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MOF-74
INORGANIC CHEMISTRY · 2015 · IF 4.762

Mixed-Metal Strategy on Metal–Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74

Dengrong Sun,Fangxiang Sun,Xiaoyu Deng,Zhaohui Li

Different amounts of Co-substituted Ni-MOF-74 have been prepared via a post-synthetic metal exchange. Inductively coupled plasma mass spectrometry, powder X-ray diffraction (XRD), N2 adsorption/desorption, and extended X-ray absorption fine structure (EXAFS) analyses indicated the successful metathesis between Co and Ni in Ni-MOF-74 to form the solid-solution-like mixed-metal Co/Ni-MOF-74. It was found that introduction of active Co into the Ni-MOF-74 framework enabled the inert Ni-MOF-74 to show activity for cyclohexene oxidation. Since Co was favorably substituted at positions more accessible to the substrate, the mixed-metal Co/Ni-MOF-74 showed superior catalytic performance, compared with pure Co-MOF-74 containing a similar amount of Co. This study provides a facile method to develop solid-solution-like MOFs for heterogeneous catalysis and highlights the great potential of this mixed-metal strategy in the development of MOFs with specific endowed functionalities.

研究领域: 材料科学 · 催化化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2020 · IF 3.99

Adenine-assisted synthesis of functionalized F-Mn-MOF-74 as an efficient catalyst with enhanced catalytic activity for the cycloaddition of carbon dioxide

Chao Feng,Shanshan Qiao,Yuan Guo,Yuehong Xie,Li Zhang,Naeem Akram,Shiang Li,Jide Wang

The development of a highly efficient renewable heterogeneous catalysts for the synthesis of cyclic carbonates by the cyclic esterification of epoxides and carbon dioxide under relatively mild reaction conditions is of great significance in the territory of chemical fixation of carbon dioxide (CO 2 ). This work comprises on a functional catalytic material F-Mn-MOF-74 using an effective competitive coordination strategy, adenine (Ad) as alkali source and competitive ligand, introduced onto the synthetic Mn-MOF-74. An F-Mn-MOF-74 crystal having a spherical structure and being functionalized is obtained, and lone pair of electrons on the nitrogen atom in the adenine can compete with 2,5-hydroxyterephthalic acid for coordination. The alkalinity exhibited by adenine is beneficial to enhance the catalytic properties of the crystal in the cycloaddition reaction of epoxide with carbon dioxide. Further catalytic experiments showed that the functionalized F-Mn-MOF-74 crystal combined with tetrabutylammonium bromide in the lacking of solvent showed excellent catalytic activity in the cycloaddition reaction of styrene oxide and carbon dioxide. Under the optimal reaction conditions after screening (100 °C and 10 bar CO 2 pressure), the yield of cyclic carbonate was as high as 99 %. The excellent catalytic performance for other epoxides also confirmed that F-Mn-MOF-74 catalytic material is universal in its application. The catalytic performance of the catalyst was not significantly decreased after being recycled seven times, attributed to its excellent stability. The possible mechanism for the synergistic effect of Lewis acid-base properties of functionalized F-Mn-MOF-74 catalytic material with cocatalyst is also proposed.

研究领域: 化学工程 · 催化材料 · 环境科学
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ACS Applied Nano Materials · 2018 · IF 0

Ultrasmall Metal–Organic Framework Zn-MOF-74 Nanodots: Size-Controlled Synthesis and Application for Highly Selective Colorimetric Sensing of Iron(III) in Aqueous Solution

Jiuhai Wang,Yadi Fan,Hang-wei Lee,Changqing Yi,Changming Cheng,Xin Zhao,Mo Yang

Here, a novel colorimetric sensing platform for highly selective detection of Fe3+ in aqueous solutions was developed based on zero-dimensional Zn-MOF-74 [Zn2(DOBDC), DOBDC = 2,5-dihydroxyterephthalic acid] nanodots. The first ultrasmall Zn-MOF-74 nanodots with the average size within 10 nm were successfully synthesized by manipulating the initial conditions with a diluted material system. It was found that the ultrasamll MOF nanodots had a highly selective interaction with Fe3+ and showed a specific blue colorimetric change in aqueous solution. The highly dispersive nature in aqueous solution and high surface-to-volume ratio help MOF-74 nanodots closely interact with the targeted Fe3+ ions with a low limit of detection of 1.04 μM and a fast response within seconds. Finally, we demonstrate that the selective Fe3+ sensing mechanism of Zn-MOF-74 nanodots is due to the selective framework disruption and the formation of Fe-DOBDC salt complex with blue color. It is the first report of nanoscale MOF based colorimetric Fe3+ sensor with low limit of detection (LOD) comparable even to fluorescent MOF based Fe3+ sensors, which could be easily observed by naked-eye without expensive fluorescence apparatuses. The good colorimetric stability in aqueous environment, low limit of detection, rapid response, and nanosize nature enable this MOF nanodot to be a good Fe3+ sensing probe for biological and environmental sensing applications.

CAS / MDL: 610-92-4 5970-45-6
研究领域: 材料科学 · 分析化学 · 环境科学
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2025 · IF 1.6

Effective removal of cobalt from aqueous solution by Mn-MOF-74 synthesized using room-temperature, water-based synthesis method

Liu Xinying,Lei Yuhan,Shi Jialin,Wang Zixuan,Zhang Wenxiu,Zhang Guanghui,Gu Ping

A novel adsorbent, Mn-MOF-74, was synthesized using a room-temperature, water-based method by assembling Mn 2+ metal nodes with 2,5-dihydroxyterephthalic acid ligands, and was further applied for Co 2+ removal. Mn-MOF-74 exhibited minimal pH dependence within a pH range of 3–8.5, achieving Co 2+ removal efficiencies between 92.5 and 96.3%, with a distribution coefficient of up to 2.9 × 10 4  mL·g −1 . A function relationship between the Co 2+ removal efficiency and the adsorbent dosage or initial concentration was proposed. The dominant removal mechanism was identified as ion exchange between Mn 2+ and Co 2+ , with chemisorption being the primary rate-limiting step.

研究领域: 环境科学 · 材料科学 · 化学工程 · 无机化学
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Nano Hybrids and Composites · 2022 · IF 0

Microstructure Evolution at High Temperatures for Co-MOF-74 as High-Efficiency Electromagnetic Absorbers

Yue Zhang,Tao Li,Shi Yu Tang,Xin Yue Xie,Ru Zeng Liang,Xiao Xiao Chu

Increasing demands of microwave absorbents require new approaches to enhance the absorbing performance. Metal−organic frameworks (MOFs) could be developed as effective absorbers owing to their outstanding features including intrinsic porosity and high specific area. Herein, novel nanostructured Co-MOF-74 composites have been successfully fabricated via a simple solvothermal method. Excellent absorption performance was achieved for the composite with a minimum reflection loss (RL) of −25.5 dB at 2.5 mm and a broad absorption bandwidth (RL < −10 dB) of 6.7 GHz. Such absorber could be developed as lightweight and high-efficiency absorbing materials, and this work provides inspiration for the design of advanced absorbers with strong dissipation capacity and broad effective bandwidth.

研究领域: 材料科学 · 电磁工程 · 纳米技术
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GREEN CHEMISTRY · 2024 · IF 9.3

Green, efficient and controllable synthesis of high-quality MOF-74 with high gravity technology

Xin-Ran Shi,Meng Qiao,Yan Wei,Ling-Xia Yun,Jie-Xin Wang,Jian-Feng Chen

MOF-74 or M2(dhtp) (M = metal ions, dhtp = 2,5-dihydroxyterephthalic acid), as a typical class of metal–organic frameworks (MOF), have garnered considerable interest due to their abundant unsaturated metal sites. However, environmental and economic limitations caused by the extensive use of organic solvents in traditional syntheses hinder their industrial applications. Although water as a green solvent is considered to be the best candidate solvent, water-based MOFs often have poor crystallinity and long synthesis time, and controlling the particle size is difficult. Herein, a water-based strategy is proposed to synthesize high-quality MOF-74–Co with controllable particle sizes in a rotating packed bed (RPB) reactor using high-gravity technology. MOF-74–Co could be rapidly prepared in the RPB, and shows a smaller and more uniform particle size, higher crystallinity, and larger specific surface area, as compared to the counterpart prepared in a traditional stirred tank reactor. Further adopting acetic acid as a modulator, the as-prepared MOF-74–Co has the highest BET surface area (1599 m2 g−1) in the reported literature so far and simultaneously possesses a high space–time yield (293 kg m−3 day−1). High-quality MOF-74–Zn and MOF-74–Ni can also be prepared, proving the generality of this strategy. Furthermore, the small-sized MOF-74–Co-78 nm exhibits a faster adsorption rate and a larger saturation adsorption capacity (298 mg g−1) for CO2 compared with large-sized samples. This study not only advances the field of green synthesis of MOFs but also paves the way for efficient manufacturing processes in MOF-74 synthesis for CO2 adsorption.

研究领域: 材料科学 · 化学工程 · 环境科学
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ANALYTICA CHIMICA ACTA · 2023 · IF 6.2

Determination of trace tellurium by photochemical vapor generation-atomic fluorescence spectrometry using bifunctional Co-MOF-74 for preconcentration and sensitization

Yuheng Lu,Chenghui Li,Yunfei Tian,Jing Hu,Xiandeng Hou

The determination of trace tellurium in real samples with complicated matrix can be rather challenging due to the low abundance and interferences. Herein, we report a new method for the highly sensitive detection of Te(IV) by photochemical vapor generation-atomic fluorescence spectrometry (PVG-AFS), utilizing Co-MOF-74 as an adsorbent and a precursor of Co 2+ ion sensitizer for preconcentration and enhanced PVG efficiency. The synthesized Co-MOF-74 can completely adsorb Te(IV) within 10 min in a wide pH range. Following filtration and re-suspension in a dilute solution of formic and acetic acid, the adsorbed Te(IV) was converted to volatile compounds under the UV irradiation and swept to AFS for detection. A limit of detection of 0.08 ng/mL for Te(IV) was obtained after a 50-fold preconcentration. The proposed method was used for analysis of various natural water samples for trace Te(IV), with satisfactory spike recoveries achieved.

CAS / MDL: 10102-20-2
研究领域: 分析化学 · 环境科学
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MICROCHIMICA ACTA · 2025 ·Vol. 192 ·期 8 ·1-12 · IF 5.3

Ozone-assisted cataluminescence sensor based on morphology-controlled TiO2@Mg-MOF-74 composite for rapid detection of N-hexane

Shi Zhaoxia,Luo Zhen,Liu Yilu,Liu Zi,Chen Xinyue,Zhang Yintang,Zhou Yanli,Xu Maotian

Four different morphologies of TiO 2 were successfully synthesized and the morphological dependence of the catalytic performance was investigated for monitoring of n -hexane. TiO 2 nanotubes showed the best catalytic performance for the cataluminescence (CTL) reaction of n -hexane because of their high specific surface area and ordered arrangement. To further enhance catalytic activity, a TiO 2 nanotube@Mg-MOF-74 composite was synthesized, which was used to construct a CTL sensor for rapid detection of n -hexane rapidly; the introduction of Mg-MOF-74 improved the adsorption capacity and selectivity. A CTL sensor was constructed based on TiO 2 nanotube@Mg-MOF-74 for the rapid detection of n -hexane, Under the optimal conditions there was a good linear relationship between CTL signal intensity and the concentration of n -hexane in the range 0.20–200.0 mg/L. The detection limit (LOD, S/N  = 3) was 0.08 mg/L. The RSD values for 11 consecutive measurements using the same sensor and 7 different sensors were 2.8% ( n  = 11) and 3.5% ( n  = 7), respectively, demonstrating good repeatability and reproducibility. Finally, the sensor was used to detect n -hexane in air samples from different workplaces, with recoveries ranging from 90.2 to 106.4%, showing good accuracy. Thus, the developed CTL sensor could be used for rapid detection of n -hexane in air, avoiding damage to health caused by excessive inhalation. Graphical abstract

研究领域: 分析化学 · 材料科学 · 环境监测 · 传感器技术
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Nanoscale · 2019 ·Vol. 11 ·期 19 ·9598-9607 · IF 6.97

Temperature controlled diffusion of hydroxide ions in 1D channels of Ni-MOF-74 for its complete conformal hydrolysis to hierarchical Ni(OH)2 supercapacitor electrodes

Shiyu Zhang,Zhendong Yang,Ke Gong,Ben Xu,Hao Mei,Haobing Zhang,Jiaxin Zhang,Zixi Kang,Youguo Yan,Daofeng Sun

Conformal hydrolysis of MOF precursors is a promising strategy to prepare hierarchical metal hydroxide electrode materials on a large scale with low cost and high efficiency. However, a complete transformation is challenging due to the normal “outside-in” conversion process. After studying the hydrolysis of Ni-MOF-74, which has regular 1D channels, we suggest that the transformation to Ni(OH)2 can occur simultaneously outside and within the precursor depending on the treatment temperature. Molecular dynamics simulations reveal that a higher temperature weakens the steric effects of OH− ions and facilitates the diffusion in the regular channels, and therefore, a complete transformation from Ni-MOF-74 to Ni(OH)2 is achieved. It is for the first time demonstrated that the 1D channels of MOFs are utilized for the complete conformal hydrolysis of Ni-MOF-74 to Ni(OH)2 electrode materials. Meanwhile, we also perform pioneering work illustrating that the complete conformal hydrolysis is the key to the improved supercapacitor performances of the MOF-derived Ni(OH)2 electrodes. The prepared Ni(OH)2 electrode under the optimized conditions has a specific capacity of 713.2 C g−1 at a current density of 1 A g−1, which is at least 28% larger than those of the Ni(OH)2 prepared at other temperatures. The detailed analyses based on CV and EIS of the obtained Ni(OH)2 electrodes indicate that the residual MOFs within electrodes due to incomplete hydrolysis significantly influence the diffusion length and diffusion efficiency of OH−, drastically lowering the supercapacitor performances.

研究领域: 材料科学 · 电化学 · 计算模拟
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Bimetallic MnZn-MOF-74 with enhanced percentage of MnIII: Efficiently catalytic activity for direct oxidative carboxylation of olefins to cyclic carbonates under mild and solvent-free condition

Ziyu Gao,Huidong Wang,Yuchen Hu,Jianmin Sun

Multi-functional MOF catalyst with oxidative- and acid- centers showed potential in olefins oxidative carboxylation to cyclic carbonates directly. In this work, a series of bimetallic MnZn-MOF-74 with different molar ratios of Mn and Zn were synthesized successfully through a one-pot facile method. Thoroughly characterization indicated that the existence of Zn regulated the valance state distribution of Mn in the obtained MnZn-MOF-74. Mn 99.3 Zn 0.7 -MOF-74 with the highest ratio of Mn III (61.3 %) performed the most efficient activity for olefin direct tandem oxidative carboxylation reaction using aqueous tert -butyl hydroperoxide oxidant under solvent-free condition of 90 °C, 1.0 MPa CO 2 and 4 h. Mn 99.3 Zn 0.7 -MOF-74 also showed satisfactory versatility and recyclability. Based on the experiments, a feasible mechanism was presented. Thanks to the high ratio of active Mn III as main oxidative center, the coordination unsaturated bimetal Mn and Zn as Lewis-acid sites, O 2– of metal − O as Lewis-base sites and combined effect with Bu 4 NBr cocatalyst, Mn 99.3 Zn 0.7 -MOF-74 presented efficient performance for the direct synthesis of cyclic carbonates from olefins. The metal Zn in MOF can regulate the valance state distribution of Mn and result in efficient catalytic property, presenting a potential avenue for direct oxidative carboxylation reaction of olefins to cyclic carbonates synthesis.

研究领域: 化学 · 材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Taming structure and modulating carbon dioxide (CO2) adsorption isosteric heat of nickel-based metal organic framework (MOF-74(Ni)) for remarkable CO2 capture

Lei Lei,Yan Cheng,Changwei Chen,Mohammadreza Kosari,Zeyu Jiang,Chi He

Though the highest CO 2 capture capacity belongs to liquid amine-solutions, solid matters capable of CO 2 capture are also highly sought, providing that, they offer at least analogous CO 2 adsorption capacity and CO 2 /N 2 selectivity. Herein, a surprisingly high-performance Ni-based metal–organic framework for CO 2 adsorption, namely MOF-74(Ni), was synthesized by a facile condensation reflux approach. It was found that the structure and CO 2 adsorption isosteric heat of MOF-74(Ni) could tune upon varying the synthesis duration under various temperatures. The optimized MOF-74(Ni)-24-140 (synthesized at 140 °C for 24 h) displays outstanding CO 2 adsorption capacity of 8.29/6.61 mmol/g at 273/298 K under normal pressure of 1.0 bar, several times higher than previously reported MOF-74-Ni (2.0/2.1 times), UTSA-16 (1.5/1.6 times), and DA-CMP-1 (3.6/4.9 times) under similar conditions. The excellent CO 2 capture capacity is associated to the abundant adsorption sites (mainly arising from the cationic Ni 2+ ions) and narrow micropore channels (mainly arising from the cage structure of Ni 2+ ions coordinated with organic linkers). Offering a high CO 2 selectivity (CO 2 /N 2  = 49) and a well-tuned isosteric heat of CO 2 adsorption (27–52 kJ/mol) besides its decent CO 2 capture capacity, MOF-74(Ni) strongly stands out as an efficient and strong CO 2 capturing material with industrial scale applicability.

CAS / MDL: 64-17-5 68-12-2 610-92-4
研究领域: 材料科学 · 环境科学
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Enhanced Enantioselective Sensing of 1,1′-Bi-2-naphthol and Mandelic Acid by Proportional Fluorescence Sensor 3DOM Zn-MOF-74-l-Trp with Hierarchical Macro–Micropore Structure

Mengyun Lu,Xinwen Jia,Wenjing Zhang,Wuduo Zhao,Ajuan Yu,Gangfeng Ouyang

The enantioselective performance of porous chiral metal–organic frameworks (CMOFs) is closely related to the pore size and uniformity of easily accessible active sites. The chiral recognition efficiency of microporous CMOFs is hindered by the restricted diffusion of the guest. Hierarchical porous chiral CMOFs with multiple pore size regimes ranging from micropores to macropores have emerged as potential candidates in chiral separation applications. 3DOM Zn-MOF-74 crystalline porous material with ordered macro–micropore structure was prepared with a general bottom-up strategy by carrying out the controllable confined growth of Zn-MOF-74 precursor in a removable three-dimensional ordered macroporous (3DOM) polystyrene (PS) template. Then l-tryptophan ( l -Trp) was introduced into MOFs by the strategy of postsynthetic modifications, and finally, a chiral hierarchical porous functional material 3DOM Zn-MOF-74-l-Trp was successfully fabricated. Based on the two luminescent centers from the achiral ligand H4DOBC and chiral ligand l-Trp, the proportional fluorescence sensor 3DOM Zn-MOF-74-l-Trp was hopeful to be applied in the field of enantioselective fluorescence sensing. The enantioselectivity factor values of microporous M-Zn-MOF-74-l-Trp for 1,1′-bi-2-naphthol (Binol) and mandelic acid (MA) were 1.08 and 1.12, respectively. In comparison, the construction of hierarchical porous structure greatly enhanced the chiral recognition performance, which may be due to the improved mass-transfer efficiency of chiral guest molecules and highly swelled accessibility to the chiral recognition sites in this CMOF composite, making the enantioselectivity factor values correspondingly increased to 1.29 and 2.26, respectively.

研究领域: 材料科学 · 化学
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