Activation of Peroxymonosulfate by CuNi@C Derived from Metal–Organic Frameworks Precursor

2018 ◽  
Vol 71 (11) ◽  
pp. 874 ◽  
Author(s):  
Xue Huang ◽  
Jing Zhang ◽  
Xiao Zhang ◽  
Qing-Ping Wu ◽  
Chun-Hui Yan

Calcined Cu-based metal–organic frameworks impregnated with nickel nitrate catalysts (CuNi@C) were synthesised. X-Ray diffraction, scanning electronic microscopy, energy dispersive X-ray spectrometry, and X-ray photoelectron spectroscopy techniques were applied for the characterisation of the synthesised catalyst, which revealed an octahedral particle shape, rough surface, and metallic copper (Cu, CuO) and nickel (Ni, NiO) particles. CuNi@C was fabricated as a novel peroxymonosulfate (PMS) activator for the oxidative degradation of Acid Orange 7 (AO7) in aqueous media. Results showed that the CuNi@C/PMS system can efficiently degrade nearly 100 % of 0.02 mmol L−1 AO7 within 60 min. In addition, the trapping experiments confirmed the participation of sulfate radicals (SO4•−) and hydroxyl radicals (HO•) as reactive species in the system. Furthermore, the effects of parameters including catalyst and PMS dosages, initial concentration of AO7, and pH were studied. Results showed that the decolourisation efficiency increased with the increase of catalyst dosage, but decreased with the increase of AO7 concentration. The optimal PMS concentration was 0.675 mmol L−1, and initial pH showed no significant effect on the degradation of AO7. Moreover, the CuNi@C could be reused four times with good activity and reusability. Findings revealed that the CuNi@C/PMS system shows potential for degrading contaminants in the environment, due to its catalytic activity and non-negligible adsorption.

2017 ◽  
Vol 76 (6) ◽  
pp. 1436-1446 ◽  
Author(s):  
Chenmo Wei ◽  
Jing Zhang ◽  
Yongli Zhang ◽  
Gucheng Zhang ◽  
Peng Zhou ◽  
...  

Sulfate radical-based advanced oxidation processes have had considerable attention due to the highly oxidizing function of sulfate radicals (SO4−·) resulting in acceleration of organic pollutants degradation in aqueous environments. A Co-Ni mixed oxide nanocatalyst, which was prepared by the sol-gel method, was employed to activate peroxymonosulfate (PMS, HSO5−) to produce SO4−· with Acid Orange 7 (AO7) selected as a radical probe. The catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). The characterization results indicated that the ingredient of the catalyst had been changed and the amount of surface hydroxyl increased significantly with the addition of Ni. Therefore, it proved that Co-NiOx catalyst was more effective than CoOx to activate PMS. Moreover, ultrasound (US) can increase the degradation rate of AO7 and US/Co-NiOx/PMS system. This study also focused on some synthesis parameters and the system reached the maximum efficiency under the condition when [PMS] = 0.4 mM, [catalyst] = 0.28 g/L, Pus = 200 W. The AO7 removal in these systems follows first order kinetics. Last but not least, quenching studies was conducted which indicated that the amount of hydroxyl radicals (·OH) increases with the increase of initial pH and SO4−· was the primary reactive oxidant for AO7 degradation.


2020 ◽  
Vol 73 (12) ◽  
pp. 1271
Author(s):  
Renata Lippi ◽  
Campbell J. Coghlan ◽  
Shaun C. Howard ◽  
Christopher D. Easton ◽  
Qinfen Gu ◽  
...  

Manganese-based metal–organic frameworks (MOFs) metalated with Rh were used as pre-catalysts for CO2 hydrogenation. Activated insitu (80% H2, 20% CO2, 350°C), the resulting templated catalysts displayed CO2 conversion of up to 20%, with CH4 as the main product. Used catalysts were compared with samples templated in 5% H2/Ar at 350°C using powder X-ray diffraction, electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. It was found that under reducing atmosphere Rh0 nanoparticles formed and organic MOF components decomposed, which allowed growth of MnO or MnCO3 and the formation of a mesh of catalytic Rh0 nanoparticles.


2020 ◽  
Vol 75 (8) ◽  
pp. 727-732
Author(s):  
Chen Zhang ◽  
Jian-Qing Tao

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.


Author(s):  
Stephen J. I. Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  

2016 ◽  
Vol 98 ◽  
pp. 70-74
Author(s):  
Andrius Laurikėnas ◽  
Jurgis Barkauskas ◽  
Aivaras Kareiva

In this study, lanthanide elements (Ln3+) and 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylic acid (TFBDC) based metal-organic frameworks (MOFs) were synthesized by precipitation and diffusion-controlled precipitation methods. Powders insoluble in aqueous media and polar solvents were obtained. The microstructure and properties of Ln3+ MOFs were evaluated and discussed. X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and fluorescence spectroscopy (FLS) were carried out to characterize Ln3+ MOF's crystallinity, the microstructure, chemical composition and optical properties.


2021 ◽  
Author(s):  
Qing-Xia Yao ◽  
Miaomiao Tian ◽  
Jun Zheng ◽  
Jintang Xue ◽  
Xuze Pan ◽  
...  

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized by using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show 1-Ln are isostructural and have 3D porous...


2014 ◽  
Vol 70 (a1) ◽  
pp. C157-C157
Author(s):  
Claire Hobday ◽  
Stephen Moggach ◽  
Carole Morrison ◽  
Tina Duren ◽  
Ross Forgan

Metal-organic frameworks (MOFs) are a well-studied class of porous materials with the potential to be used in many applications such as gas storage and catalysis.[1] UiO-67 (UiO = University of Oslo), a MOF built from zirconium oxide units connected with 4,4-biphenyldicarboxylate (BDC) linkers, forms a face centred cubic structure. Zirconium has a high affinity towards oxygen ligands making these bridges very strong, resulting in UiO-based MOFs having high chemical and thermal stability compared to other MOF structures. Moreover, UiO-67 has become popular in engineering studies due to its high mechanical stability.[2] Using high pressure x-ray crystallography we can exert MOFs to GPa pressures, experimentally exploring the mechanical stability of MOFs to external pressure. By immersing the crystal in a hydrostatic medium, pressure is applied evenly to the crystal. On surrounding a porous MOF with a hydrostatic medium composed of small molecules (e.g. methanol), the medium can penetrate the MOF, resulting in medium-dependant compression. On compressing MOF-5 (Zn4O(BDC)3) using diethylformamide as a penetrating medium, the framework was shown to have an increased resistance to compression, becoming amorphous several orders of magnitude higher in pressure than observed on grinding the sample.[3] Here we present a high-pressure x-ray diffraction study on the UiO-based MOF UiO-67, and several new synthesised derivatives built from same metal node but with altered organic linkers, allowing us to study in a systematic way, the mechanical stability of the MOF, and its pressure dependence on both the linker, and pressure medium.


2021 ◽  
Vol 9 ◽  
Author(s):  
Wang Xie ◽  
Jie Wu ◽  
Xiaochun Hang ◽  
Honghai Zhang ◽  
Kang shen ◽  
...  

By employment of amino-functionalized dicarboxylate ligands to react with d10 metal ions, four novel metal-organic frameworks (MOFs) were obtained with the formula of {[Cd(BCPAB)(μ2-H2O)]}n (1), {[Cd(BDAB)]∙2H2O∙DMF}n (2), {[Zn(BDAB)(BPD)0.5(H2O)]∙2H2O}n (3) and {[Zn(BDAB)(DBPB)0.5(H2O)]∙2H2O}n (4) (H2BCPAB = 2,5-bis(p-carbonylphenyl)-1-aminobenzene; H2BDAB = 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene); BPD = (4,4′-bipyridine); DBPB = (E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; DMF = N,N-dimethylformamide). Complex 1 is a three-dimensional (3D) framework bearing seh-3,5-Pbca nets with point symbol of {4.62}{4.67.82}. Complex 2 exhibits a 4,4-connected new topology that has never been reported before with point symbol of {42.84}. Complex 3 and 4 are quite similar in structure and both have 3D supramolecular frameworks formed by 6-fold and 8-fold interpenetrated 2D coordination layers. The structures of these complexes were characterized by single crystal X-ray diffraction (SC-XRD), thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements. In addition, the fluorescence properties and the sensing capability of 2–4 were investigated as well and the results indicated that complex 2 could function as sensor for Cu2+ and complex 3 could detect Cu2+ and Ag+via quenching effect.


2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.


2020 ◽  
Vol 75 (4) ◽  
pp. 347-352
Author(s):  
Liang Liang ◽  
Chen-Dong Pan ◽  
Jun Wang

AbstractA new Cu(II) metal-organic framework, [Cu(BMIOPE)(Br-BDC)]n (1) [Br-H2BDC = 5-bromo-isophthalic acid, BMIOPE = 4,4′-bis(2-methylimidazol-1-yl)diphenyl ether], has been hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis, and single-crystal X-ray diffraction. Complex 1 possesses a unique two-fold interpenetrating two-dimensional framework with sql topology. The photocatalytic property of complex 1 for oxidative degradation of methyl orange and methylene blue with hydrogen peroxide was examined under UV irradiation.


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