CN110180529A - A kind of preparation method of MOF as precursor synthesis catalysis material - Google Patents
A kind of preparation method of MOF as precursor synthesis catalysis material Download PDFInfo
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- CN110180529A CN110180529A CN201910434392.5A CN201910434392A CN110180529A CN 110180529 A CN110180529 A CN 110180529A CN 201910434392 A CN201910434392 A CN 201910434392A CN 110180529 A CN110180529 A CN 110180529A
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- -1 cation salt Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000011160 research Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000001000 micrograph Methods 0.000 description 12
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 6
- 229910002915 BiVO4 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A kind of preparation method of MOF as precursor synthesis catalysis material, belongs to catalyst field.The present invention is in such a way that MOF is as precursor synthesis catalysis material, first, synthesize the metal organic frame MOF (such as CAU-17) of the stable bismuth of pattern homogeneous structural, MOF and aqueous metal salt are stirred under water bath condition, the mixed liquor centrifugal drying that will be formed after stirring, and calcine at a certain temperature, the catalysis material for maintaining MOF appearance frame can be obtained.The method of the present invention period is short, yield is big, technological operation is simple, and properties of product are stable, catalytic performance is good, and do not easily cause secondary pollution.It is suitble to scale of mass production, there is more wide scientific research and practical value.
Description
Technical field
Preparation method the present invention relates to a kind of MOF (metal organic frame) as precursor synthesis catalysis material belongs to
In catalyst field.
Background technique
In recent years, it is seen that photoresponse photochemical catalyst has obtained extensive research, because of its relatively narrow forbidden bandwidth, suitable energy
Band position, the excellent characteristics such as stable chemical property have bright application prospect in numerous research fields, especially drop in light
The application for solving organic pollutant and photocatalysis Decomposition aquatic products oxygen etc. has become current research hotspot.[1]
Currently, the synthetic method of catalysis material has very much, common high-temperature solid phase reaction method, chemical precipitation method, colloidal sol-
Gel method, hydrothermal/solvent thermal method, microwave assisting method[2]Deng.Hydrothermal/solvent thermal method is situated between using water or organic solvent as reaction
Matter is to compare typical method in inorganic material synthesis, closed reactor (autoclave) is put into after different solutions are mixed
In heated, by causing self-generated pressure, constitute high temperature and high pressure environment and carry out a kind of effective ways of synthetic material.Yu J
Deng[3]BiVO is successfully realized using solvent-thermal method4Synthesis, ammonium metavanadate and bismuth nitrate are uniformly mixed with certain proportion, adjust
Mixed liquor is transferred in reaction kettle after section pH value and obtains the BiVO of different-shape according to certain heating schedule4.To current
Until, it is had not been reported by MOF as the method for precursor synthesis catalysis material.
[1]Tan H L,Amal R,Ng Y H.Alternative strategies in improving the
photocatalytic and photoelectrochemical activities of visible light-driven
BiVO 4:a review[J].Journal of Materials Chemistry A,2017,5(32):16498-16521..
[2]Suarez C M,Hernández S,Russo N.BiVO4as photocatalyst for solar
fuels production through water splitting:a short review[J].Applied Catalysis
A:General,2015,504:158-170.
[3]Yu J,Kudo A.Effects of structural variation on the photocatalytic
performance of hydrothermally synthesized BiVO4[J].Advanced Functional
Materials,2006,16(16):2163-2169.
Summary of the invention
The purpose of the present invention is to provide one kind using MOF as precursor synthesis catalysis material preparation method and purposes,
And the catalysis material being prepared by this method, to be widely used in scientific research and industrial production.
A kind of preparation method of MOF as precursor synthesis catalysis material, comprising the following steps:
(1) dispersant solution for selecting suitable organic solvent to synthesize as MOF；
(2) both soluble organic ligand and dispersant solution are mixed, by magnetic agitation, obtains clear solution；
(3) metal cation salt and above-mentioned solution are mixed, mix well it, obtains uniform solution；
(4) above-mentioned mixed solution is subjected to hydrothermal crystallizing；
(5) entire liquid is removed, is sufficiently washed, and centrifugal drying, obtain metal salt.
(6) deionized water stirring in water bath at a certain temperature is added in metal salt, obtains clear solution；
(7) MOF is added in above-mentioned solution, water-bath continues to stir certain time at the same temperature after mixing；
(8) entire liquid is removed, is sufficiently washed, and centrifugal drying；
(9) presoma by above-mentioned acquisition is calcined in Muffle furnace, and atmosphere is air；
(10) by the collection of products after calcining, product is obtained.
Wherein, the organic solvent is absolute methanol solution；The soluble ligand is trimesic acid；The metal from
Alite is five nitric hydrate bismuths；The metal salt is ammonium metavanadate, ammonium metatungstate, Ammonium Molybdate Tetrahydrate.
Further, in step (2), by soluble organic ligand and dispersant solution in the ratio of 0.05-0.12mol/L
Mixing, mixed temperature are 15-30 DEG C, and the time is to be allowed to mix for 5-30 minutes.
Further, in step (3), the mixed proportion of metal cation salt and step (2) described clear solution is 0.01-
0.05mol/L。
Further, in step (4), the crystallization carries out in crystallizing kettle known in the field.The crystallization condition
It can be various conditions commonly used in this field, but in preferred situation, the condition of the crystallization includes that crystallization temperature is 100-
140 DEG C, crystallization time is 18-30 hours.
Further, in step (5), the centrifugal rotational speed is 6000-10000 rpms, and centrifugation time is 5-10 points
Clock；Washing process is that anhydrous methanol cleans 2-4 times；Drying temperature is 60-80 degrees Celsius, and drying time is 6-24 hours.
Further, in step (6), metal salt and deionized water are mixed in 0.01-0.05mol/L ratio, water-bath temperature
Degree is 60 DEG C, and the time is to be allowed to mix for 5-10 minutes.
Further, in step (7), additional proportion is the MOF of 0.01-0.05mol/L, and bath temperature is 60 DEG C, stirring
Time is 2-5 hours.
Further, in step (8), the centrifugal rotational speed is 6000-10000 rpms, and centrifugation time is 2-5 points
Clock；Washing process is alternately cleaning 2-4 time of deionized water dehydrated alcohol；Drying temperature is 70 degrees Celsius, drying time 6-24
Hour.
Further, in step (9), calcining heating rate is 5-10 DEG C/min, is raised to 450-600 DEG C, keeps the temperature 2-4h.
The present invention is in such a way that MOF is as precursor synthesis catalysis material, firstly, synthesis pattern homogeneous structural is stablized
Bismuth metal organic frame MOF (such as CAU-17), MOF and aqueous metal salt are stirred under water bath condition, after stirring
The mixed liquor centrifugal drying of formation, and calcine at a certain temperature, the catalysis material for maintaining MOF appearance frame can be obtained.
In material synthesis processes, (only hydrothermal synthesis is calcined in air, is not related to true for used simple process safety
Sky, the complex environments such as special calcination atmosphere), instrument is simple (key instrument is beaker, centrifuge, hydro-thermal case, Muffle furnace), and
Period is short, yield is big, technological operation is simple.
In short, the invention patent synthesis technology is easy to operate, it is suitble to scale of mass production, properties of product are stable and do not easily cause
Secondary pollution.Thus it has more wide scientific research and practical value.
Invention advantage:
The present invention uses a kind of preparation method of MOF as precursor synthesis catalysis material, and synthesis cycle is short, is suitble to big
The material structure of large-scale production, acquisition is stablized, and catalytic performance is good.Therefore, this synthetic method is expected to be widely used in novel
In the research and production of catalyst material.
Detailed description of the invention
Fig. 1 is one x-ray powder diffractogram of embodiment, is shown as the characteristic diffraction peak of CAU-17；
Fig. 2 embodiment one is electron scanning micrograph, and Rod-like shape is presented in display CAU-17；
Fig. 3 is one x-ray powder diffractogram of embodiment, is shown as BiVO4Characteristic diffraction peak；
Fig. 4 is one electron scanning micrograph of embodiment, shows BiVO4Maintain the Rod-like shape of presoma；
Fig. 5 is one electron scanning micrograph of embodiment, is shown rodlike for 100-200nm little particle composition；
Fig. 6 is one BiVO of embodiment4Degradation of methylene blue efficiency chart；
Fig. 7 is two x-ray powder diffractogram of embodiment, shows Bi2WO6For the characteristic diffraction peak of main phase；
Fig. 8 is two electron scanning micrograph of embodiment, shows that Rod-like shape is presented in the material；
Fig. 9 is two electron scanning micrograph of embodiment, is shown rodlike for 100-200nm little particle composition；
Figure 10 is three x-ray powder diffractogram of embodiment, is shown as Bi2Mo3O12Characteristic diffraction peak；
Figure 11 is three electron scanning micrograph of embodiment, shows that Rod-like shape is presented in the material；
Figure 12 is electron scanning micrograph.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment.It will be understood by those skilled in the art that
Following embodiment is merely a preferred embodiment of the present invention, and in order to more fully understand the present invention, thus should not be regarded as limiting this hair
Bright range.For those skilled in the art, the invention may be variously modified and varied, all in spirit of the invention
Within principle, made any modification, equivalent replacement or improvement etc. be should all be included in the protection scope of the present invention.Under
The experimental method in embodiment is stated, is conventional method unless otherwise specified；Experimental material used, unless otherwise specified,
It is purchased from conventional biochemical reagent manufacturers.
Centrifugation uses table model high speed centrifuge (XiangYi H-1650) in following embodiment；Scanning electron microscope (SEM) photograph uses awkward silence at a meeting
Transmitting scanning electron microscope (Hitachi S-4800) obtains；X-ray diffraction spectra is by powder x-ray diffraction (Hitachi
U-3010 it) obtains.
Embodiment one:
At 25 DEG C, 1.5g is weighed to benzenetricarboxylic acid (H3BTC), a clean beaker is taken, the anhydrous methanol of 60mL is measured, then
The drug of weighing is added thereto, being put into ultrasonic machine ultrasound is well dispersed in drug in absolute methanol solution, mixes to
All dissolutions weigh five nitric hydrate bismuths (0.3g) and beaker are added, stir evenly after middle solution is uniformly dissolved, molten to solution
After solution is uniform, equivalent is poured into several reaction kettles, and then reaction kettle is put into hydro-thermal case, and 120 DEG C of reactions are for 24 hours.End of reaction
Afterwards, product is centrifuged after five minutes in 10000r/min, is placed in 60 DEG C of baking ovens dry 12h, is finally obtained BiMOF material, x is penetrated
Line powder diffractogram (Fig. 1) is shown as the characteristic diffraction peak of CAU-17, and electron scanning micrograph (Fig. 2) shows the material
Rod-like shape is presented.Weigh 0.1053g ammonium metavanadate (NH4VO3), a clean beaker is taken, the deionized water of 50mL is measured, it will
The drug of weighing is added thereto, and for 60 DEG C of stirring in water bath to clarifying, beaker is added in the BiMOF for weighing the above-mentioned synthesis of 0.5022g, is continued
60 DEG C of stirring in water bath 3h after being centrifuged mixed solution 10000r/min 2 minutes, are placed in 70 DEG C of baking ovens dry 12h, and in Muffle
450 DEG C are warming up to 5 DEG C/min in furnace, heat preservation 2h calcining obtains yellow powder BiVO4.Its x-ray powder diffractogram (figure
3) it is shown as BiVO4Characteristic diffraction peak；Electron scanning micrograph (Fig. 4) shows that Rod-like shape is presented in the material；Scanning
Electron micrograph (Fig. 5) shows that rodlike is that 100-200nm little particle is constituted, and is passed through shown in Fig. 4, BiVO4Rodlike
Length is at 2-5 μm or so.And BiVO as shown in Figure 64Degradation of methylene blue efficiency chart, in 300W xenon lamp, optical filter wavelength <
420nm, the lower methylene blue for capableing of the interior degradation 95% or so of 40min of irradiation.
Embodiment two
At 25 DEG C, 1.5g is weighed to benzenetricarboxylic acid (H3BTC), a clean beaker is taken, the anhydrous methanol of 60mL is measured, then
The drug of weighing is added thereto, being put into ultrasonic machine ultrasound is well dispersed in drug in absolute methanol solution, mixes to
All dissolutions weigh five nitric hydrate bismuths (0.3g) and beaker are added, stir evenly after middle solution is uniformly dissolved, molten to solution
After solution is uniform, equivalent is poured into several reaction kettles, and then reaction kettle is put into hydro-thermal case, and 120 DEG C of reactions are for 24 hours.End of reaction
Afterwards, product is centrifuged after five minutes in 10000r/min, is placed in 60 DEG C of baking ovens dry 12h, is finally obtained BiMOF material.It weighs
0.2216g ammonium metatungstate ((NH4)6H2W12O40·xH2O), a clean beaker is taken, the deionized water of 50mL is measured, by weighing
Drug is added thereto, and for 60 DEG C of stirring in water bath to clarifying, beaker is added in the BiMOF for weighing the above-mentioned synthesis of 0.5022g, continues 60 DEG C of water
Bath stirring 3h after being centrifuged mixed solution 10000r/min 2 minutes, is placed in 70 DEG C of baking ovens dry 12h, and in Muffle furnace with
5 DEG C/min is warming up to 450 DEG C, and heat preservation 2h calcining obtains product.Its x-ray powder diffractogram (Fig. 7) shows Bi2WO6Based on
The characteristic diffraction peak of phase；Electron scanning micrograph (Fig. 8) shows that Rod-like shape is presented in the material；Scanning electron microscope is shone
Piece (Fig. 9) shows that rodlike is that 100-200nm little particle is constituted, and is passed through shown in Fig. 8, and rodlike length is at 2-5 μm or so.
Embodiment three
At 25 DEG C, 1.5g is weighed to benzenetricarboxylic acid (H3BTC), a clean beaker is taken, the anhydrous methanol of 60mL is measured, then
The drug of weighing is added thereto, being put into ultrasonic machine ultrasound is well dispersed in drug in absolute methanol solution, mixes to
All dissolutions weigh five nitric hydrate bismuths (0.3g) and beaker are added, stir evenly after middle solution is uniformly dissolved, molten to solution
After solution is uniform, equivalent is poured into several reaction kettles, and then reaction kettle is put into hydro-thermal case, and 120 DEG C of reactions are for 24 hours.End of reaction
Afterwards, product is centrifuged after five minutes in 10000r/min, is placed in 60 DEG C of baking ovens dry 12h, is finally obtained BiMOF material.It weighs
0.5308g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28), a clean beaker is taken, the deionized water of 50mL is measured, by the drug of weighing
It is added thereto, for 60 DEG C of stirring in water bath to clarifying, beaker is added in the BiMOF for weighing the above-mentioned synthesis of 0.5022g, is continued 60 DEG C of water-baths and is stirred
Mix 3h, after mixed solution 10000r/min is centrifuged 2 minutes, be placed in 70 DEG C of baking ovens dry 12h, and in Muffle furnace with 5 DEG C/
Min is warming up to 450 DEG C, and heat preservation 2h calcining obtains product.Its x-ray powder diffractogram (Figure 10) is shown as Bi2Mo3O12's
Characteristic diffraction peak；Electron scanning micrograph (Figure 11) shows that Rod-like shape is presented in the material；Electron scanning micrograph
(Figure 12) shows that rodlike is that 100-200nm little particle is constituted, and is passed through shown in Figure 11, and rodlike length is at 2-5 μm or so.
The Applicant declares that the present invention is explained by the above embodiments detailed features and method detailed of the invention, but
The invention is not limited to above-mentioned detailed features and method detaileds, that is, do not mean that the present invention must rely on above-mentioned detailed features
And method detailed could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to this hair
The bright equivalence replacement for selecting component and the addition of auxiliary element, the selection of concrete mode etc. and other in the common skill in this field
Within the scope of knowledge, the various change made under the premise of not departing from present inventive concept all falls within the present invention to art personnel
Protection scope and the open scope within.
Claims (9)
1. a kind of preparation method of MOF as precursor synthesis catalysis material, it is characterised in that preparation step is as follows:
(1) dispersant solution for selecting suitable organic solvent to synthesize as MOF；
(2) both soluble organic ligand and dispersant solution are mixed, by magnetic agitation, obtains clear solution；
(3) metal cation salt and above-mentioned solution are mixed, mix well it, obtains uniform mixed solution；
(4) above-mentioned mixed solution is subjected to hydrothermal crystallizing；
(5) entire liquid is removed, is sufficiently washed, and centrifugal drying, obtain metal salt；
(6) deionized water stirring in water bath at a certain temperature is added in metal salt, obtains clear solution；
(7) MOF is added in above-mentioned solution, water-bath continues to stir certain time at the same temperature after mixing；
(8) entire liquid is removed, is sufficiently washed, and centrifugal drying；
(9) presoma by above-mentioned acquisition is calcined in Muffle furnace, and atmosphere is air；
(10) by the collection of products after calcining, product is obtained；
Wherein the organic solvent is absolute methanol solution；The soluble ligand is trimesic acid；The metal cation salt
For five nitric hydrate bismuths；The metal salt is ammonium metavanadate, ammonium metatungstate, Ammonium Molybdate Tetrahydrate.
2. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (2)
In, soluble organic ligand and dispersant solution are mixed in the ratio of 0.05-0.12mol/L, mixed temperature is 15-30
DEG C, the time is to be allowed to mix for 5-30 minutes.
3. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that metal ion
Salt and step (2) described clear solution are mixed in 0.01-0.05mol/L ratio.
4. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (4)
Described in crystallization condition include crystallization temperature be 100-140 DEG C, crystallization time be 18-30 hours.
5. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (5)
In, the centrifugal rotational speed is 6000-10000 rpms, and centrifugation time is 5-10 minutes；Washing process is anhydrous methanol cleaning
2-4 times；Drying temperature is 60-80 degrees Celsius, and drying time is 6-24 hours.
6. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (6)
In, metal salt and deionized water are mixed in 0.01-0.05mol/L ratio, bath temperature is 60 DEG C, and the time is to make for 5-10 minutes
Mixing.
7. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (7)
In, additional proportion is the MOF of 0.01-0.05mol/L, and bath temperature is 60 DEG C, and mixing time is 2-5 hours.
8. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (8)
In, the centrifugal rotational speed is 6000-10000 rpms, and centrifugation time is 2-5 minutes；Washing process is that deionized water is anhydrous
Ethyl alcohol alternately cleaning 2-4 times；Drying temperature is 70 degrees Celsius, and drying time is 6-24 hours.
9. preparation method of the MOF as shown in claim 1 as precursor synthesis catalysis material, it is characterised in that step (9)
In, calcining heating rate is 5-10 DEG C/min, is raised to 450-600 DEG C, keeps the temperature 2-4h.
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| CN111715300A (en) * | 2020-06-22 | 2020-09-29 | 江南大学 | Zinc ferrite/Bi-MOF/tannic acid composite visible light catalyst |
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| CN113333002A (en) * | 2021-06-12 | 2021-09-03 | 景德镇陶瓷大学 | Preparation method of CdS quantum dot-loaded bismuth oxide composite visible light catalytic material and product prepared by same |
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| CN113398956A (en) * | 2021-06-17 | 2021-09-17 | 西安石油大学 | Visible-light-responsive BiOI photocatalyst and preparation method and application thereof |
| CN113398956B (en) * | 2021-06-17 | 2023-08-04 | 西安石油大学 | BiOI photocatalyst with visible light response and preparation method and application thereof |
| CN114790017A (en) * | 2022-04-28 | 2022-07-26 | 南京林业大学 | Method for treating dye and/or heavy metal wastewater and special composite material thereof |
| CN114835233A (en) * | 2022-06-01 | 2022-08-02 | 闽江学院 | Method for rapidly removing chloride ions in wastewater by using bismuth-based metal organic framework material |
| CN114835233B (en) * | 2022-06-01 | 2023-09-12 | 闽江学院 | Method for rapidly removing chloride ions in wastewater by bismuth-based metal organic framework material |
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