查找使用阿拉丁产品的科研文献

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.

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.

Enhancing polymer compatibility and dispersibility of nanofiller via Zn2+-PVAm synergistically modified UIO-66-(COOH)2 for preparing high-performance CO2-separation MMMs

Zhiyuan Huang,Ye Yuan,Weifan Wang,Hao Zheng,Zhi Wang

Mixed matrix membranes (MMMs) have demonstrated remarkable advantages in gas separation applications through the synergistic integration of polymeric matrices and nanostructured reinforcements. While these advanced composite thin-film materials exhibit substantial potential for CO 2 separation, their industrial-scale implementation confronts threefold challenges: elevated manufacturing costs, interfacial compatibility optimization between nanofillers and polymer matrices, and performance enhancement requirements for achieving superior separation efficiency. In this study, the green and economical nanofiller UIO-66-(COOH) 2 (denoted as UC) was strategically selected. A novel strategy involving synergistic modification using Zn 2+ and polyvinylamine (PVAm) was developed to address the critical challenge of severe particle agglomeration and sedimentation. This phenomenon, caused by intense electrostatic interactions between the strongly negatively charged UC and the cationic polymer PVAm during surface modification, was effectively mitigated through the proposed cooperative modification mechanism, resulting in the successful synthesis of P@UC-Zn exhibiting exceptional dispersibility and enhanced compatibility with the polymeric matrix. The fabricated P@UC-Zn-PVAm/mPSf MMMs containing 35 wt% filler exhibited remarkable CO 2 permeance (3250 GPU) and selectivity (166) under feed gas conditions (CO 2 /N 2  = 15/85 vol%, feed pressure: 2 bar). Furthermore, the optimized MMMs demonstrated robust operational stability in simulated flue gas tests and showed potential for applications in carbon dioxide-methane and carbon dioxide-hydrogen separations.

Cu-based methanol steam reforming catalyst supported by heat conduction enhanced GO+UiO-66 composite MOF material for long-term stable hydrogen production

Wantong Wang,Shun Liu,Wenda Wu,Yimei Zhang,Xiaoze Du

Cu-based methanol steam reforming (MSR) catalysts are generally facing the fatal problems of easy sintering at high temperatures and poor long-term stability. In this study, we synthesized a series of Cu-based MSR catalysts supported by pure UiO-66 MOF and GO + UiO-66 composite materials with varying GO oxidation degrees and mass fractions through conventional thermal solvent impregnation. Comprehensively analysis revealed that both the specific surface area and thermal conductivity of the Cu@GO + UiO-66 catalysts exhibited positive correlations with those of their corresponding support materials. The optimal-performing [email protected]  wt%GO-0.3+UiO-66 catalyst demonstrated exceptional MSR catalyst performance, achieving 98.50 % methanol conversion at 300 °C with an inlet flow rate of 0.014 ml/min (4.18 h −1 ), while maintaining remarkably low CO selectivity (2.02 %) and high hydrogen productivity (6.82mmol/(min·g)). It also showed outstanding stability with only 10.38 % and 8.06 % decrease in methanol conversion and hydrogen productivity after continuous operation of 96 h. The excellent catalytic performance and stability were attributed to the significant and well-dispersed Cu loading (28.04 wt%), the high specific surface area of 128.83 m 2 /g (BET) and the enhanced thermal conductivity of 0.80W/(m·K) which were achieved through the use of the modified-0.01 wt%GO-0.3+UiO-66 support. Moreover, a minor amount of GO in the support was conducive to the formation of Cu + , and the abundant oxygen vacancies inside the catalyst could further stabilize the Cu + active sites, resulting in the formation of Cu–Zr-O x interfacial structures and the strong interaction between Cu species and the support, which effectively enhanced the catalytic performance and stability of the catalyst.

Construction of a highly sensitive Cd(II) and Pb(II) simultaneous detection electrochemical sensor based on CNTs/UiO-66-NH₂@AuNPs composite material

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.

In-situ silver-bridged interfaces drive Z-scheme coupling on iron-doped NH2-UiO-66(Zr)/silver iodide for efficient aqueous antibiotic degradation

Haileyesus Hatano Haitosa,Osman Ahmed Zelekew,Pu Chen,Daniel Manaye Kabtamu,Weimao Yan,Hong Wang,Yi-nan Wu

Fluoroquinolone antibiotics like ciprofloxacin (CIP) pose environmental risks when released into water. Herein, a visible-light-active Fe-doped NH 2 -UiO-66(Zr)@AgI Z -scheme heterostructure was prepared via an ion exchange precipitation method. By varying AgI content, reduced particle size and enhanced charge separation for efficient photodegradation was achieved. The optimum composition (Fe-UNH@AgI-20) exhibited a 95.2 % degradation efficiency toward CIP after 60 min of visible-light irradiation. It also showed high removal efficiencies for tetracycline, lomefloxacin, and Rhodamine B. Reaction kinetics followed pseudo-first-order behavior, with rate constants significantly higher than those of pristine NH 2 -UiO-66(Zr) and AgI. The catalyst maintained 85.1 % activity after cycles, indicating good stability. Scavenger tests and electron paramagnetic resonance (EPR) analyses identified holes (h + ), superoxide radical (•O 2 − ), and hydroxyl radical (•OH) as key reactive species. Fe doping enhanced visible-light absorption and created defect sites, while AgI introduction promoted charge separation and suppressed AgI photocorrosion. Under irradiation, a small fraction of Ag + was reduced to metallic Ag, forming an electron bridge that switched the initial type-II heterojunction to a Z -scheme configuration. This Z-scheme mechanism efficiently separated carriers, facilitated generation of ROS, and enabled thorough mineralization of CIP; toxicity predictions showed most products were less mutagenic than CIP, confirming reduced ecological risk. The findings demonstrate that the Fe-doped NH 2 -UiO-66(Zr)@AgI heterostructure is a promising photocatalyst for antibiotic-contaminated wastewater remediation.

Controllable Preparation of Novel UiO-66-NH2/g-C3N5 Thin-Film Nanocomposite Nanofiltration Membranes with Efficient Photocatalytic Pollutant Removal and Anti-Fouling Ability

Tian Jianghao,Xiao Min,Li Shifeng,Bu Ruiying,Yang Xin,Zhang Hongling,Chen Xiaoyang

To overcome membrane permeation selectivity defects and mitigate membrane fouling, a novel nanocomposite, UiO-66-NH 2 /g-C 3 N 5 (UNCN), was designed and synthesized. Notably, this composite overcomes the inherent limitations of UiO-66-NH 2 (limited visible light absorption) and g-C 3 N 5 (low specific surface area). The optimal composite ratio was determined to be 3:7 through systematic optimization. The UNCN-3:7 nanocomposite was then embedded into the polyamide selective layer on polysulfone via in situ interfacial polymerization under optimal conditions, resulting in a thin film nanocomposite (TFN) Nanofiltration membrane. Characterization revealed that the UNCN-3:7 Nanocomposites were uniformly distributed within the polyamide (PA) matrix. The resulting TFN Nanofiltration membrane possessed an ultrathin, positively charged selective layer with enhanced hydrophilicity, evidenced by a reduction in water contact angle from 60.3° to 47.3°. It exhibited a 43% increase in pure water permeability compared to the unmodified thin film composite (TFC) membrane (52.7 vs. 36.9 L·m −2 ·h −1 ·bar −1 ), while maintaining an excellent Na 2 SO 4 retention rate (> 96%). Furthermore, the membrane demonstrated excellent photocatalytic degradation performance, superior anti-fouling properties (flux recovery rate > 92%), and stable long-term operation. These results indicate that the construction of the novel UNCN nanocomposite Nanofiltration membrane presents an effective strategy to address membrane fouling issues.