MOLECULES
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2022
·Vol. 27
·期 21
·7246
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IF 4.927
Lifang Chen,Xiangzhu Ye,Ting Zhang,Hao Qin,Hongye Cheng,Zhiwen Qi
Zirconium-based metal-organic frameworks (MOFs) have attracted extensive attention owing to their robust stability and facile functionalization. However, they are generally prepared in common volatile solvents within a long reaction time. Here, we introduced environmentally friendly, cheap, and acid-based tunable deep eutectic solvents (DESs) formed from 2-methyl imidazole (MIm) and p-toluenesulfonic acid (PTSA) which significantly accelerated the assembly of zirconium-based MOF (UiO-66) without any aggressive additives. PTSA in acidic DES and ZrOCl2preliminarily formed Zr(IV) oxo organic acid framework, whereas basic DES completely dissolved the ligand of UiO-66. The strong hydrogen bond effect of PTSA and MIm efficiently accelerated the linker exchange between zirconium oxo organic coordination in acidic DES and benzenedicarboxylate linker in weak basic DES within a reaction time of 2 h at 50 °C. Thus, UiO-66 was quickly assembled with small particle sizes and used as an excellent catalyst for the acetalization of benzaldehyde and methanol. Therefore, the developed synthesis approach provides a new green strategy to quickly prepare and design various structures of metal-based compounds under mild reaction conditions.Keywords:deep eutectic solvent;metal organic framework;UiO-66;acid-base;acetalization
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DALTON TRANSACTIONS
·
2022
·Vol. 51
·期 10
·4043-4051
·
IF 4.569
Yiming Wang,Xu Zhu,Xinyue Zhang,Jianwei Zheng,Hong Li,Nianyi Xie,Ying Guo,Hong-bin Sun,Gang Zhang
The treatment of mercury pollutants in water has been wide concern. Adsorption is a promising method for mercury removal that has been extensively studied. Nevertheless, the secondary application of the immobilized Hg is seldom investigated. In this paper, the Hg adsorption behavior of UiO-66 bearing sulfhydryl groups is studied. The research shows that the porous structure and sulfhydryl groups of UiO-66-SH can effectively promote the removal of mercury from water. In addition, this work also pushes forward the sequential application of the recovered adsorbent, which contains the adsorbed mercury that may cause secondary pollution. The recovered waste adsorbent, UiO-66-S-Hg, was successfully used as an efficient catalyst for transfer vinylation, which produces value-added products, vinyl benzoates. Eight vinyl esters have been successfully synthesized with a yield of up to 89%. This methodology provides a promising way for not only the treatment of mercury contamination, but also secondary pollution protection and the resource utilization of immobilized Hg.
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Nano Research
·
2024
·
IF 9.5
Li Rushuo,Ban Tao,Zhao Danfeng,Lin Jing,Liu Zhiyuan,Wang Linmeng,Huang Xiubing,Tao Zhiping,Wang Ge
Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further to synthesize heterogeneous catalyst with highly dispersed RuNi nanoparticles (Ru 1 Ni 1.5 @UiO-66(Ce)-12 h). The construction of Ce-O-Ru/Ni heterogeneous interfaces and Ni–Ru bonds provide electron transfer channels from Ce-oxo clusters and Ni species to Ru species. Furthermore, the microenvironment and electronic structure of Ru 0 active sites were synergistically regulated by adjusting the content of metal-organic frameworks (MOFs) defects and Ni promoter, thereby enhancing the adsorption and activation ability of H–H and C=C bonds. Therefore, Ru 1 Ni 1.5 @UiO-66(Ce)-12 h achieved dicyclopentadiene saturated hydrogenation (100% conversion) to tetrahydrodicyclopentadiene (∼ 100% selectivity) under mild condition (35 °C, 1 MPa) with only 25 min. Meanwhile, the sample exhibited excellent structural stability after 6 cycles test. This study provides a promising strategy for the rational design of remarkable noble metal-based catalysts for practical applications.
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ACS Applied Materials & Interfaces
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2025
·
IF 8.2
Yuhao Liu,Xuyi Wang,Liping Chen,Ming Cheng,Hua Wang,Jiaojiao Shang,Dan Zheng,Beibo Zhang,Jianwu Lan,Shaojian Lin
Heavy metal contamination in water poses a serious global environmental challenge. In particular, hexavalent chromium (Cr (VI)) is particularly concerning due to its carcinogenicity and genotoxicity. In this work, core–shell NH2–UiO-66@UiO-67 nanoparticles (NPs) were in situ stepwise grown on sulfonated polypropylene (PP) nonwoven to fabricate a multifunctional composite (NH2–UiO-66@UiO-67/PP composite nonwoven) for efficient removal of Cr (VI). As expected, the resulting NH2–UiO-66@UiO-67/PP composite nonwoven exhibited dual functionality for efficient Cr (VI) remediation: simultaneous adsorption and visible-light-driven photocatalytic reduction, accompanied by effective sequestration of the resulting Cr (III), due to the presence of NH2–UiO-66@UiO-67 NPs. Under visible light irradiation, the composite achieved exceptional performance, reducing Cr (VI) concentrations from 0.608 mg/L to below 0.004 mg/L and lowering total Cr concentrations from 0.876 mg/L to below 0.004 mg/L, corresponding to a removal efficiency of over 99.6%. The mechanism was elucidated as an integrated adsorption-reduction-fixation process. More importantly, the composite demonstrated outstanding recyclability, retaining 80.0% of its removal efficiency after five regeneration cycles, highlighting its practical potential. Therefore, the as-obtained NH2–UiO-66@UiO-67/PP composite nonwoven can be viewed as a highly efficient material for treating Cr (VI)-contaminated wastewater through an adsorption-photocatalytic reduction pathway.
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高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Ying Gao,Ruibin Yang,Qinqin Chen,Xinhao Shen,Dapeng Li,Juanhong Li,Feng Liu,Jianhua Wu,Sanjian Ma,Guoliang Dai,Dongmei Wang,Lei Xie,Zixia Lin,Xin Liu
The large-scale production of iron sludge and the safety issues of H2O2 usage are two limitations in the promotion and application of the Fenton reaction. To further solve the problems, an active hydrogen reduction strategy was proposed. Herein, the reducing property of active hydrogen was utilized to simultaneously generate H2O2 in situ and accelerate the regeneration of ferric in the reaction process. The composite metal–organic frameworks (MOFs) Pd@UiO-66(Zr) and Pd@UiO-66(Zr)-2OH, which were stable under acidic conditions, were synthesized for hydrogen activation. Under the condition of only trace amounts of ferrous and hydrogen added, both catalysts showed excellent performance in the degradation experiments of trimethoprim. The kobs of the Pd@UiO(Zr)-66-mediated system is 0.0487 min–1, which is 1.67 times that of Pd@UiO-66(Zr)-2OH. In the pollutant degradation reaction system constructed by these two materials, both of the hydroxyl radicals and singlet oxygen play a dominant role. The Bader charge analysis showed that the charge transfer from Pd to the MOF host was higher on Pd@UiO-66(Zr) than Pd@UiO-66(Zr)-2OH, which could be a key factor in distinguishing the catalytic activity of the catalysts. In addition, both catalysts showed excellent stability over six cycles. Nearly 100% degradation of trimethoprim could be achieved. This study provides some reference for the control of emerging pollutants by UiO-66(Zr) series materials.
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PubMed
高影响因子
Journal of CO2 Utilization
·
2025
·
IF 8.4
Zhongqi Zhang,Yingjie Shen,Aosen Zhang,Yuan Zhai,Ziqing Wang,Kun Jiang,Heyun Wang
In this study, imidazole carboxylate was introduced into the structure of UiO-66 as a secondary ligand. Subsequently, a novel imidazole ligand zirconium-based UiO-66-Im- X material was prepared, which was used to catalyze the direct synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO 2 ) and methanol. The influence of imidazole carboxylate content on the physicochemical properties and catalytic performance of the UiO-66-Im- X catalyst was studied. The results showed the addition of imidazole carboxylate increased the number of ligand defects in the Zr 6 formula unit, which significantly enhanced the α-acidic sites of the UiO-66-Im- X catalyst. UiO-66-Im-0.2 with a good crystal structure exhibited the highest surface area, pore volume, and acidic sites and demonstrated the best catalytic activity. At 3.5 MPa, 140 °C, and a reaction time of 8 h, the DMC yield reached 0.9335 %. In addition, the catalytic effect of UiO-66-Im-0.2 exceeded 90 % after four recycling iterations, demonstrating excellent reusability. The in-situ infrared spectroscopy results and density functional theory (DFT) calculations demonstrated that the incorporation of the imidazole ring significantly enhanced the adsorption capacity of CO 2 molecules and reduced its adsorption energy on the UiO-66-Im-0.2 catalyst.
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JOURNAL OF ENVIRONMENTAL MANAGEMENT
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2025
·
IF 8.4
Chuan Peng,Jing Zhao,Jin Huang,Yongge Yao,Xinlin Chen,Junfeng Zhang,Xiaolong Yu
Rubidium (Rb), a critical strategic metal with extensive applications in energy storage, electronics, and nuclear medicine, faces extraction challenges due to its low natural abundance and dispersed occurrence. To address the inefficiency and selectivity limitations of conventional extraction methods, this study synthesized a core-shell composite metal-organic framework (MOF) material, KCoFC@UiO-66, via a solvothermal coordination strategy. The material synergistically integrates the ion-exchange capability of potassium cobalt hexacyanoferrate (KCoFC) with the hierarchical porosity and structural stability of zirconium 1,4-dicarboxybenzene MOF (UiO-66). Structural characterization confirmed the core-shell architecture, where the KCoFC core facilitates selective Rb capture via ion exchange and cyano coordination, while the UiO-66 shell enhances Rb enrichment through electrostatic interactions and size-selective sieving. Adsorption kinetics followed a pseudo-second-order model, indicating chemisorption dominance, while isotherm studies aligned with Freundlich and Dubinin-Radushkevich models, revealing heterogeneous multilayer adsorption. The composite demonstrated remarkable selectivity for rubidium, achieving a recovery rate of 98.7 % from lithium tailing leachates, along with notable regeneration stability, retaining 86.2 % of its capacity after five cycles. This performance can be ascribed to the ability of UiO-66 to inhibit the aggregation of KCoFC and to the effects of pore confinement. This work establishes a multi-mechanistic adsorption paradigm combining ion exchange, electrostatic attraction, and pore confinement, offering a scalable solution for Rb recovery from complex matrices.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xianjie Wang,Yaning Zhao,Hengsheng Wei,Yi Wang,Jingdong Gou,Jinhui He,Xue Ma,Louwei Cui,Liuyi Pan,Jiaojiao Liu,Dong Li
The separation of coal-derived C8 cyclohexane isomers, particularly cis-1,3-dimethylcyclohexane (cis-1,3-DMCH) and ethylcyclohexane (ECH), remains challenging due to their similar molecular structures and physicochemical properties, while research on cycloalkane isomer separation is limited. A series of functionalized UiO-66 derivatives (UiO-66, UiO-66-(CH 3 ) 2 , UiO-66-OH, and UiO-66-NO 2 ) were synthesized via solvothermal methods and systematically evaluated for their adsorption and separation performance toward C8 cyclohexane isomers through single-component and competitive batch adsorption experiments, dynamic breakthrough tests, and molecular simulations. Among the investigated materials, UiO-66-NO 2 demonstrated superior selectivity (α = 5.10) for cis-1,3-DMCH over ECH, with excellent regeneration stability over multiple cycles, significantly outperforming commercial activated carbons and zeolites. Mechanistic studies revealed that the enhanced selectivity arises from a dual mechanism combining geometric confinement effects and electronic recognition, where the oblate geometry and larger dipole moment of cis-1,3-DMCH enable preferential adsorption through strengthened C-H···O and C-H···NO 2 interactions, as confirmed by calculated binding energies (−37.15 kJ/mol for cis-1,3-DMCH vs. -22.13 kJ/mol for ECH) and diffusion coefficients. This work demonstrates rational MOF functionalization for efficient cycloalkane isomer separation, providing a promising strategy for coal-derived naphtha valorization.
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Catalysts
·
2025
·Vol. 16
·期 1
·33
·
IF 4
Yao Li,Zaixiao Ren,Juan Bai,Keju Sun,Ziwei Song,Shaotong Song
This study systematically investigates how organic ligand modifications—chain length adjusting and functional group incorporation—regulate the catalytic performance of UiO-66 derivatives for CO2-to-dimethyl carbonate (DMC) conversion. Through multi-technique characterization (Py-IR, TGA, FT-IR, XPS, etc.) and catalytic tests, Lewis acid/basic sites (LAS/LBS), bulk defects and electron density effects were identified as the three key factors to govern the catalytic activity. The bulk defects were believed to enhance mass transfer. Notably, MOF-801 (shortest ligand) and UiO-66-Br (electron-withdrawing-Br) achieved the highest TOFs of 0.86 h−1and 1.10 h−1, respectively. While LAS/LBS and electron-rich Zr clusters promote methanol activation, defect-enhanced mass transfer dominated over electronic effects in boosting DMC yield. These insights highlight the tunability of MOFs for CO2utilization via rational ligand design.
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高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Ziyao Mi,Xuzhen Liu,Yue Zhang,Bo Wang,Hongyu Guo,Yufeng Chen,Yanyan Du,Xinyu Wang,Xiaojun Hu,Jingxian Jiang
The discharge of industrial effluents containing heavy metal ions and organic dyes has laid heavy burdens on ecosystem, meanwhile, drawing extensive scientific attention globally. In this work, CdS/UiO-66-NH 2 heterojunction was uniformly loading on the aerogel skeleton composed of cellulose (CNF), chitosan (CS) and montmorillonite (MMT). The fabricated composite aerogel noted as CUN-CCMA was equipped with light density, a large specific area and a robust three-dimensional interpenetrating network. The MMT not only reinforced the mechanical stability of the aerogel, but also regulated the distribution of the heterojunction. The CUN-CCMA could adsorb various organic dyes and heavy metal ions, and the maximum adsorption capacities for methylene blue (MB) and Cu 2+ were 111.5 mg/g and 45.1 mg/g, respectively. The corresponding adsorption processes were in better consistence with the pseudo-second-order kinetic model and the Freundlich isotherm. The hydrogen bonding, electrostatic interaction, π-π stacking and chelating effect might be attributed to the adsorption mechanism. Most importantly, the removal efficiency of MB with a high concentration of 300 mg/L could reach 94 % when synergistic effect of adsorption and visible light photocatalytic degradation was exerted. The active species that played vital roles during the photodegradation process were recognized as ·OH and · O 2 − . Furthermore, the CUN-CCMA demonstrated an excellent reusability. These outstanding characteristics of CUN-CCMA broadened its application prospects in complicated sewage treatment.
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高影响因子
MICROCHEMICAL JOURNAL
·
2026
·
IF 5.1
Zhenyu Wang,Tong Qi,Hebin Sun,Ningran Wang,Wenbin Zhang,Jianlong Zhao,Liancheng Zhao,Lijuan Liang
The creation of dependable analytical platforms capable of detecting multiple heavy metal ions (HMIs) concurrently continues to be a significant challenge in environmental monitoring. This study introduces an innovative composite sensing material composed of gold nanoparticles (AuNPs) modified UiO-66-NH 2 metal organic frameworks (MOFs) and carbon nanotubes (CNTs) for simultaneous detection of multiple HMIs. UiO-66-NH 2 , with its extensive specific surface area and three-dimensional porous framework, facilitates effective ion diffusion and target preconcentration. The interconnected CNTs network significantly enhances electron transfer kinetics and expands the electroactive surface area, as confirmed by cyclic voltammetry (CV) analyses. AuNPs can effectively amplify electrochemical reactions and enhance the sensitivity of electrochemical detection. The thoughtful design of this sensing material amalgamates the unique benefits of its constituents. This sensing material attains remarkably low limits of detection (LOD), which is 0.021 μg·L −1 for Cd 2+ and 0.008 μg·L −1 for Pb 2+ , showcasing outstanding resistance to interference in complex environments. The potential applicationsapplications of MOF-based composites in the electrochemical sensors of HMIs are expanded by this methodology.
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JOURNAL OF HAZARDOUS MATERIALS
·
2020
·
IF 9.038
Weixia Yang,Meijie Cheng,Yong Han,Xueli Luo,Chunhua Li,Wenzhi Tang,Tianli Yue,Zhonghong Li
Here, inspired by the poisoning process of heavy metal in human body that the accidental ingested heavy metal can anchor to the functional groups of DNA/protein/enzyme to exert their toxicities during the rapid blood circulation, we developed the adsorbent that enveloped Etched UiO-66 with abundant functional groups into chitosan (CTS) aerogel to capture Pb(II) and Cd(II) in aqueous and apple juice. SEM, XRD and FTIR spectra were used to characterize the Etched UiO-66/CTS aerogel. The results showed that Etched UiO-66/CTS aerogel has a three-dimensional porous structure, and –OH groups of CTS interact with Zr(IV) of Etched UiO-66 to form the stable UiO-66/CTS aerogel. Benefiting from the intrinsic properties of porous and abundant functional groups, Etched UiO-66/CTS aerogel exhibits satisfactory adsorption capacities of 654.9 mg g −1 for Pb(II) and 343.9 mg g −1 for Cd(II) at 45 °C. Moreover, the aerogel shows excellent removal efficiencies of 98.21% for Pb(II) and 98.70% for Cd(II) with initial concentration of 1.0 mg L −1 in apple juice with little effect on the quality of apple juice. This strategy of mimetic heavy metal ions’ poisoning behavior opens up a new avenue for the removal of heavy metal ions in complex matrices.
研究领域:
环境科学
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材料科学
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吸附技术
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食品安全
·
纳米材料
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危险品化学品经营许可证（带存储）