查找使用阿拉丁产品的科研文献

Direct sulfhydryl ligand derived UiO-66 for the removal of aqueous mercury and its subsequent application as a catalyst for transfer vinylation

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.

A UIO-66/tannic acid/chitosan/polyethersulfone hybrid membrane-like adsorbent for the dynamic removal of dye and Cr (VI) from water

Peng Shi,Xingkang Hu,Ming Duan

The water-soluble pollutant including dye and heavy metal was a challenge to the water and environment. Adsorption was among one of the most promising technique for the recycle of dye but it usually required a long contact time. A membrane-like adsorbent was fabricated by mixing and depositing tannic acid, chitosan and metal organic framework (MOF, UIO-66) on polyethersulfone (PES) membrane in this study. The material was dense enough to conduct filtration like a membrane to remove both the anionic and cationic dye (acid brilliant scarlet and methylene blue), as well as Cr(VI) from water. When the ratio of MOF/Chitosan was 30% and the pH for mixing was 3.5, the pollutant removal reached 99% in the filtration for 200 min. The adsorbent in the dynamic filtration showed a pollutant loading capacity 3 times of the capacity in the static adsorption, which was caused by the enhanced driving force brought by the concentration polarization in the filtration. The particle size of the TA/CS/MOF mixture were characterized by dynamic light scattering as well as Zeta potential , FTIR, XRD , TEM and XPS . The morphology of membrane was observed by SEM. The result showed that the MOF played as core to disperse the tannic acid-chitosan mixture to improve the pollutant removal. TEM showed the TA/CS mixture formed an uniform coating outside the MOF particle at the pH of 3.5. The pseudo 1st order and pseudo 2nd order model fitted the adsorption kinetics well, while the Elovich model did not fit very well.

Solid-State Synthesis of Defect-Rich Zr-UiO-66 Metal–Organic Framework Nanoparticles for the Catalytic Ring Opening of Epoxides with Alcohols

Haojie Zhao,Beili Yi,Xiaomeng Si,Lei Cao,Longxing Su,Yanli Wang,Lien-Yang Chou,Jin Xie

Perfect crystals do not exist; however, the introduction of defects can tailor the physical and chemical properties of materials. Defects in metal–organic frameworks (MOFs) have been demonstrated to be important in many applications, including but not limited to catalysis, gas separation, and energy storage. While a few liquid-phase synthesis methods have been reported to prepare defect-rich UiO-66, the heavy use of organic solvents may cause irreversible environmental problems. Here, we present a green, rapid, and facile solid-state synthesis approach to prepare UiO-66. All UiO-66 crystals remain in the nanometer size due to the limited diffusivity of growth species in solid-state synthesis without a large quantity of the solvent. The defect concentrations can be fine-tuned by the content of ethanol addition. Defect-rich UiO-66 shows excellent catalytic activity to the ring opening of epoxides with alcohols. This work provides insights into the large-scale production of defect-rich MOFs.

Water-stable metal–organic framework (UiO-66) supported on zirconia nanofibers membrane for the dynamic removal of tetracycline and arsenic from water

Xiaoqian Zhang,Qing Dong,Yuping Wang,Ze Zhu,Zhenfeng Guo,Jichao Li,Ying Lv,Yuk Tak Chow,Xinqiang Wang,Luyi Zhu,Guanghui Zhang,Dong Xu

Water-soluble pollutants including pharmaceuticals and personal care products (PPCPs) and inorganic arsenic have posed challenges to water and the environment. In this work, the water-stable metal–organic framework UiO-66 was loaded on electrospinning zirconia nanofibers membrane via the in-situ solvothermal method. This novel composite membrane had increased surface area, good adsorption performance, and could dynamically remove contaminants from polluted water. Adsorption performance of the composite membrane for tetracycline (TC) and As(III) were investigated using batch experiments. The maximum adsorption capacities were 59.27 mg/g for TC and 143.95 mg/g for As(III). The membrane’s dynamic removal efficiency for TC and As(III) could reach over 90% and 80%, respectively, at a relatively high flux of 60 L/(m 2 ·h), and could be generated and reused. pH values had strong impacts on the electrostatic interaction force, thus influenced the absorption efficiency. The adsorption mechanisms were studied by experimental characterizations and DFT calculations, and the results showed that direct interaction, hydrogen bond and ligand exchange were the main driving forces, and Zr O bond played a significant role in this process. Based on the self-supporting structure and good adsorption performance, we believe this novel composite membrane could find notable applications in wastewater decontamination.

Functionalized UiO-66-NO2 for selective separation of coal-derived C8 cyclohexane isomers: A dual mechanism of geometric confinement and electronic recognition

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.

Fast Assembly of Metal Organic Framework UiO-66 in Acid-Base Tunable Deep Eutectic Solvent for the Acetalization of Benzaldehyde and Methanol

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

Molecular sieving meets ion exchange: KCoFC@UiO-66 as a multi-functional adsorbent for high-efficiency rubidium recovery from lithium tailing leachate

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.

Construction of NH2–UiO-66@UiO-67-Decorated Polypropylene Nonwovens for Efficient Removal of Cr (VI) via Synergistic Adsorption and Photocatalytic Reduction

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.

UiO-66 Particles Decorated with Ag/Au Nanoparticles as SERS Sensors for Detecting Harmful Patina in Trace Analysis of Ancient Bronze Art

Yahui Zhang,Xia Huang,Jiachang Chen,Jiyuan Li,Shen Zhou,Junying Chen

Quantitative analysis of harmful patina components on the surface of bronzeware is crucial as patina can corrode artifacts. Surface-enhanced Raman spectroscopy (SERS) has a common application in surface analysis. However, there exists an absence of documented investigations concerning the quantitative analysis of detrimental patina, particularly the chloride patina. To achieve high sensitivity in targeting harmful patina, we report a fabrication method for constructing Ag/Au alloys in the pores and on the surface of UiO-66 (zirconium 1,4-dicarboxybenzene metal–organic framework) nanomaterials, resulting in Ag/Au/UiO-66 nanoparticle monolayers formed by self-assembly at the oil–water interface. By incorporating them onto the surface of PVA hydrogel, we obtained SERS sensor devices with excellent flexibility, outstanding optical transparency, and ultrahigh activity. These sensor devices efficiently sample irregular surfaces and detect micrometer-scale specimen. They significantly enhance the Raman characteristic peaks of measured objects, facilitating precise analysis of the patina composition on the surface of bronze artifacts. The Raman peak at 118 cm–1 was boosted from 367 to 11,909 for detecting harmful patina, and the enhancement factor of the SERS substrate was calculated to be 3.6 ×1010 for detecting the Raman peak of rhodamine 6G (R6G), which could be easily detected at 610 cm–1 at a concentration of 10–13 mol/L (M). The Raman peaks at 610 cm–1 from the SERS substrate could also be readily detected. By grafting the organic fluorescent group amino-MQAE onto the surface of Ag/Au/UiO-66 nanoparticles (NPs), the content of harmful patina on the surface of bronze artifacts treated for different durations was indirectly determined. These results indicate the successful construction of the Ag/Au alloy on the surface of UiO-66 NPs, resulting in SERS sensor devices with excellent flexibility, optical transparency, and ultrahigh sensitivity.

UiO-66@TiO2/Au heterojunction-like SERS substrate based on adsorption-induced aggregation for detection of thiamethoxam and triazophos in apple juice

Shengqiao Gao,Qingyi Wei,Hongbin Pu

Heterojunction-like substrates have drawn significant attention in surface enhanced Raman spectroscopy (SERS) owing to their multi-enhancement characteristics. In this study, the core-shell architectures of UiO-66@ TiO 2 were fabricated for capture and enrichment of organophosphorus pesticides (OPs) in solution. After absorption of OPs, the SERS-active nanoparticles of Au were assembled on the core-shell architectures to form UiO-66@TiO₂/Au substrate via Au-S bonding between OPs molecule and AuNPs and electrostatic interactions between UiO-66@TiO 2 and Au, resulting in adsorption-induced aggregation of Raman signal for OPs. The proposed method of adsorption-induced aggregation could be used for detecting thiamethoxam and triazophos in apple juice with detection limit of 3.51 μg/L and 0.66 μg/L, respectively. Furthermore, the satisfactory recovery rates, ranging from 91.98 % to 104.31 % for thiamethoxam and from 91.47 % to 116.47 % for triazophos, indicated that the prepared heterojunction-like substrate could be potentially used for trace detecting OPs in foods.

Modulating the Overall Properties of PEO/NaTFSI Electrolytes via UiO-66 Fibrous Membranes with Different Functional Groups for Solid-State Sodium Metal Batteries

Wen Qin,Wenhao Pan,Jialing Zhang,Junyan Tang,Jiming Huang,Mi Tang,Zhengbang Wang

Solid-state sodium metal batteries (SSMBs) have emerged as one of the next-generation rechargeable batteries due to their low-cost, high-energy-density, and desirable safety. However, their applications mainly depend on high-performance solid-state electrolytes. Herein, a series of polymer electrolytes is developed by compositing PEO/NaTFSI electrolytes into the PAN/UiO-66-X (X = NH2, NO2, F) nanofiber membranes, and the PAN/UiO-66-X are prepared by in situ growth of UiO-66-X MOFs on the PAN electrospinning nanofiber membranes. All the recovered PEO/PAN/UiO-66-X composite electrolytes possess a highly compact structure with a thickness of around 40 μm. The continuous dense UiO-66-X coatings not only improve mechanical strength of the electrolytes but also provide continuous Na+ transport pathways for high ionic conductivity. In addition, the interconnected pore structure with abundant Lewis acidic metal sites demonstrates strong anion-trapping effects for a high ionic transfer number. As a result, all of the batteries assembled with PEO/PAN/UiO-66-X electrolytes exhibit outstanding rate performance and cycling stability. In particular, the PEO/PAN/UiO-66-X electrolyte is the best with the highest ionic transfer number of 0.87, which could deliver more than 7000 h at 0.1 mA cm–2 in Na//Na symmetric cell and more than 600 cycles at 1C in NVP//Na full cell.

In Situ Determination of Chloride Ions Using a Novel Double-Layer Membrane Optical Fiber Sensor Modified with the UiO-66-NH2/Lucigenin Complex

Chloride quantification is crucial for environmental monitoring, marine research, and the durability assessment of geotechnical infrastructures, yet accurate measurement in complex aqueous and soil matrices remains challenging. Optical fiber sensors offer distinct advantages, including resistance to electromagnetic interference, high sensitivity and low cost. Unfortunately, existing fiber-optic chloride sensors are often limited by insufficient sensitivity, poor anti-ion interference, inadequate portability, and an inability to perform long-term in situ monitoring. Herein, a novel fluorescent optical fiber chloride sensor based on UiO-66-NH2/lucigenin composite is fabricated, in which the mixture formed lucigenin encapsulated with UiO-66-NH2is immobilized within a dual-layer membrane composed of an inner cellulose acetate (CA) matrix and an outer polyvinyl alcohol (PVA) membrane. The chloride-responsive fluorescent probe operates on the principle of fluorescence quenching. The dual-layer sensitive membrane is engineered to significantly enhance sensitivity, linearity, and stability for long-term monitoring. Furthermore, the portable device eliminates the constraints of bulky optical systems and mitigates instability caused by photobleaching, enabling reliable in situ chloride detection in water, soil, and geotechnical environments. Experimental results confirm the superior analytical performance of the sensor across various soil and aquatic media. This work represents a notable advancement in the field of fluorescent optical fiber sensors and holds substantial promise for practical applications.