhou,Fei Wu,Jinping Yuan,Linan Hu,Qiang Zhang,Wenge Yang,Yonghong Hu
Tetracycline (TC) is a persistent broad-spectrum antibiotic that poses significant threats to human health and the environment. Herein, we developed an ultrasensitive photoelectrochemical (PEC) biosensor for rapid TC detection. The sensor utilizes a flexible Si-doped carbon fiber membrane derived from polyacrylonitrile and dimethyldiethoxysilane as a conductive substrate. After coating with poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS), a ternary UiO-66-NH 2 /Ag/g-C 3 N 4 Z-scheme heterojunction is assembled as the photoactive core, followed by electrostatic immobilization of laccase to achieve specific TC recognition. Electrochemical characterization confirmed that laccase improved both the biocatalytic activity and electron-transfer efficiency of the electrode. Combined with transient photocurrent measurements and molecular dynamics simulations, the sensing mechanism was shown to be dominated by steric hindrance arising from TC occupation of the laccase active site, followed by oxygen consumption, yielding a detection limit of 0.012 μM over 0-30 μM TC (R 2 = 0.993). UV diffuse reflectance spectra (UV-DRs), Mott–Schottky analysis (M-S), and electron paramagnetic resonance (EPR) measurements further verified that the Ag-mediated Z-scheme pathway significantly enhanced carrier separation. With excellent stability and anti-interference performance in real river water and complex matrices, this work provides an effective strategy for antibiotic detection by integrating flexible carbon-based substrates with advanced Z-scheme photocatalytic systems.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Bin Zhao,Yue Li,Min Sun,Zhaohui Zhang,Liang Wang,Jiaxue Yao
The growing concern over pharmaceutical and personal care products (PPCPs) in drinking water sources underscores a serious public health risk. Although polyamide (PA) nanofiltration (NF) membranes are highly effective at removing PPCPs, their performance for neutral and hydrophobic PPCPs requires improvement. To overcome this challenge, we fabricated a hydrophilic NF membrane containing a calcium alginate (CaAlg) hydrogel interlayer and UiO-66-NH 2 nanofillers (PA/UiO-66-NH 2 /CaAlg) to reduce membrane affinity for hydrophobic PPCPs. A fishnet-like structure was created on the membrane surface, which enhanced the effective area for filtration. Consequently, the water permeance of the PA/UiO-66-NH 2 /CaAlg membrane reached 22.7 L·m −2 ·h −1 ·bar −1 , representing an 83 % increase over the control thin-film composite (TFC) membrane. The hydrophilic CaAlg interlayer also restricted the diffusion of piperazine (PIP), thereby slowing its interfacial polymerization with trimesoyl chloride (TMC). This resulted in a highly hydrophilic PA film, evidenced by a water contact angle below 10°. The reduced adsorption of hydrophobic PPCPs on this hydrophilic surface diminished the driving force for their penetration. Furthermore, the inherent hydrophilicity of the CaAlg hydrogel interlayer suppressed the diffusion of hydrophobic PPCPs across the membrane. As a result, the removals for hydrophobic methylparaben (MP), propylparaben (PP), bisphenol A (BPA), and benzylparaben (BP) were significantly enhanced. The selectivity ( A/B ) for BPA increased by more than four times compared to that of the TFC membrane. This study demonstrates that integrating a hydrogel interlayer with MOF nanofillers offers a promising approach for developing high performance NF membranes that exhibit both improved water permeance and superior PPCP removal.
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BIOMACROMOLECULES
·
2026
·
IF 5.9
Zehui Wei,Shuxian Ge,Yukai He,Lina Mu,Shuangxian Yan,Yu Cheng,Tiantian Gao,Kefan Xie,Miaomiao Zhang,Suhong Wang,Mei Tian
Carbohydrate antigen 15-3 (CA15-3) is an important biomarker for early breast cancer diagnosis and therapeutic monitoring. This work presents an ultrasensitive fluorescent probe based on a dual-ligand peptides/UiO-66-NH2@AYG composite for CA15-3 detection. Dual-ligand peptides (GTTFSNYW and MHYLEYPF) target distinct CA15-3 epitopes, enhancing the binding affinity and specificity. The peptides are immobilized on UiO-66-NH2, whose high surface area supports efficient loading of the fluorescent reporter Acridine Yellow G (AYG). This probe demonstrates exceptional performance with a linear detection range of 0.05–1.5 pg/mL (R2 = 0.9981) and an ultralow detection limit of 0.004147 pg/mL. Practical validation in spiked mouse serum shows recovery rates of 91.57–103.7%, while clinical testing with serum samples from 10 cancer patients reveals a strong correlation with ELISA results (r = 0.9944, P < 0.001). This robust platform offers significant potential for cost-effective, early cancer screening in primary healthcare settings.
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TRANSACTIONS OF TIANJIN UNIVERSITY
·
2025
·
IF 8.5
Song Yanyan,Sun Zhichao,Sun Jiamin,Liu Ying-Ya,Wang Anjie,Peng Chong
The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry. In this study, we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO 2 /UiO-66-NH 2 hybrid material with abundant oxygen vacancies, enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde. By optimizing the solvothermal treatment duration, the composite (UiO-66-NH 2 -2 h) achieves a 74.1% conversion of benzyl alcohol with > 99% selectivity toward benzaldehyde under mild conditions, substantially outperforming pristine UiO-66-NH 2 . Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall, uniformly dispersed ZrO 2 nanoparticles (~ 2.3 nm) within the MOF matrix, while simultaneously generating abundant oxygen vacancies, as confirmed by XPS, EPR, and HRTEM analyses. The defect-mediated electronic structure of the ZrO 2 /UiO-66-NH 2 hybrid enhances visible-light absorption, facilitates charge carrier separation, and promotes efficient activation of O 2 into superoxide radicals (·O 2 − ), the primary reactive species. Transient photocurrent measurements and electrochemical impedance spectroscopy further verify the improved charge separation efficiency. The synergistic interplay between oxygen vacancies and the intimate ZrO 2 /UiO-66-NH 2 interface provides a unique defect-mediated charge transfer pathway, distinguishing this system from conventional heterojunctions. This study demonstrates a facile, one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts, offering a scalable route for solar-driven organic synthesis. Graphical
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IRANIAN POLYMER JOURNAL
·
2023
·Vol. 32
·期 8
·979-990
·
IF 3.1
Fu Mengjie,Wang Chun,Lai Xing,Xiao Changfa,Ding Ying
In terms of nanofiltration (NF) membrane development, the properties of membrane substrates and thin-film composite (TFC) structures have become an important factor to determine the separation performances of NF membrane. In this paper, the method of interfacial polymerization assisted by spacer spraying was used to construct the striped structure at nanometer scale. Nanoscale striped structure was prepared successfully on PPTA (poly( p -phenylene terephthamide)) NF surface with 1.3 g/L of UiO-66-NH 2 in the aqueous phase, and the morphology gradually changed to “point shaped” structure when 2.6 g/L of UiO-66-NH 2 in the aqueous phase. The optimized PPTA/UiO-66-NH 2 NF (PU4) membranes were used for dye/salt separation of methylene blue (MB). Compared with the nascent PPTA NF membranes, it showed a higher MB rejection rate of 98.6%, along with permeation flux of 19.79 L/m 2 \(\cdot\) h \(\cdot\) MPa. The salt separation order of the PU4 membrane was Na 2 SO 4 > MgSO 4 > MgCl 2 > NaCl. The rejection rates were 96.3%, 85.4%, 53.2%, and 18.4%, respectively. Under strong acid and alkali conditions, the separation performance was rejected 86.5%, better under alkaline conditions. More importantly, after a six-time recycle, the PU4 membrane showed no significant change in separation performance, suggesting its excellent stability. The novel strategy in this study provided an approach to develop advanced UiO-66-NH 2 membranes toward sustainable molecular separation in environmental applications. Graphical abstract
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JOURNAL OF APPLIED POLYMER SCIENCE
·
2022
·Vol. 139
·期 31
·e52724
·
IF 3.057
Chunhui Du,Jintai Hu,Fen Chen
Polypropylene (PP) porous flat membrane is ultrathin and has high porosity, which is suitable for the support of forward osmosis (FO) membrane. However, its high hydrophobicity is its Achilles heel. In this study, dopamine and UiO-66-NH 2 were co-deposited onto the surface of PP support, and then interfacial polymerization was performed to fabricate a thin-film nanocomposite (TFN) FO membrane. The reaction-generated polydopamine improved the hydrophilicity of PP membrane, and at the same time enhanced the adhering of UiO-66-NH 2 to the support. The experimental results indicated that the UiO-66-NH 2 nanoparticles were anchored evenly on the surface of the support, which improved the water flux of FO membrane from 11.1 LMH (TFC, TFN-0 without UiO-66-NH 2 ) to 20.7 LMH (TFN-0.1, with 0.1 wt% UiO-66-NH 2 ) using 1 mol/L NaCl as the draw solution in FO mode. Compared with TFC membrane, TFN-0.1 membrane also exhibited relative lower specific salt flux (~0.252) and structural parameter (~379 μm). When separating sodium alginate foulant, the normalized water flux recovery ratio of TFN-0.1 was remained 0.89, and most of the fouling was reversible, as for TFC membrane the data decreased to 0.76 after 2 cycles of operation. These results suggested that UiO-66-NH 2 modified FO membrane exhibited good permeation and antifouling property.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2023
·
IF 6.1
Qin Zhang,Lijiao Fan,Wenbin Liu,Yuming Xie,Jiangang Li,Guolin Huang
The core–shell structure UiO-66-NH 2 @Ni-MOF was prepared by in-diffusion growth of 2D Ni-MOF on UiO-66-NH 2 using PVP (polyvinylpyrrolidone) as a structural guide. It was applied to the adsorption of U(VI) in aqueous solution. The materials were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive spectrometer (EDS). The UiO-66-NH 2 @Ni-MOF adsorption to U(VI) was investigated experimentally. The study showed that the adsorption of U(VI) onto UiO-66-NH 2 @Ni-MOF was endothermic and spontaneous. At pH 5.00 and 308 K, the adsorption capacity was 581.40 mg/g according to Langmuir model. In addition, the adsorption process can be described by the pseudo-second-order kinetic model. The adsorption capacity was kept at 83.83% of its original one after five sorption–desorption cycles, a promising indication for repetitive usage.
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2023
·Vol. 30
·期 51
·111039-111050
·
IF 5.8
Dong Shiwen,Liu Xuan,Kong Xianxian,Dong Feilong,Yu Yan,Wang Lizhang,Wang Da,He Zhiqiao,Song Shuang
Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been proved as efficient catalysts for photocatalytic hydrogen (H 2 ) evolution, thanks to their tunable functionalities, permanent porosity, excellent visible light response, and physicochemical stability. Herein, a series of photocatalysts (termed NUBC) was fabricated by loading different amounts of Zr-UiO-66-NH 2 (NU) onto a benzoic acid–modified covalent triazine–based framework (BC) based on post-synthetic covalent modification. The resulting NUBC catalysts exhibited a type-II Z-scheme heterojunction structure formed via the amide covalent bonds between the amine groups on NU and carboxyl groups on BC. The optimal loading of NU on BC is 30 wt.% (30NUBC) and the corresponding photocatalytic H 2 evolution rate was 378 μmol h −1 g −1 , almost 445 and 2 times than that of NU and BC, respectively. The synergistic effect between the type-II Z-scheme heterojunctions and amide bonds was conducive to boosting visible light harvesting and facilitating charge transportation and separation. Furthermore, the prepared NUBC catalysts show great reusability and stability. Overall, this work sheds light on the design of novel MOF/COF hybrid materials and provides a systematic exploration of their photocatalytic H 2 evolution properties.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jiayou Liu,Xiaoxiang Huang,Lizhen Hu,Penglei Liu,Liuhu Jia,Keiko Sasaki,Zhongchao Tan,Hesheng Yu
Simultaneous avoidance of secondary air pollution and catalyst deactivation remains a challenge for existing photocatalytic removal of nitric oxide (NO). Herein, a photocatalysis-adsorption (P-A) heterojunction is synthesized for eco-friendly NO removal by facilely grinding Pd single atoms (Pd 1 ) anchored g-C 3 N 4 (48CN/Pd) with UiO-66-NH 2 (UION). Under visible-light irradiation, the 40UION-CN/Pd composite shows 93.91 % of NO removal efficiency with only 2.73 % of NO 2 emissions and negligible catalyst deactivation. The DeNO x index increases remarkably from −0.66 for 48CN/Pd to 0.86 for 40UION-CN/Pd. Furthermore, the synthesized P-A heterojunction efficiently removes NO from real flue gases produced by a domestic coal-fired stove and from SO 2 -rich flue gases. The mechanism exploration based on experimental investigations and density functional theory (DFT) calculations reveals that UION captures the NO 2 selectively produced by 48CN/Pd, simultaneously suppressing NO 2 emissions and refreshing active sites for NO photooxidation. Moreover, the results of X-ray photoelectron spectroscopy (XPS), charge density difference calculation, energy-resolved distribution of electron traps (ERDT) and in-situ Kelvin probe force microscopy (KPFM) reveal that the built-in electric field and Type-II heterojunction formed between 48CN/Pd and UION promote the separation of photogenerated carriers, enhancing the catalytic activity of the composite. This work provides an innovative strategy to avoid NO 2 emission and catalyst deactivation during photocatalytic NO removal.
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