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MOLECULES · 2025 ·Vol. 30 ·期 1 ·180 · IF 4.6

Electrochemical Sensor Based on Co-MOF for the Detection of Dihydromyricetin in Ampelopsis grossedentata

Xiaojing Si,Yue Huang,Mei Han,Liqiang Luo

Dihydromyricetin (DMY), as the main active ingredient inAmpelopsis grossedentata, is a naturally occurring flavonoid that has attracted extensive attention for its multiple biological activities. For the quick and accurate measurement of DMY, a novel electrochemical sensor based on a glassy carbon electrode (GCE) modified with a cobalt metal-organic framework (Co-MOF) was proposed in this work. The Co-MOF was synthesized via a single-step hydrothermal process using Co(NO3)2·6H2O. Fourier infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were used to study the morphology and structure of the synthesized Co-MOF. Utilizing differential pulse voltammetry and cyclic voltammetry methods, the effectiveness of DMY electro-oxidation on the Co-MOF/GCE was examined. The results showed that, in comparison to the bare GCE, the electro-oxidation peak current of DMY was considerably increased by the Co-MOF/GCE. The detection limit was 0.07 μM, and the peak current demonstrated two linear relationships in the ranges of 0.2−20 μM and 20−100 μM, with the linear equations of Ip (μA) = 0.4729c (μM) + 1.0822 (R2= 0.9913) and Ip (μA) = 0.0939c (μM) + 8.4178 (R2= 0.9971), respectively. The average DMY content inAmpelopsis grossedentatasamples was measured to be 3.275 μM, with a good recovery of 108.27% and a relative standard deviation value of 3.46%. The proposed method is simple, rapid and sensitive and can be used for the determination of DMY inAmpelopsis grossedentata.

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FUEL · 2024 · IF 6.7

Evolutionary trends and photothermal catalytic reduction performance of carbon dioxide by MOF-derived MnOx

Dou Chuanchuan,Liu Yuling,Shu Hao,Li Shuaishuai,Shi Qiyuan,Luo Xinzeng

Metal oxide catalysts derived from MOFs can inherit the excellent performance from their parent MOFs, possess abundant surface defects and high stability, and have attracted widespread interest in multiphase catalysis. In this study, we used Mn-MOF as a precursor and systematically investigated the evolution of MnO x catalysts by setting different calcination temperatures and times. XRD, SEM, TEM, Fourier transform infrared spectroscopy (FTIR), N 2 adsorption–desorption analysis, XPS, H 2 -TPR, CO 2 -TPD, electrochemical characterization, and other methods were used to investigate the structural characteristics, microstructure, surface properties, and photoelectric properties of the catalysts. The catalytic performance of the catalysts was also investigated through photocatalytic carbon dioxide hydrogenation reduction tests. Research has shown that calcination temperature and time have a significant impact on the phase structure and surface properties of MnO x , and the physicochemical properties of derived MnO x can be controlled by controlling calcination temperature and time. Among them, MnO x -500 has a wider light absorption range, better electron transfer performance, richer oxygen vacancies, and excellent separation performance of photo generated charge carriers, resulting in higher photocatalytic CO 2 hydrogenation and reduction performance. Its CO yield and selectivity reached 7420 μmol/g/h and above 99 %, respectively. This study provides valuable references for the preparation, optimization, and utilization in CO 2 photothermal catalytic conversion of MnO x catalysts derived from MOFs.

CAS / MDL: 6156-78-1 554-95-0
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Green synthesis and high-performance fluoride ion removal using lanthanum-modulated MOF-808 (Zr)

Guangqin Shi,Ting He,Haian Li,Zhao Yang,Wu Lei,Mingzhu Xia,Yu Tao

In a water solution and with a low reaction temperature of 85 °C, the green preparation of lanthanum-modulated MOF-808 (Zr) was realized, the obtained La-MOF-808 have smaller grain size, larger specific surface area, higher pore volume and larger average pore diameter. When the molar ratio of La: Zr=1:1, 1L-MOF-808 had the best fluoride ion removal performance, and its maximum adsorption capacity for F - reached 101.4 mg/g, which was higher than that of the unmodulated MOF-808 and some other reported fluorine adsorbents. Meanwhile, the regeneration experiment demonstrated that even after five cycles, 1L-MOF-808 retained 73.8 % of its initial adsorption capacity, highlighting its commendable reusability. In addition, when 1L-MOF-808 was applied to actual fluorine-containing wastewater, with the fluoride ion concentration of 25.3 mg/L and an adsorbent dosage of 0.6 g/L, 1L-MOF-808 exhibited excellent resistance to anionic interference (SO 4 2- , Cl - ), the concentration of fluoride ions in effluent was lower than 10 mg/L, meeting the stipulations of fluoride ion discharge outlined in GB39371–2020. Further adsorption mechanism investigation revealed that 1L-MOF-808's affinity for F - was attributed to electrostatic interaction and ligand exchange. Overall, the as-synthesized 1L-MOF-808 not only presents an environmentally friendly approach to producing MOF materials without organic solvents but also develops a new strategy for the design of high-performance adsorbent for effectively removing fluoride ions from wastewater.

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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING · 2024 · IF 4.2

Fast response triethylamine sensor based on MOF-derived coral flower-like Fe-doped Co3O4

Qi Ding,Hairong Li,Weining Liu,Dandan Huang,Xi Tan,Mingyang Zhao,Qionglin Cheng,Ming Yi,Yaqian Ren

Triethylamine (TEA) is easily volatilized and poses a huge health hazard. Therefore, the rapid detection of TEA is of great significance in environmental protection and industrial applications. In this paper, coral flower-like Fe-doped Co 3 O 4 was prepared using Co-MOF-74 as precursor. Compared with the pure Co 3 O 4 , Co 3 O 4 doped with 2 mol% Fe has better gas sensing performance of TEA. At an optimum operating temperature of 199 °C, the response to 100 ppm TEA is 21.2, five times higher than that of the pure Co 3 O 4 , with a short response recovery time (13 s/15 s). In addition, the gas sensor exhibits a certain selectivity and anti-humidity stability, with a minimum detection limit of 1 ppm at operating temperature. The higher Co 2+ /Co 3+ content in the sensor promotes the reaction of TEA with ionized oxygen, and amplifies the resistance change by adjusting the carrier concentration. Meanwhile, the introduction of Fe enriches the content of vacant oxygen and provides sufficient sites for the reaction and diffusion of TEA, further enhancing the sensing performance. In addition, Co 3 O 4 and Fe 2 O 3 combine to form p-n heterojunction , which helps to accelerate the gas adsorption-desorption process and improve the sensitive response speed. It creates a new design idea for the rapid detection of TEA gas by P-type metal-oxide semiconductors at relatively low operating temperatures.

CAS / MDL: 610-92-4 67-56-1
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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

Fluorescent Eu-MOF@nanocellulose-based nanopaper for rapid and sensitive detection of uranium (Ⅵ)

Yuqing Deng,Shan Jiang,Zifei Yan,Youlu Chu,Weibing Wu,Huining Xiao

Radioactive uranium leaks into natural water bodies mainly in the form of uranyl ions (UO 2 2+ ), posing ecological and human health risks. Fluorescent europium-based metal-organic frameworks (Eu-MOFs) have been demonstrated to be effective fluorescent sensors for UO 2 2+ , but the large size, powder state and poor dispersity limit their further application. In this work, fluorescent Eu-MOFs were in-situ grown on TEMPO-oxidized cellulose nanofibers (TOCNFs), which is the first time that spherical Eu-MOF crystals with sizes below 10 nm were prepared. Fluorescence spectral analysis revealed a nine-fold increase in the fluorescence intensity of TOCNF@Eu-MOF compared to Eu-MOF. The nanocomposites achieved rapid and sensitive fluorescence quenching to UO 2 2+ through the “antenna effect” and unsaturated Lewis basic sites on the ligands binding with UO 2 2+ . Moreover, TOCNF@Eu-MOF demonstrated excellent selectivity and anti-interference for UO 2 2+ detection. For the nanopaper-based sensor made from TOCNF@Eu-MOF, the Stern-Volmer quenching constant ( K SV ) was calculated as 8.21 × 10 4  M −1 , and the lowest limit of detection (LOD) was 6.6 × 10 −7  M, significantly lower than the 1.32 × 10 −6  M of Eu-MOFs. In addition, the nanopaper exhibited good fluorescence stability and cyclic detection performance, enabling the rapid and convenient detection of UO 2 2+ in the aqueous phase within 30 s by simple dipping.

CAS / MDL: 63557-10-8
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Highly porous MOF integrated with coordination polymer glass membrane for efficient CO2/N2 separation

Ning Li,Chao Ma,Ziyue Wang,Dudu Li,Zhihua Qiao,Chongli Zhong

The MOF crystal-glass composites (CGC) membrane, comprising a MOF crystal and MOF glass matrix, represents a novel self-supported membrane that has been effectively applied in gas separation. Nevertheless, the typical MOF glass matrix requires a higher operating temperature (>400 °C), which constrains its combination with a multitude of MOF crystals characterized by high porosity and low decomposition. In this work, Zn-P-dmbIm (coordination polymer) was chosen as the glass matrix, and MIL-101 crystal with high porosity were integrated at an operating temperature of 190 °C. Furthermore, the intrinsic low porosity of a g Zn-P-dmbIm can be enhanced by the incorporation of higher porosity MIL-101, which possessed a high specific surface area (from ∼1.7 m 2 /g to 401 m 2 /g) and porosity (from ∼0.0014 cm³/g/nm to 0.5605 cm³/g/nm) of the CGC. The intimate combination of MIL-101 and a g Zn-P-dmbIm by in - situ melting to reduce the interfacial defects, which also provides a robust foundation for effective CO 2 /N 2 separation. In CO₂/N₂ (50/50, v/v) mixed gas conditions, the MIL-101/ a g Zn-P-dmbIm membrane demonstrated a impressively high CO₂ permeability of 18670 barrer and CO₂/N₂ selectivity of 61, exceeding the CO₂/N₂ upper bound. The variable pressure (1-12 bar) and long-term stability (120 h) of the CGC membrane exhibited enhancing separation stability. Hence, the self-supported MIL-101/ a g Zn-P-dmbIm membrane demonstrated effective CO₂/N₂ separation performance, which had the potential to significantly extend the scope of applications for MOF crystal-glass matrices.

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INORGANIC CHEMISTRY COMMUNICATIONS · 2024 · IF 4.4

Heteropolyacids promoted NiMo/MOF catalyst for catalytic oxidation of lignin dimers in oxygen atmosphere

Xiaohui Yang,Qi Ye,Fei Ge,Minghao Zhou

Lignin, as an important biomass resource, has significant research value in its oxidative cleavage process. Nickel-based metal catalysts could selectively depolymerize lignin. A series of heteropolyacid doped nickel based bimetallic catalysts Ni 4 Mo 1 -MOF-x(x represented heteropolyacid)were prepared by hydrothermal method, which were calcined to catalyze the oxidative cleavage of lignin model compound (2-phenoxy-1-acetophenone). The catalyst Ni 4 Mo 1 -MOF-SiWA-0.1(500) showed the best catalytic performance in methanol solvent under conditions of 160 °C, 4 h, 0.5 MPa oxygen pressure, where the conversion rate was nearly 100 % and the yields of phenol and benzoic acid were 54.5 % and 23.3 %, respectively. The catalysts were well characterized to explore the catalytic performance during the oxidation of lignin dimer. This study could provide some interesting and useful information for the catalytic oxidation of lignin to biomass-derived chemicals.

CAS / MDL: 68-12-2
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Heteropolyacid promoted lignin-MOF derived spherical catalyst for catalytic hydrogen transfer of 5-hydroxymethylfurfural

Jiantao Su,Xiaohui Yang,Hui Shi,Shuangquan Yao,Minghao Zhou

Catalytic conversion of biomass-derived value-added chemicals was of great significance for the utilization of renewable biomass resources to instead of fossil chemicals. Biomass-derived lignin was regarded as an important support and 5-hydroxymethylfurfural (HMF) was a vital platform chemical derived from cellulose. Herein, a series of lignin-MOF hybrid catalysts were prepared and modified with different heteropolyacids (HPAs), which were then successfully introduced into the selective conversion of HMF to 5-hydroxymethylfurfuryl alcohol (MFA). The effect of different HPA, calcination temperature, etc. were all studied, and all catalysts were well characterized. It was confirmed that silicotungstic acid modified catalyst (Ni 3 Co-MOF-LS@HSiW) exhibited the best catalytic performance, while the highest conversion of HMF was up to 100%, with the best MFA yield of 86.5%. The finding in this study could provide novel insights for the utilization of lignin and preparation of value-added biomass-derived chemicals.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Hierarchically engineered flexible COF/CNT-MOF composite membrane with interpenetrated pores for water purification

Yanyun Hou,Zhengjun Su,Yuhuan Wu,Jing Ma

Covalent organic frameworks (COFs) have shown great potential in separation applications owning to their tunable framework and rich chemical properties. However, preparing flexible COF membrane with precise separation performance is challenging. Herein, inspired by the “brick–mortar” structure, we designed a flexible COF composite membrane with the synergy of carbon nanotube (CNT) and metal–organic framework (MOF) through a multi-interface regulation strategy. Specifically, CNT (sand) was inserted in COF interlayers (brick) for improved flexibility. To achieve better molecular-sieving effect of the membrane, MOF (cement) was confined grown in the pores of COF/CNT composite. The formed heterogeneous structure endows the COF composite membrane with interpenetrated molecular sieving pores. As a result, the obtained COF composite membrane exhibits good flexibility. Meanwhile, the COF composite membrane shows high permeability and rejection ratios for dyes because of the precise sieving pores. This facile strategy presents an attractive insight into the development of other advanced membranes for broad application prospects.

CAS / MDL: 693-98-1
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Janus Separation-Sensing Membrane Hosted with Enzyme@MOF Nanoreactor for Real-Time Blood Sensing

Fangbing Wang,Jing Ren,Qiwen Peng,Hongyi Sun,Qiankun Zeng,Yongheng Zhang,Guoyue Shi,Min Zhang

Plasma separation, rich in biomarkers crucial for diagnosis, is conventionally achieved via high-speed centrifugation, a method hindered by its blood usage, lengthy processes, and complex operations, which delays detection. We introduced a novel real-time blood sensing method based on a Janus membrane and enzymes @MOFs. Asymmetric driving of the janus membrane can realize spontaneous separation of plasma and prevent hemolysis during direct separation. Glucose oxidase (GOx), uric acid oxidase (UOx) and horseradish peroxidase (HRP) were encapsulated in a hydrophilic organometallic framework (MOFs) to construct an enzyme cascade nanoreactor. Embedding enzyme in hydrophilic MOFs not only retains the natural conformation of free enzyme but also improves the brittleness of enzyme, endows MOFs with new biological functions, and expands its sensing application. Using 3,3′,5,5′-tetramethylbenzidine (TMB) as a chromogen and a custom app for color interpretation, we achieved real-time visualization of glucose (Glu) and uric acid (UA) at a 50 μM limit. The system accurately analyzed serum samples, matching commercial kits and showing promise for portable, personalized diagnostics.

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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Improving Proton-Conducting Stability by Regulating Pore Size of MOF Materials through Mixed Grinding

Jie Liu,Wenxuan Yan,Yingying Ma,Xinran Li,Jiajun Zhong,Xiaofeng Zheng,Zhe Liu

An effective strategy to improve the proton conductivity of metal–organic frameworks (MOFs) is to regulate the pore size of composite materials. In this work, composite materials of MOF-808@MOG-808-X (X is the mass ratios of MOF-808 to MOG-808) was successfully prepared by grinding and blending. MOF-808@MOG-808-1:2 was optimal for its suitable pore structure, which facilitates the practical construction of hydrogen bonding networks, promotes rapid and stable proton conduction, and enables the proton conductivity, achieving a 1 + 1 > 2 effect. At 353 K and 93% relative humidity (RH), the maximum proton conductivity of MOF-808@MOG-808-1:2 reaches 1.08 × 10–1 S·cm–1. Next, MOF-808@MOG-808-1:2 was blended with chitosan (CS) to obtain composite proton exchange membranes (PEMs), namely, CS@MOF-808@MOG-808-1:2-Y (Y = 5%, 10%, or 15%) with the maximum proton conductivity reaching 1.19 × 10–2 S·cm–1 at 353 K and 93% RH for CS@MOF-808@MOG-808-1:2-10% with additional stability. The conductive mechanisms of the composite materials were revealed by activation energy calculation. This investigation not only proposes a simple grinding–blending method for the development of MOF-doped composite materials for proton conductivity but also provides a producting material basis for future applications of MOFs in proton exchange membrane fuel cells (PEMFCs).

CAS / MDL: 554-95-0
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Defect-Engineered MOF-801/Sodium Alginate Aerogel Beads for Boosting Adsorption of Pb(II)

Mengshuo Du,Yingying Wang,Youyu Cao,Wenzhi Tang,Zhonghong Li

Metal–organic frameworks (MOFs) are attractive adsorbents for heavy metal capture due to their superior stability, easy modification, and adjustable pore size. However, their inherent microporous structure poses challenges in achieving a higher adsorption capacity. Defect engineering is considered a simple method to create hierarchical MOFs with larger pores. Here, we employed l-aspartic acid as a mixed linker to bind Zr4+ clusters in competition with fumaric acid of MOF-801 to create defects, and the pore size was increased from 4.66 to 15.65 nm. Mercaptosuccinic acid was subsequently used as a postexchange ligand to graft the resultant MOF-801 by acid-ammonia condensation to further expand the pore size to 22.73 nm. Notably, the −NH2, −COOH, and −SH groups contributed by these two ligands increased the adsorption sites for Pb(II). The obtained defective MOF-801 with larger pores was thereafter loaded onto sodium alginate to form aerogel beads as adsorbents, and an adsorption capacity of 375.48 mg/g for Pb(II) was achieved, which is ∼51 times that of pristine MOF-801. The aerogel beads also exhibited outstanding reusability with a removal efficiency of ∼90.23% after 5 cycles of use. The adsorption mechanism of Pb(II) included ion-exchange interaction, as well as chelation interactions of Pb–O, Pb–NH2, and Pb–S. The versatile combination of defect engineering and composite beads provides novel inspirations for MOF modification for boosting heavy metal adsorption.

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