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Zr-MOF
ANALYTICAL CHEMISTRY · 2020 · IF 6.785

Specific Coordination between Zr-MOF and Phosphate-Terminated DNA Coupled with Strand Displacement for the Construction of Reusable and Ultrasensitive Aptasensor

Weiwei Qiu,Feng Gao,Natsumi Yano,Yusuke Kataoka,Makoto Handa,Weiqiang Yang,Hidekazu Tanaka,Qingxiang Wang

Electrochemical aptasensors involved in chemical labeling are often single-use and sensitivity-limited because the probes are commonly single-point labeled and irreversible. In this work, the specific coordination between Zr4+ and phosphate group (−PO43–) was employed to construct a new aptasensor that is highly sensitive and reusable, using Ochratoxin A (OTA) as the test model. The OTA binding aptamer (OBA) was hybridized with the thiolated supporting sequence (TSS) immobilized on the surface of a gold electrode. The UiO-66 with a formula of [Zr6O4(OH)4(BDC)6], one of the class of Zr metal–organic frameworks (MOFs), was then particularly grafted on the terminal of OBA through the specific coordination between Zr4+ and 5′-PO43–, i.e., the Zr–O–P coordination bond. Similarly, as much as the 5′-PO43– and 3′-methylene blue dual-labeled sequences (DLS) were further assembled on UiO-66 due to the large surface area of MOF and rich active sites of Zr4+. Owing to the specific coordination for signal amplification, the developed aptasensor shows greatly enhanced sensitivity. A wide detection range from 0.1 fM to 2.0 μM and an ultralow detection limit of 0.079 fM (S/N = 3) for OTA were obtained. Additionally, the TSS can rehybridize with a new OBA to regenerate the aptasensor but without complicated pretreatments, enabling a aptasensor that is readily reusable for OTA detection. The aptasensor was successfully applied for OTA detection in the red wine samples, demonstrating a promising prospect for food safety monitoring.

研究领域: 生物化学 · 食品安全检测 · 纳米材料科学
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Journal of Materials Chemistry A · 2016 ·Vol. 4 ·期 14 ·5159-5166 · IF 8.262

A mercapto functionalized magnetic Zr-MOF by solvent-assisted ligand exchange for Hg2+ removal from water

Lijin Huang,Man He,Beibei Chen,Bin Hu

A facile preparation of magnetic MOF composites with flexible mercapto group pendants in their pores is realized through solvent-assisted ligand exchange (SALE) under mild conditions in water, and terephthalate in UIO-66 is replaced with mercaptoacetic acid (MAA). After the SALE processing, the crystallinity, porosity, and superparamagnetism of the mercapto functionalized magnetic Zr-MOF (MFC-S) are well maintained, and the obtained MFC-S exhibits a higher adsorption capacity (282 mg g−1) for Hg2+ than that of the magnetic Zr-MOF (MFC-O). Furthermore, the prepared MFC-S can be regenerated easily by liquid desorption after adsorption of metal ions and be reused more than 5 times without obvious decrease in removal performance. The proposed SALE method for the preparation of mercapto functionalized magnetic MOF composites (MFCs) is easy-to-operate and low cost, providing not only a reliable porous MFC platform for the removal of metal ions, but also a simple and efficient synthesis route for the preparation of functionalized MFCs which cannot be achieved through conventional approaches.

研究领域: 材料科学 · 环境科学 · 化学工程
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ELECTROCHIMICA ACTA · 2021 · IF 6.901

Separator modified by Co-porphyrin based Zr-MOF@CNT composite enabling efficient polysulfides catalytic conversion for advanced lithium-sulfur batteries

Xuanhe Hu,Tian Huang,Shipeng Wang,Shangjun Lin,Zihao Feng,Lai-Hon Chung,Jun He

The shuttle effect of soluble polysulfides as one of the primary bottlenecks has retard the widespread use of lithium-sulfur (Li-S) batteries. In this work, a new functional separator coating composed of pristine zirconium metal-organic framework (Co-PCN-222) with catalytic cobalt-porphyrin linker decorated carbon nanotubes (PCN@CNT) was presented for addressing this problem. Benefiting from powerful adsorption and catalytic activity of the uniformly dispersed cobalt and nitrogen sites in porphyrin linkers as well as the fast electron transport network provided by highly conductive CNT, the polysulfide redox kinetics is greatly boosted and the shuttle effect is inhibited to a large extent. Accordingly, the Li-S batteries coupling with PCN@CNT coated separator delivers a specific capacity as high as 1157 mAh g −1 at 0.1 C, good rate capability with a reversible capacity of 696 mAh g −1 under 2 C as well as excellent cyclic performance with a low average capacity attenuation rate of 0.067% upon 500 cycles at 1 C. This work will open up great opportunities in the development of pristine MOFs-based separator coating for advanced Li-S batteries.

CAS / MDL: 7704-34-9
研究领域: 材料科学 · 电化学 · 能源存储技术
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Fabrication and adsorption mechanism of chitosan/Zr-MOF (UiO-66) composite foams for efficient removal of ketoprofen from aqueous solution

Jian Chen,Jinbo Ouyang,Wenqian Chen,Zepeng Zheng,Zhen Yang,Zhirong Liu,Limin Zhou

Porous chitosan/Zr-MOF (UiO-66) composite foams (CSF@UiO-66) were facilely prepared by grafting UiO-66 into polymerized chitosan using epichlorohydrin as the linking agent. The flexible foams with high loadings of UiO-66 exhibited low density (15.0 ∼ 23.4 mg/cm 3 ) and superior liquid–solid separation performance. The hierarchical pores and abundant functional groups contributed to the effective removal of ketoprofen (KPF) from water by the composite foams, achieving a maximum adsorption capacity of 209.7 mg/g at pH 4, outperforming most reported adsorbents. Batch adsorption experiments demonstrated that the adsorption of KPF could be described by the Langmuir isotherm and pseudo-second-order kinetic model. Importantly, the composite foams showed excellent performance even in the presence of some ions and good reusability for engineering applications. Furthermore, density functional theory (DFT) calculations revealed that the adsorption mechanism between the composite foams and KPF could be attributed to hydrogen bonding and π-π interaction. In essence, this work provides an innovative strategy for the fabrication of a blocky composite foam with high loadings of MOF for efficient adsorptive removal of KPF in liquids, which can overcome the disadvantages of agglomeration due to small particle size and poor stability of MOFs.

研究领域: 环境科学 · 材料科学
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RSC Advances · 2020 ·Vol. 10 ·期 33 ·19149-19156 · IF 3.119

A built-in self-calibrating luminescence sensor based on RhB@Zr-MOF for detection of cations, nitro explosives and pesticides

Liu Yang,Yu-Long Liu,Cheng-Guo Liu,Ying Fu,Fei Ye

A RhB@Zr-MOF composite with dual-emission properties was successfully constructed, which comprises a zirconium-based metal–organic framework and the luminescent dye molecule, Rhodamine B (RhB), embedded via the encapsulation method. The fluorescence intensity ratio of the two emissions was found to be ca. 370 nm/590 nm for RhB@Zr-MOF. The fluorescence intensity values of the two emissions of RhB@Zr-MOF can also be affected by the structures of analytes containing different organic groups. Due to the existence of the dual-emission properties in RhB@Zr-MOF, the relative fluorescence intensity of the emission peaks was introduced as a detection index instead of absolute fluorescence intensity. RhB@Zr-MOF, which possesses the characteristics of a built-in self-calibrating fluorescence sensor, was investigated for detecting cations, nitroaromatics and pesticides. Aside from high sensitivity and selectivity, recyclability is the most important property for sensing pesticides. This work shows that RhB@Zr-MOF can maintain its stability after 5 cycles of detecting nitenpyram, with LOD of 0.2 μM. These results demonstrate that dye@MOFs with dual-emission properties can be employed as multifunctional fluorescence sensors for different types of analytes, and that RhB@Zr-MOF provides a new paradigm for analyte sensing.

研究领域: 材料科学 · 分析化学 · 环境科学
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Construction of a sensitive electrochemical biosensor for detecting protein kinase A activity based on NH2-Zr-MOF@Thi signal amplification

Xue Men,Rong Li,Aiwen Su,Yanli Zhang,Lian-Xun Gao,Chengxin Wu,Hongbin Wang,Wenrong Yang,Pengfei Pang

Protein kinase A (PKA) plays a significant role in the regulation of biological activities by the phosphorylation of the specific proteins or substrate peptides. The highly sensitive and reusable electrochemical biosensor has been developed to detect PKA activity based on the specific coordination between Zr 4+ and phosphate group. In this strategy, the specially designed substrate peptide can be anchored on the surface of gold electrode by Au-S bond. In the presence of adenosine triphosphate (ATP) and PKA, the substrate peptide is phosphorylated. Due to the large surface area of MOF and rich Zr 4+ active sites, signal molecule Thionine (Thi) can be absorbed into the cavity of NH 2 -Zr-MOF by the electrostatic interaction to form NH 2 -Zr-MOF@Thi signal probe. The phosphorylated peptide is linked to NH 2 -Zr-MOF@Thi probe because of the strong coordination interaction between Zr 4+ and phosphate group. Therefore, the number of Thi close to the electrode surface is increased and the response signal experiences amplification, markedly enhancing the sensitivity of the detection of PKA activity, which provides an excellent electrochemical sensing platform for PKA activity detection. The response signal of the electrochemical biosensor is proportional to the logarithm of PKA concentration, ranging from 0.05 U mL −1 to 100 U mL −1 , and the limit of detection of this biosensor for PKA is 0.017 U mL −1 when the signal-to-noise ratio is 3. In particular, the proposed method can selectively distinguish the target from other interferents, and can be used to screen potential small molecule inhibitors and detect PKA activity in complex cell samples. Therefore, the developed electrochemical biosensor can be used as a new way for the determination of PKA activity and the screening of its inhibitors in the future.

研究领域: 生物化学 · 分析化学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Facile preparation of magnetic Zr-MOF for adsorption of Pb(II) and Cr(VI) from water: Adsorption characteristics and mechanisms

Chen Wang,Chao Xiong,Yali He,Chen Yang,Xiteng Li,Jianzhong Zheng,Shixing Wang

A novel magnetic Zr-MOF named Ni 0.6 Fe 2.4 O 4 -UiO-66-PEI was synthesized by modifying UiO-66-NH 2 with Ni 0.6 Fe 2.4 O 4 and polyethyleneimine and its sorption characteristics for two representing heavy metals Pb(II) and Cr(VI) in water were examined. This material showed good thermal stability and was sufficiently magnetic to allow effective solid-liquid separation. The material had a maximum adsorption capacity of 273.2 mg/g for Pb(II) at pH 4.0 and 428.6 mg/g for Cr(VI) at pH 3.0, as obtained from the model fitting by the Hill equation. The sorption kinetics for both heavy metals on the material was fast, with adsorption equilibrium established in 60 min and 30 min for Pb(II) and Cr(VI), respectively. Model fitting of the kinetic data showed that Pb(II) and Cr(VI) sorption on Ni 0.6 Fe 2.4 O 4 -UiO-66-PEI followed the pseudo-second-order model. This material had good selectivity for competing ions, and still hold fairly good binding capacities after 5 times of regeneration. Adsorption mechanisms for Pb(II) and Cr(VI) by Ni 0.6 Fe 2.4 O 4 -UiO-66-PEI were proposed by analyzing FTIR, XPS and the electrokinetic property of the material. Specifically, Pb(II) adsorption on Ni 0.6 Fe 2.4 O 4 -UiO-66-PEI could be attributed to chelation of Pb(II) with the imine/amine functional groups in the material’s matrix, while Cr(VI) adsorption might stem from a combination of electrostatic attraction, chelation and redox reaction. It seems that Ni 0.6 Fe 2.4 O 4 -UiO-66-PEI could be used as a green and environmental-friendly material for heavy metals removal, particularly from acidic water streams.

CAS / MDL: 68-12-2 111-30-8
研究领域: 环境科学 · 材料科学
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JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS · 2019 · IF 2.752

Gel-like ZnO/Zr-MOF(bpy) nanocomposite for highly efficient adsorption of Rhodamine B dye from aqueous solution

Wen Cui,Xiaoli Kang,Xiaoying Zhang,Xudong Cui

A highly efficient Rhodamine B (RhB) adsorbent based on a gel-like ZnO/Zr-metal-organic framework (ZnO/Zr-MOF) composite was prepared by reacting ZnO nanoparticles with glacial-acetic-acid-modulated Zr-MOF(bpy) via a sample solvothermal method. Introduction of ZnO greatly improved the texture properties of the parent Zr-MOF(bpy), and the resulting material exhibited an agglomerate morphology consisting of numerous quadrate nanoparticles, which is quite different from the cubo-polyhedron morphology of Zr-MOF(bpy). In this way, this composite showed a considerable RhB absorption capacity from aqueous solution in a wide pH range. The adsorption kinetics , isotherms and thermodynamics of the RhB adsorption by ZnO/Zr-MOF(bpy) were discussed and confirmed that this adsorption process satisfied pseudo-second-order kinetics and the Langmuir model, and was a spontaneous exothermic process. Moreover, the excellent adsorption performance is likely related to the synergism of hydrogen bonding , electrostatic interactions and π–π interactions between the ZnO/Zr-MOF(bpy) nanocomposite and RhB. The excellent texture properties of ZnO/Zr-MOF(bpy) promote the adsorption and diffusion of RhB on it, which is also crucial during the adsorption process.

研究领域: 环境科学 · 材料科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Cu2+-functionalized Zr-MOF triggers O-phenylendiamine oxidation for ultrasensitive ratiometric fluorescence detection of nerve agent simulant

You Lei,Yuting Gao,Yi Xiao,Pengcheng Huang,Fang-Ying Wu

Developing a fluorescence sensor capable of precisely identifying highly toxic nerve agents has become a focus of research, given that they are easily available and can be used by terrorists to threaten the security of the world. In this work, we designed a ratiometric fluorescence sensing platform with Cu 2+ -modified UiO-66-NH 2 (Cu 2+ @UiO-66-NH 2 ) and o-phenenediamine (OPD) as signal indicators and successfully used for the liquid and gas detection of the nerve agent simulant diethyl chlorophosphate (DCP). UiO-66-NH 2 obtained oxidase activity by simple Cu 2+ modification, which catalyzed the oxidation of OPD to give a yellow fluorescent product 2, 3-diaminophenazine (DAP). In this detection system, the fluorescence of UiO-66-NH 2 was greatly enhanced by blocking the ligand metal charge transfer (LMCT) process inside the framework by DCP. At the same time, the amino group of DAP was phosphorylated by DCP, and the attenuation of DAP fluorescence was observed by the static quenching effect. In addition, the Cu 2+ @UiO-66-NH 2 /OPD loaded agarose hydrogel device can be used to detect DCP vapor with naked eyes and showed satisfactory detection result (LOD: 6.65 ppb).

研究领域: 化学传感器 · 环境科学 · 材料科学
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MICROCHIMICA ACTA · 2024 ·Vol. 192 ·期 1 ·1-11 · IF 5.3

MnO2 nanoparticles enhance the activity of the Zr-MOF matrix electrochemical sensor for efficiently identifying ultra-trace tetracycline residues in food

Tian Siyu,Wang Jiahui,Jie Yu,Ding Zhu,Wang Xiao,Wang Jijiang,Hou Xiangyang

A novel nanobiosensor was constructed by in situ locating nanometer MnO 2 particles with controllable size and morphology in a Zr-MOF substrate to serve as an electrochemical probe. The synergistic effect of the two components, Zr-MOFs with high specific surface area and compatibility as a carrier for MnO 2 , resulted in improved electrochemical activity and excellent electrochemical identification performance for the MnO 2 @Zr-MOF/GCE biosensor. Under optimized experimental conditions and using CV and DPV technology, the biosensor showed a wide linear detection range (2–200 μM), a low detection limit (2.577 × 10 −8  M), a recovery range (106.26–115.01%), and maximum relative standard deviation (5.155) for tetracycline (TC) identification. The recognition mechanism of the sensor was investigated adopting Laviron adsorption theory. The applicability of the sensor was verified through practical measurements. Overall, the MnO 2 @Zr-MOF/GCE sensor possesses the advantages of fast analysis speed, high sensitivity, high selectivity, and simple operation, making it suitable for detecting trace amounts of TC in food. Graphical abstract

研究领域: 分析化学 · 食品安全
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FUEL · 2024 · IF 6.7

A research on the synthesis process of Zr-MOF derived Ni-based catalysts for CO2 methanation: The role of Ce promoter, method of Ni introduction and calcination condition

Shenghua Liu,Xiaoqian Feng,JinXin Xu,Jiaxin Wang,Yonghua Zhao,Huan Wang,Qijian Zhang

CO 2 methanation is a potential way for the re-utilization of CO 2 . MOF derivations are promising candidates for commonly used Ni-based catalysts due to their high porosity and confinement effect. Herein, we systematically investigated the synthetic pathway of Zr-MOF-derived Ni-based catalysts. It is found that Ce addition can effectively improve the thermostability, specific surface area and Ni dispersion of the derived Ni/CeO 2 -ZrO 2 catalyst. It can also enhance the adsorption of CO 2 by the generation of O v and improve CO 2 methanation activity. Calcination the MOF in inert gas leads to the formation of CNTs and amorphous carbon. Amorphous carbon results in less interaction between NiO and CeO 2 as well as low amount of O v , leading to lower catalytic activity than the catalyst calcinated in air. Compared with impregnation method, one-pot solvothermal method leads to much higher specific surface area for both MOF and derived oxides. It also benefits the uniform dispersion of NiO and higher amount of O v . Therefore, it shows better catalytic activity and is proved to be a better method for Ni introduction. In the catalysts we discussed, St-ZrCeNi (Ce addition, one-pot solvothermal method, calcination in air) shows the highest CO 2 conversion and good CH 4 selectivity due to its high specific area and more O v . It also shows good stability (>50 h) and good intrinsic activity. This research reveals the roles of several important factors in the synthesis process of Zr-MOF derived Ni-based catalysts. It also gives new insights for the design and synthesis for other MOF derived catalysts.

研究领域: 材料科学 · 催化化学 · 环境科学
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Flexible Zr-MOF anchored polymer nanofiber membrane for efficient removal of creatinine in uremic toxins

Wenyan Li,Yumei Li,Xinggui Wen,Yakun Teng,Jing Wang,Tianyi Yang,Xiang Li,Lijuan Li,Ce Wang

High-performance and low-cost hemodialysis membranes are urgently needed by patients suffering from end-stage renal disease. Here, we designed a flexible multifunctional Zr-MOF anchored polyacrylonitrile (PAN) nanofiber membrane (UAPNFM), which has good adsorption, dialysis, and regeneration ability. A novel adhesive layer modification method was used to make UIO-66-(COOH) 2 nanocrystals grow in-situ on the composite nanofibers . The UIO-66-(COOH) 2 nanocrystals were uniformly and stably anchored on the nanofibers with the content of 54.99 wt%. The obtained UAPNFM has the capability to effectively remove uremic toxins with excellent retain protein rate. The Langmuir isotherm and pseudo-second-order kinetic model can be applied to better describe the adsorption process . The maximum adsorption capacity of UAPNFM for creatinine reached 168.63 mg/g. After 4 h of simulate dialysis, the clearance rate of creatinine was 82.48% and the protein retention rate of bovine serum albumin (BSA) by the UAPNFM was 93.09%. In addition, after four cycles, the removal efficiency for creatinine still remained at 82.31%. The results show that the UAPNFM has good regenerability. Moreover, the composite nanofiber membrane exhibited satisfactory blood compatibility. Therefore, this unique flexible Zr-MOF anchored polymer composite nanofiber membrane with an outstanding creatinine removal performance provides a new opportunity for cost reduction for clinical hemodialysis.

研究领域: 生物医学工程 · 材料科学 · 肾脏病学
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