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Heliyon · 2024 · IF 3.4

M-Ni-Co MOF (M=Zn, Fe, Mn) for high-performance supercapacitors by adjusting its morphology

Yige Yan,Mohan Huang,Yongsheng Wang,Dawei He,Jiaqi He

Metal-organic frameworks (MOF) have been wildly synthesised and studied as electrode materials for supercapacitors, and bimetallic MOF of Ni and Co has been broadly studied to enhance both specific capacitance and stability of supercapacitors. Herein, a best performance (about 320 F/g) of Ni–Co bimetallic MOF was found in a uniform preparation condition by adjusting the ratio of Ni to Co. Then tiny third metal ion was introduced, and we found that the morphology of material has a significant change on the original basis. Furthermore, certain ions (Zn, Fe, Mn) introduced make a huge improvement in capacitance based on Ni–Co MOF of 320 F/g. The result shows that Zn–Ni–Co MOF, Fe–Ni–Co MOF and Mn–Ni–Co MOF perform specific capacitance of 1135 F/g, 870 F/g and 760F/g at 1 A/g, respectively. Meanwhile, the asymmetric supercapacitor (ASC) was constructed by Zn–Ni–Co MOF as positive electrode and active carbon (AC) as negative electrode. The Zn–Ni–Co MOF//AC ASC possesses a energy density of 58 Wh/kg at a power density of 775 W/kg. This research provides a new methods to regulate the morphology of MOF and a novel viewpoint for assembling high-performance, low-price, and eco-friendly green energy storage devices.

研究领域: 材料科学 · 能源存储技术
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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 37 ·16323-16330 · IF 2.7

Defective Fe/Co-MOF with abundant oxygen vacancies as an efficient oxidase mimic for colourimetric and sensitive determination of tetracycline

Xiaoyue Yue,Chaoyun Wu,Chenxu Hao,Yanhong Bai

The abuse of tetracycline (TC) has led to serious threats to human health and the environment. Therefore, the rapid and sensitive detection of tetracycline is of particular importance. Herein, we successfully synthesised a bimetallic nanozyme D-Fe/Co-MOF with oxidase activity and established a colourimetric sensor. The complex of Fe2+ in D-Fe/Co-MOF and TC can release hydroxyl radicals (˙OH) and promote the oxidation of TMB. As a result, the colour of the detection system significantly changes, enabling the sensitive colourimetric detection of TC. Compared with the existing Fe/Co-MOF sensor, D-Fe/Co-MOF can effectively reduce the detection error caused by hydrogen peroxide decomposition, improving the accuracy of TC detection. Under the optimal conditions, the absorbance at 652 nm showed a good linear relationship with TC concentration in the range of 0.35–220 μg mL−1. The detection limit was as low as 0.0719 μg mL−1, considerably lower than the national safety standard. The proposed colourimetric sensor was also successfully used for the detection of TC in actual milk samples, and the results were in good agreement with those obtained via liquid chromatography. The proposed strategy for the detection of TC in food is expected to contribute to ensuring food safety and human health.

CAS / MDL: 7646-79-9 100-21-0
研究领域: 生物化学 · 环境科学 · 食品安全
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 23 ·11341-11349 · IF 3.925

In situ composite of Co-MOF on a Ti-based material for visible light multiphase catalysis: synthesis and the photocatalytic degradation mechanism

Chentao Hou,Xiaoping Yuan,Miaomiao Niu,Yijie Li,Liping Wang,Mingyuan Zhang

The in situ synthesis method was used to grow Co-based one-dimensional MOF Co-PYDC (CP) on a pre-synthesized TiO2/TiOF2 (TOF) material which was used to treat tetracycline antibiotic wastewater. Through the degradation of tetracycline hydrochloride (TCH) under simulated sunlight, the photocatalytic activity of the synthesized samples was investigated. The results showed that the 5% CP/TOF photocatalyst exhibited the best photocatalytic performance on tetracycline hydrochloride degradation. The adsorption efficiency of TCH was 48% in the dark reaction for 0.5 h, and the removal efficiency reached 85% under 1.5 h simulated sunlight, which was much higher than those of TOF and CP monomers. Among them, the prepared 5% CP/TOF nanocomposite had a lower bandgap energy (2.63 eV), a larger specific surface area (52.01 m−2 g−1) and a lower electron–hole recombination rate. The synthesized CP/TOF photocatalyst showed promising application potential in antibiotic wastewater treatment. Moreover, the detected superoxide radical was the main active species, which further explained the degradation pathway and catalytic mechanism of the CP/TOF photocatalytic degradation of TCH, following the z-type heterojunction model. In this study, a CP/TOF composite material for photocatalytic degradation of tetracycline wastewater was designed and developed, which provided experimental methods and ideas for the practical treatment of wastewater.

研究领域: 环境科学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 18 ·8507-8514 · IF 3.3

Morphology control in the synthesis of [Mo3S13]2−/Co-MOF-74 composite catalysts and their application in the oxygen evolution reaction

Jianxia Gu,Jingting He,Haiyan Zheng,Chunyi Sun

The novel composite electrocatalysts [Mo3S13]2−/Co-MOF-74 have been successfully prepared by using a simple solvothermal method. The morphology of composite catalysts can be effectively controlled by regulating the amount of [Mo3S13]2− because the addition of [Mo3S13]2 can affect the nucleation rate of Co-MOF-74. After the optimization, [Mo3S13]2−/Co-MOF-74 with spindle-like morphology displays remarkable OER electrocatalytic activity with a low overpotential (368 mV) to afford the current density of 10 mA cm−2 and a small Tafel slope of 90.6 mV dec−1, which is almost on a par with IrO2/C (358 mV, 89.1 mV dec−1). Besides, this composite catalyst can continuously work for about 17 h with almost negligible attenuation in current density. Such an excellent electrocatalytic OER performance of [Mo3S13]2−/Co-MOF-74 benefits from the good morphology obtained by the introduction of a moderate amount of [Mo3S13]2− as well as the synergistic effect between the [Mo3S13]2− and Co-MOF-74. This work provides new insight into the development of MOF-based electrocatalysts for the OER.

研究领域: 材料科学 · 电化学
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Journal of Water Process Engineering · 2024 · IF 6.3

Magnetic recyclable Co-MOF derivate-modified steel slag for tetracycline removal by integrated adsorption and Fenton-like catalysis

Caihong Fang,Longhui Nie,Heng Chen,Yiqiong Yang

As a category of emerging pollutants, the wide occurrence of antibiotics in water bodies has adverse effects on aquatic organisms. Herein, a Co-MOF derivate-modified magnetic steel slag (MSS@Co-CN) was fabricated and used to remove tetracycline hydrochloride (TCH), a representative antibiotic, from wastewater by the synergistic effect of adsorption and Fenton-like oxidation . MSS@Co-CN exhibited a high adsorption capacity ( q max  > 416.6 mg/g) and a strong Fenton-like catalytic oxidation capacity for TCH (80 % removal efficiency within 5 min) by activating peroxymonosulfate (PMS) in a wide pH range (pH = 2–11). The TCH adsorption on MSS@Co-CN, with equilibrium reached within 30 min, was proved to be an exothermic multilayer adsorption process by the Freundlich and Temkin models. It also exhibits excellent stability of catalytic activity in five adsorption-oxidation cycles. The superoxide anion radicals and singlet oxygen were the main active species in the Fenton-like reaction. The concentration of leaching iron ion (0.03 mg/L, far below the standard for surface water) after the reaction was significantly reduced after Co-CN modification. Furthermore, the good magnetic property of MSS@Co-CN makes it easily separatable from water, showing good application potential. This work is expected to provide insight into the fabrication of highly efficient catalysts for antibiotic removal by the synergistic effect of adsorption and Fenton-like catalysis.

研究领域: 环境科学 · 材料科学 · 化学工程
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MICROPOROUS AND MESOPOROUS MATERIALS · 2021 · IF 5.455

The activation of Co-MOF-74 with open metal sites and their corresponding CO/N2 adsorptive separation performance

Xiaowu Liang,Pengfei Wang,Congli Li,Min Yuan,Qi Shi,Jinxiang Dong

CO is an important raw material and the separation of CO/N 2 in blast furnace gas can supply an abundant source of CO. Metal organic frameworks (MOFs) containing open metal sites are capable of selectively binding to CO over N 2 . However, the open metal sites easily bind to guest molecules during the preparation and activation process. In this study, typical MOFs containing open metal sites (Co-MOF-74) were used to investigate the activation behavior and corresponding CO/N 2 adsorptive separation performance. To characterize the removal and decomposition of guest molecules, TG-MS and NMR analysis of MOF-74 prepared under different activation conditions were performed. During the heat and vacuum process, the guest H 2 O and methanol (MeOH) molecules in Co-MOF-74 were first removed at 150 °C under vacuum. The aim of high temperature activation at 300 °C is the decomposition of a small amount of bind N,N-dimethylformamide (DMF) and terminal ligands occupying the open metal sites in Co-MOF-74. In addition, H 2 O molecules occupy the open metal sites of Co-MOF-74 during the filtration and MeOH wash steps under air, which is accompanied by the removal of a portion of DMF. The CO adsorption (298 K and 1 bar) and the CO/N 2 selectivity (Ideal adsorbed solution theory: 50:50, v/v) of Co-MOF-74 activated at 300 °C was 6.07 mmol/g and 384, respectively, which was higher than that of the other activated Co-MOF-74 samples and was attributed to the effective removal of guest molecules. Our results may guide the activation of MOFs, which contain open metal sites.

CAS / MDL: 10026-22-9 68-12-2
研究领域: 材料科学 · 化学工程
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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Promoting photoelectrochemical water oxidation of BiVO4 photoanode via Co-MOF-derived heterostructural cocatalyst

Dan Wang,Jiangli Gu,Hanlin Wang,Mingzhuang Liu,Yichun Liu,Xintong Zhang

The sluggish surface reaction kinetic is the bottleneck limiting the photoelectrochemical (PEC) water oxidation of BiVO 4 photoanode, especially for the porous structured BiVO 4 with high surface area. Here, Co-based metal–organic frameworks (MOFs) were modified on porous BiVO 4 photoanode followed by calcining in the N 2 atmosphere, forming BiVO 4 -MOF-N 2 photoanode. The MOF-derived heterostructural cocatalysts significantly enhanced the photocurrent density of BiVO 4 -MOF-N 2 , reaching 2.32 mA·cm −2 (1.23 V vs RHE), about 1.15 times that of BiVO 4 -MOF and 2.64 times that of pristine BiVO 4 . The comparative study of BiVO 4 -MOF-N 2 , BiVO 4 -MOF, and pristine BiVO 4 photoanodes suggested that the Co-MOF-derived heterostructural cocatalyst had a much stronger effect on promoting the surface reactions than pure MOF. The BiVO 4 -MOF-N 2 photoanode had the highest charge transfer efficiency of 63.1 % at 1.3 V vs RHE and the lowest charge transfer resistivity compared with BiVO 4 and BiVO 4 -MOF. Both Co-active centers and conductive carbon matrix contributed to the enhanced charge transfer of BiVO 4 -MOF-N 2 photoanode. A MOF-loading-time dependent PEC performance of BiVO 4 photoanode also indicated that the intermediate charge transfer process from BiVO 4 to active centers strongly affected the final charge transfer and PEC performances. This work provides new insights into the design of high-performance photoelectrochemical electrodes based on heterostructural cocatalysts.

研究领域: 材料科学 · 能源科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

Co-MOF-74 derived Co3O4/graphene heterojunction nanoscrolls for ppb-level acetone detection

Ya Xiong,Xiao Chang,Xurong Qiao,Kun Li,Lei Zhu,Fujun Xia,Xiaofang Li,Qingbin Zheng,Wei Xing,Qingzhong Xue

For the first time, Co-MOF-74 derived Co 3 O 4 /graphene heterojunction nanoscrolls (Co 3 O 4 /GNS) structure is synthesized by a simple one-step hydrothermal strategy and subsequent calcination process. Theoretically, the growth mechanism of Co 3 O 4 /GNS is revealed by molecular dynamic simulation, demonstrating that a high loading of Co-MOF-74 nanoparticles is needed for effective rolling of GO. The sensor based on Co 3 O 4 /GNS exhibits high response of 58.1 (34-fold enhancement compared with that of Co 3 O 4 ), short response/recovery time of 12 s/66 s (157 s/200 s for Co 3 O 4 ) toward 1 ppm acetone at 190 °C and superior selectivity, which are much better than those of most reported acetone sensors. Moreover, the Co 3 O 4 /GNS can even detect as low as 50 ppb acetone with a notable response (1.24). The appreciable response together with rapid response/recovery of Co 3 O 4 /GNS is attributed to the large heterojunction interface between Co 3 O 4 and graphene nanoscroll and high-speed gas transfer pathways provided by nanoscroll. This unique structure design is believed to offer guidance for generalizable synthesis of metal oxide/GNS that can be effectively applied in the fields of ppb-level gas detection.

CAS / MDL: 6147-53-1
研究领域: 材料科学 · 化学传感器 · 纳米技术
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2020 · IF 7.489

Protonated g-C3N4 cooperated with Co-MOF doped with Sm to construct 2D/2D heterojunction for integrated dye-sensitized photocatalytic H2 evolution

Sheng Zhao,Jing Xu,Min Mao,Lingjiao Li,Xuanhao Li

A dye-sensitive photocatalytic H 2 evolution reaction (HER) system with photogenerated carrier directed conduction was constructed. The protonated g-C 3 N 4 combines with the sheet-like Co MOF to form a 2D/2D heterojunction via electrostatic self-assembly. The protonated g-C 3 N 4 and 2D Co-MOF directionally adsorb Eosin Y (EY) and triethanolamine (TEOA) molecules through hydrogen bond and complexation to achieve a whole photocatalytic system. The integral structure effectively facilitates the utilization of dye sensitizer and hole sacrificial agent to achieve the effective and stable photocatalytic H 2 evolution capacity. The photocatalytic hydrogen evolution rate of g-C 3 N 4 after protonation is 1.88 times as high as that of the original g-C 3 N 4 . On the basis of 2D/2D heterojunction, Co MOF is doped with rare earth element Sm. The 4f electrons and the difference valences (Sm 3+ and Co 2+ ) further suppress the reorganization of photogenerated excitons to achieve highly efficient photocatalytic HER. The directional coupling of sensitizer and electron sacrificial agent combined with rare earth element doping makes the photocatalytic HER rate of the composite material reached 73.42 μmol . h −1 within 5 h under simulated sunlight.

研究领域: 材料科学 · 光化学 · 能源科学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 22 ·10682-10689 · IF 3.925

A two-dimensional thin Co-MOF nanosheet as a nanozyme with high oxidase-like activity for GSH detection

Miaomiao Han,Mengzhen Ren,Zhaohui Li,Lingbo Qu,Lanlan Yu

Nanozymes with the advantages of excellent enzyme-mimicking activity, low cost and high stability have displayed great application potential in diverse fields as replacements for natural enzymes. In this study, a new nanozyme based on an ultrathin two-dimensional metal–organic framework nanomaterial D-ZIF-67 was prepared and characterized. D-ZIF-67 exhibited remarkable oxidase-like activity, which was attributed to the large specific surface area of the two-dimensional sheet structure, as well as its numerous exposed active sites compared with crystal MOFs. In the catalytic process of D-ZIF-67, the hydroxyl radical and superoxide anion played an essential role and facilitated the oxidation of the substrate 3,3′,5,5′-tetramethylbenzidine (TMB) by oxygen. The reducing agent glutathione (GSH) inhibited the catalytic activity of D-ZIF-67 besides reducing the oxidized oxTMB, based on which a simple, sensitive and accurate colorimetric method was developed to determine GSH, with the detection limit of 229.2 nM. This work mainly proposes a new two-dimensional metal–organic framework with high oxidase-like activity and provides a simple and practical platform for visual GSH detection by naked eyes.

研究领域: 生物化学 · 分析化学 · 材料科学
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MATERIALS RESEARCH BULLETIN · 2023 · IF 5.4

Achieving high-efficiency and broad bandwidth with low filler loading for hierarchical Fe3O4/Co-MOF absorbers

Wenjie Hou,Yan Xing,Claudia Li,Tong Li,Dong Liu,Lusi Ernawati,Jaka Sunarso,Xiuxia Meng

Metal-organic frameworks (MOFs) with intrinsic porosity and high specific surface area have aroused broad interests as a promising electromagnetic (EM) absorbing material. However, the introduction of magnetic components in MOFs has remained as a formidable obstacle for subsequent development. Herein, Fe 3 O 4 /Co-MOF composites were fabricated via a facile and scalable co-precipitation process. The microstructure and morphology of the composites were characterized and the combination of hollow Fe 3 O 4 and Co-MOFs was found to contribute towards the dissipation of incident waves due to the magnetic-dielectric synergistic effect. Impressive microwave absorption ability was obtained with a minimum reflection loss of –56.1 dB over a qualified bandwidth (7.9 GHz) at 2.0 mm. Moreover, the radar cross section simulation further confirmed the effective suppression of radar wave scattering using Fe 3 O 4 /Co-MOF composites. This study provides a versatile strategy for designing magnetic-dielectric composites based on MOFs as effective and broadband microwave absorbers.

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

Modified montmorillonite synergizes with Co-MOF@PBO fabric to improve the wear resistance of PBO/phenolic resin composites

Yanling Wang,Zhaozhu Zhang,Mingming Yang,Junya Yuan,Peilong Li,Meng Liu

Co-MOF (cobased metal-organic frame) nanosheets were developed onto the surface of PBO (poly(p-phenylene benzobisoxazole)) fabric, and OMMT (modified montmorillonite) was incorporated into phenolic resin synergistically to improve the wear resistance of PBO/phenolic resin composites. Co-MOF nanosheets with a large specific surface area exhibited strong interlocking and excellent compatibility between the fabric and resin. In addition, OMMT possessed excellent affinity with phenolic resin and a larger lamellar space, and then polymer chains could be conveniently entangled into interlayers, which further confined the movement of molecular chains caused by friction heat. In addition, a weak interlayer force was conducive to facilitating the formation of a uniform and robust transfer-film on the counterpart. It was demonstrated that the Co-MOF@PBO/OMMT composites presented optimal tribological behavior due to the synergistic effect between interfacial modification and OMMT reinforcement.

研究领域: 材料科学 · 表面工程
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