CN102380424B - Heteropoly acid zeolite coated rare earth-organic framework material and its preparation method - Google Patents
Heteropoly acid zeolite coated rare earth-organic framework material and its preparation method Download PDFInfo
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- CN102380424B CN102380424B CN 201110266883 CN201110266883A CN102380424B CN 102380424 B CN102380424 B CN 102380424B CN 201110266883 CN201110266883 CN 201110266883 CN 201110266883 A CN201110266883 A CN 201110266883A CN 102380424 B CN102380424 B CN 102380424B
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Abstract
The invention relates to a heteropoly acid zeolite coated rare earth-organic framework material, which has a chemical formula of [Dy48(NO3)48(bpdc)48(PW12O40)(TBA)3]*140H2O, wherein bpdc is 2,2'-bipyridyl-6,6'-dicarboxylic acid, TBA is tetrabutylammonium hydroxide. The method for preparing the material comprises the following steps: adding a mixed solvent of methanol and chloroform in a mixture of dysprosium nitrate, manganese chloride, H2bpdc, H3PW12O40 and TBA, reacting at the temperature of 80 DEG C for 48 hours, filtering and washing to obtain the rare earth-organic framework material. The material can be used as a photocatalyst for methylene blue degradation reaction. The invention has the advantages that the material is the heteropoly acid zeolite coated rare earth-organic frameworkmaterial with an initial rho type structure, the material has good photodegradation effect on methylene blue, and the preparation technology is simple. The method of the invention provides theoretical basis for large scale popularization and application of purifying industrial sewage by polyoxometallate photocatalysis.
Description
[technical field]
The present invention relates to the technology of preparing of solid-supported catalyst, particularly a kind of coating heteropoly acid zeolite type rare earth-organic framework materials and preparation method thereof.
[background technology]
The catalyst of design synthesizing efficient practicality is becoming the important component part of chemical industry.Homogeneous catalyst shows very high activity and selectivity in a large amount of synthetic reactions, but because its unstable difficulty of separating with recovery causes their application to be restricted.By with the supported method energy of homogeneous catalyst so that it is convenient to recovery and reuse.In recent years, the novel solid-supported catalyst of a class has attracted people's interest gradually.Here it is functional metal-organic framework materials.They are connected to form the network structure with unlimited extension by the coordination of metal and part.These materials are insoluble under certain reaction media, have therefore had the potentiality as heterogeneous catalysis.Very important characteristics of this material are their hole sizes, and shape and chemical environment can be regulated by selecting suitable construction unit (metal ion and organic ligand).The metal-organic framework materials of bibliographical information is mainly used in some simple, direct catalytic reactions at present, and used metal-organic framework materials kind is single, does not have the advantage in conjunction with multiple catalysts.Photocatalysis has important theory significance and real value as the binding site of photochemistry and catalytic chemistry.There are many chemical reactions to improve reaction rate by photocatalysis, and make harsh reaction condition become gentle condition.
[summary of the invention]
The objective of the invention is for above-mentioned technical Analysis, a kind of coating heteropoly acid zeolite type rare earth-organic framework materials and preparation method thereof is provided, this material heat endurance is high, organic degradation reaction in the aqueous solution is presented higher photocatalytic activity, and its preparation technology is simple, easy to implement to promote.
Technical scheme of the present invention:
A kind of coating heteropoly acid zeolite type rare earth-organic framework materials, chemical formula is: [Dy
48(NO
3)
48(bpdc)
48(PW
12O
40) (TBA)
3] 140H
2O, wherein bpdc is 2,2 '-bipyridyl-6,6 '-dicarboxylic acids (2,2'-bipyridine-6,6'-dicarboxylic acid), TBA are TBAH (tetrabutylammonium hydroxide); Complex is the cubic system that the dissymmetrical structure unit is constructed, and space group is Pn-3n, and cell parameter is: a=b=c=29.1293 (4)
α=β=γ=90 °; Be in dodecahedral eight-coordinate Dy (III) in this complex and be one and have tetrahedron macromolecular architecture unit [Dy
48(NO
3)
48(bpdc)
48], the assembling of this tetrahedron construction unit has formed the zeolite structured rare earth-organic framework materials of coating heteropllyacids with rho type topological structure, and this material has α-cage structure, and its aperture is 17.6
Loaded by heteropoly acid is in α-cage.
A kind of preparation method of described coating heteropoly acid zeolite type rare earth-organic framework materials comprises the steps:
1) at Dy (NO
3)
36H
2O, MnCl
24H
2O, H
2Bpdc, H
3PW
12O
40(C
4H
9)
4In the mixed solution of NOH, adding volume ratio is methyl alcohol and the chloroform mixed solvent of 1:1, under 80 ° of C, carries out hydro-thermal reaction, and the reaction time is 48h;
2) speed with 1.4 ° of C/h is cooled to 25 ° of C, is the methyl alcohol of 1:1 and the washing of chloroform mixed solvent 3 times with volume ratio after filtering, must target product after the drying.
Described Dy (NO
3)
36H
2O, MnCl
24H
2O, H
2Bpdc, H
3PW
12O
40(C
4H
9)
4The mol ratio of NOH is 10:10:20:1:5.
The amount ratio of described methyl alcohol and chloroform mixed solvent and mixed material is 10mL:300-330mg.
A kind of application of described coating heteropoly acid zeolite type rare earth-organic framework materials, the photochemical catalyst for the methylene blue degradation reaction comprises the steps:
1) will coat heteropoly acid zeolite type rare earth-organic framework materials is suspended in the aqueous solution of methylene blue of new preparation, lucifuge stirs 30min under the room temperature, this material is uniformly dispersed in solution and material surface and methylene blue molecule between reach the balance of adsorption-desorption;
2) open light source and carry out light-catalyzed reaction, vigorous stirring solution and communicate with air in the course of reaction, the temperature of reaction system is 20 ± 2 ° of C.
The concentration of described aqueous solution of methylene blue is 50mg/L, and the amount ratio that coats heteropoly acid zeolite type rare earth-organic framework materials and aqueous solution of methylene blue is 0.15g:100mL.
Advantage of the present invention and good effect:
This coats heteropoly acid zeolite type rare earth-organic framework materials, has very high heat endurance, and all insoluble in water neutralizes other common solvents, also very stable in air, thermogravimetric analysis only shows and just can decompose more than the C at 370 °; Because it has special Surface Physical Chemistry character, thereby organic degradation reaction in the aqueous solution is presented higher photocatalytic activity, overcome the low and few shortcoming of surface-active point of polyoxometallate specific area; And the separation of catalyst is very convenient with recovery, and catalyst circulation is used and do not found that catalytic activity has obvious change 3 times, and finds no the phenomenon of catalyst activity component seepage in the catalytic process; This material preparation, technique is simple, easy to implement, and applying on a large scale for polyoxometallate light catalytic purifying trade effluent provides theoretical foundation.
[description of drawings]
Fig. 1 is [Dy
48(NO
3)
48(bpdc)
48] schematic diagram of basic structural unit of framework.
Fig. 2 coats heteropoly acid zeolite type rare earth-organic framework materials tomograph for this.
Fig. 3 coats under heteropoly acid zeolite type rare earth-organic framework materials ultraviolet light 4 kinds of dyestuff degraded figure for this.
Fig. 4 coats heteropoly acid zeolite type rare earth-organic framework materials catalytic cycle figure for this.
[specific embodiment]
Embodiment:
A kind of preparation method of described coating heteropoly acid zeolite type rare earth-organic framework materials comprises the steps:
1) with 98mg Dy (NO
3)
36H
2O (0.2mmol), 40mg MnCl
24H
2O (0.2mmol), 98mgH
2Bpdc (0.4mmol), (58mg H
3PW
12O
40(0.02mmol) and 18mg (C
4H
9)
4Put into the polytetrafluoroethylliner liner of the hydrothermal reaction kettle of 23mL after NOH (0.1mmol) mixes, adding the 10mL volume ratio is methyl alcohol and the chloroform of 1:1, at 80 ° of C reaction 48h;
2) speed with 1.4 ° of C/h is cooled to 25 ° of C, is the methyl alcohol of 1:1 and the washing of chloroform mixed solvent 3 times with the 2mL volume ratio after filtering, must target product after the drying.This product gray has polyhedron-shapedly, and the productive rate that calculates based on metal Dy is 52%.
The crystal structure determination of prepared coating heteropoly acid zeolite type rare earth-organic framework materials:
Supernova type X-ray single crystal diffractometer is adopted in crystal structure determination, uses Mo K alpha ray (λ=0.71073 through the graphite monochromatization
) be incident radiation, with
Scan mode is collected point diffraction, obtains cell parameter through least square refinement, utilizes the SHELXL-97 direct method to solve crystal structure from the difference Fourier electron-density map, and through Lorentz and polarity effect correction.All H atoms are synthetic and definite through desirable position calculation by difference Fourier.The actual crystal determination data sees Table 1.
The crystallographic data of table 1 Coordination Polymer
The structure of prepared coating heteropoly acid zeolite type rare earth-organic framework materials is seen Fig. 1, Fig. 2.
The dissymmetrical structure unit of this material is as shown in Figure 1: crystal belongs to cubic system, and space group is Pn-3n, and cell parameter is: a=b=c=29.1293 (4)
α=β=γ=90 °; Independently Dy (III) ion is arranged on a kind of crystallography, a nitrate anion and 1 part bpdc in this material in asymmetric cell.As shown in Figure 1, each Dy (III) is eight-coordinate, and wherein 2 nitrogen-atoms are from part bpdc, and four oxygen atoms also have 2 oxygen atoms from nitrate anion from 3 part bpdc independently.Each part bpdc connects 3 Dy (III) atom, O1 wherein, and O2, O3 are connected two Dy (III) atom with O4; N1, N2,1 Dy of O1 and O4 chelating (III) atom.Two carboxyls of part bpdc have determined the topological structure of complex.Being in dodecahedral eight-coordinate Dy (III) is a macromolecular architecture unit (MBB, molecular building block).This unit is four connections, therefore can be considered to a tetrahedron construction unit (TBU, tetrahedral building unit).By the assembling of this unit, formed and had the zeolite structured metal-organic framework materials of rho type class.The basic construction unit of this framework is [Dy
48(NO
3)
48(bpdc)
48].The crystal structure unit volume of complex is 8 times of traditional inorganic zeolite volume.Comprise a α-cage with 17.6A ° of aperture in the basic construction unit of this framework, wherein loaded by heteropoly acid is in this cage, as shown in Figure 2.
A kind of application of described coating heteropoly acid zeolite type rare earth-organic framework materials, the photochemical catalyst for the methylene blue degradation reaction comprises the steps:
1) to be suspended in the concentration of the new preparation of 100mL be in the aqueous solution of methylene blue of 50mg/L to coating heteropoly acid zeolite type rare earth-organic framework materials that 0.15g is prepared, lucifuge stirs 30min under the room temperature, this material is uniformly dispersed in solution and material surface and methylene blue molecule between reach the balance of adsorption-desorption;
2) open light source and carry out light-catalyzed reaction, vigorous stirring solution and communicate with air in the course of reaction, the temperature of reaction system is 20 ± 2 ° of C.
Light-catalysed detection method:
The variation of dye strength is by Jasco V-570UV-VIS spectrophotometer measurement in the photocatalysis experiment.In certain time interval, take out reaction suspension, the centrifugal supernatant liquor that obtains and the variation that records the dye solution absorbance by UV-VIS spectrum are converted into concentration.
In order to prove that this material is used for the catalytic effect of the photochemical catalyst of methylene blue degradation reaction, alternative has been selected three kinds of dyestuff tester rhodamine Bs, methyl orange and Congo red, with the identical process conditions of methylene blue under carry out under ultra violet lamp photocatalysis experiment relatively, the photocatalysis testing result is seen Fig. 3, Fig. 4.
Testing result shows: before ultra violet lamp, the concentration of methylene blue has descended 47%, as shown in Figure 3, has shown the strong adsorption of complex for substrate.Since in the strong adsorption of catalyst surface so that under ultra violet lamp, obtain relatively high conversion ratio.Although catalyst is stronger for Congo red absorption, conversion ratio does not have the methylene blue height.This may be to have relatively large and more complicated structure so that its hard degradation owing to Congo red.And catalyst is also not obvious for the adsorption effect of other two kinds of dyestuffs, to such an extent as to conversion ratio is relatively low.After reaction was finished, catalyst can be separated from solution by centrifugal filtration.Reacted solution does not have UV absorption at 190-300nm, and proving does not have the drop of heteropoly acid to go out.In addition, we have carried out again the analysis of ICP-AES to solution, do not detect the existence of W, have proved that further catalyst has the characteristic of typical heterogeneous catalysis.Catalyst reuses after treatment.Its degrading activity to methylene blue still remains unchanged for 3 times afterwards in repeated test, as shown in Figure 4.In order better to study the catalytic activity of complex, we select methylene blue to carry out dynamics research as reaction model.This degradation process is followed first-order kinetics, is consistent with the Langmuir-Hinshelwood kinetic model.The slope of the straight line that obtains by linear regression is first order rate constant k
AppObtain the k of catalyst through match
AppValue is 0.0126min
-1Ultraviolet lighting after 120 minutes the palliating degradation degree to methylene blue reach 90%.The result shows that this material has significant light degradation effect to methylene blue.
Claims (6)
1. one kind coats heteropoly acid zeolite type rare earth-organic framework materials, and it is characterized in that: chemical formula is: [Dy
48(NO
3)
48(bpdc)
48(PW
12O
40) (TBA)
3] 140H
2O, wherein bpdc is 2,2 '-bipyridyl-6,6 '-dicarboxylic acids, TBA are TBAH; Complex is the cubic system that the dissymmetrical structure unit is constructed, and space group is Pn-3n, and cell parameter is: a=b=c=29.1293 (4)
α=β=γ=90 °; Be in dodecahedral eight-coordinate Dy (III) in this complex and be one and have tetrahedron macromolecular architecture unit [Dy
48(NO
3)
48(bpdc)
48], the assembling of this tetrahedron construction unit has formed the zeolite structured rare earth-organic framework materials of coating heteropoly acid with rho type topological structure, and this material has α-cage structure, and its aperture is 17.6A °, and loaded by heteropoly acid is in α-cage.
2. a preparation method who coats as claimed in claim 1 heteropoly acid zeolite type rare earth-organic framework materials is characterized in that comprising the steps:
1) at Dy (NO
3)
36H
2O, MnCl
24H
2O, H
2Bpdc, H
3PW
12O
40(C
4H
9)
4In the mixed solution of NOH, adding volume ratio is methyl alcohol and the chloroform mixed solvent of 1:1, under 80 ° of C, carries out hydro-thermal reaction, and the reaction time is 48h;
2) speed with 1.4 ° of C/h is cooled to 25 ° of C, is the methyl alcohol of 1:1 and the washing of chloroform mixed solvent 3 times with volume ratio after filtering, must target product after the drying.
3. the preparation method of described coating heteropoly acid zeolite type rare earth-organic framework materials according to claim 2 is characterized in that: described Dy (NO
3)
36H
2O, MnCl
24H
2O, H
2Bpdc, H
3PW
12O
40(C
4H
9)
4The mol ratio of NOH is 10:10:20:1:5.
4. the preparation method of described coating heteropoly acid zeolite type rare earth-organic framework materials according to claim 3, it is characterized in that: the amount ratio of described methyl alcohol and chloroform mixed solvent and mixed material is 10mL:300-330mg.
5. application that coats as claimed in claim 1 heteropoly acid zeolite type rare earth-organic framework materials is characterized in that: be used for the photochemical catalyst of methylene blue degradation reaction, comprise the steps:
1) will coat heteropoly acid zeolite type rare earth-organic framework materials is suspended in the aqueous solution of methylene blue of new preparation, lucifuge stirs 30min under the room temperature, this material is uniformly dispersed in solution and material surface and methylene blue molecule between reach the balance of adsorption-desorption;
2) open light source and carry out light-catalyzed reaction, vigorous stirring solution and communicate with air in the course of reaction, the temperature of reaction system is 20 ± 2 ° of C.
6. the according to claim 5 application of described coating heteropoly acid zeolite type rare earth-organic framework materials, it is characterized in that: the concentration of described aqueous solution of methylene blue is 50mg/L, and the amount ratio that coats heteropoly acid zeolite type rare earth-organic framework materials and aqueous solution of methylene blue is 0.15g:100mL.
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| CN104478759A (en) * | 2014-12-04 | 2015-04-01 | 华东师范大学 | Preparation method for synthesizing imine through photo-catalytic oxidation of amine |
| CN106000467B (en) * | 2016-06-03 | 2019-01-15 | 台山市傅诚纺织厂有限公司 | A kind of photochemical catalyst and preparation method thereof for rhodamine B degradation |
| CN105968378B (en) * | 2016-06-20 | 2019-03-01 | 吉林大学 | A method of with heteropoly acid ligand synthesizing rare-earth-heteropoly acid coordination polymer |
| CN106215197B (en) * | 2016-07-25 | 2019-02-19 | 南开大学 | A kind of zeolite type metal-organic framework material and preparation method thereof based on gadolinium ion |
| CN106366102B (en) * | 2016-08-08 | 2018-02-16 | 河南大学 | Waugh manganese molybdates that a kind of dysprosium-isonicotinic acid includes and its preparation method and application |
| CN107312026B (en) * | 2017-06-20 | 2019-03-26 | 安徽师范大学 | With the rare earth samarium complex and preparation method of photocatalytic degradation of dye function and application |
| CN107335470B (en) * | 2017-06-20 | 2019-11-26 | 安徽师范大学 | Rare earth neodymium metal-organic framework catalysis material and preparation method thereof and application |
| CN109794299B (en) * | 2018-12-25 | 2022-02-01 | 中国石油天然气股份有限公司 | Hydrogenation catalyst, preparation method thereof and distillate oil hydrofining method |
| CN109794298B (en) * | 2018-12-25 | 2022-02-01 | 中国石油天然气股份有限公司 | Hydrofining catalyst and preparation method thereof, and distillate oil hydrofining method |
| CN115536855B (en) * | 2022-08-12 | 2024-01-26 | 吉林化工学院 | Preparation method and application of polyacid-based europium complex |
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| CN1978585A (en) * | 2006-12-01 | 2007-06-13 | 南开大学 | Rare earth-earth element-three-metal complex type photoluminescent material, and its preparing method and use |
| CN101412908A (en) * | 2008-11-28 | 2009-04-22 | 南开大学 | Synthesis and use of rare earth Eu or Y and Eu mixing complex type photoluminescent material |
| CN102002061A (en) * | 2010-11-12 | 2011-04-06 | 南开大学 | Porous copper coordination polymer material as well as preparation method and application thereof |
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| CN1978585A (en) * | 2006-12-01 | 2007-06-13 | 南开大学 | Rare earth-earth element-three-metal complex type photoluminescent material, and its preparing method and use |
| CN101412908A (en) * | 2008-11-28 | 2009-04-22 | 南开大学 | Synthesis and use of rare earth Eu or Y and Eu mixing complex type photoluminescent material |
| CN102002061A (en) * | 2010-11-12 | 2011-04-06 | 南开大学 | Porous copper coordination polymer material as well as preparation method and application thereof |
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