CN111701620A - Synthetic method of tungsten trioxide/ZIF-8 composite catalyst - Google Patents
Synthetic method of tungsten trioxide/ZIF-8 composite catalyst Download PDFInfo
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- CN111701620A CN111701620A CN202010234551.XA CN202010234551A CN111701620A CN 111701620 A CN111701620 A CN 111701620A CN 202010234551 A CN202010234551 A CN 202010234551A CN 111701620 A CN111701620 A CN 111701620A
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- tungsten trioxide
- zif
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- deionized water
- methylimidazole
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 35
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 239000004246 zinc acetate Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010626 work up procedure Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 8
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052751 metal Chemical group 0.000 description 1
- 239000002184 metal Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the technical field of photocatalysis, and particularly relates to a synthesis method of a tungsten trioxide/ZIF-8 composite catalyst, which at least comprises the following steps: (1) dispersing tungsten trioxide nano sheets in deionized water, adding a 2-methylimidazole water solution into the tungsten trioxide nano sheets, and carrying out ultrasonic treatment for 5-15 min; (2) dropwise adding 2-methylimidazole water solution, and stirring for 8-15 min; (3) adding the prepared zinc acetate aqueous solution, and stirring at room temperature for 1.5-2.5 h; (4) washing with a washing solution and drying to obtain the target product. Tungsten trioxide has higher oxidation-reduction potential, ZIF-8 is a crystalline porous material, has higher specific surface area, porous structure and abundant Lewis basic sites, has higher adsorption capacity, and prepares a compound by combining the advantages of the tungsten trioxide and the ZIF-8, and can effectively improve the adsorption capacity of the tungsten trioxide.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a synthetic method of a tungsten trioxide/ZIF-8 composite catalyst.
Background
Photocatalysis, which is the triggering of the cleavage of many chemical bonds under mild conditions by photoelectrons or holes generated by solar radiation, has been used to date for the decomposition of a variety of chemical bonds, such as C = O, C-C, C-H, N ≡ N. Generally, the photocatalytic reaction mainly comprises three steps: firstly, reactant molecules are adsorbed and activated on the surface of a photocatalyst; the second step is the transfer of the photocatalytic carrier between the reactant molecules and the photocatalyst; the third step is the analytical escape of the product. Firstly, the adsorption and activation of reactant molecules are key steps of the next photocatalytic reaction, the adsorption of the reactant molecules is facilitated due to the large surface area and the porous structure, and the adsorbed molecules can be activated due to unsaturated bonds on the surface. Tungsten trioxide nanosheets are reported to have a relatively high redox potential, however, tungsten trioxide has a surface area that is compromised and has very limited adsorption capacity. The ZIF-8 is a most basic unit consisting of 2-methylimidazole and metal atoms Zn, and has a higher specific surface area, a porous structure and rich Lewis base sites due to the special structure of the ZIF-8, so that the enrichment of substrate molecules is facilitated, a large number of active sites can be provided, the adsorption energy of the substrate molecules is reduced, the ZIF-8 has higher adsorption capacity, and the ZIF-8 has remarkable advantages in photocatalytic reaction.
Disclosure of Invention
The invention provides a synthesis method of a tungsten trioxide/ZIF-8 composite catalyst, and aims to provide a composite for enhancing the adsorption capacity of tungsten trioxide. The specific contents are as follows:
a synthetic method of a tungsten trioxide/ZIF-8 composite catalyst at least comprises the following steps:
(1) dispersing tungsten trioxide nano sheets in deionized water, adding a 2-methylimidazole water solution into the tungsten trioxide nano sheets, and carrying out ultrasonic treatment for 5-15 min;
(2) dropwise adding 2-methylimidazole water solution, and stirring for 8-15 min;
(3) adding the prepared zinc acetate aqueous solution, and stirring at room temperature for 1.5-2.5 h;
(4) washing with a washing solution and drying to obtain the target product.
Preferably, the preparation method of the tungsten trioxide nanosheet comprises the following steps: dissolving sodium tungstate dihydrate and polyvinylpyrrolidone in deionized water; and then dropwise adding acetic acid to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave for reaction for 7-9 hours, naturally cooling to room temperature to obtain a crude product, and carrying out post-treatment on the crude product to obtain the tungsten trioxide nanosheet.
Preferably, the work-up of the crude product comprises at least the following steps: centrifuging the crude product to collect powder, washing the powder with deionized water and absolute ethyl alcohol for 6-8 times to obtain a wet product, and drying the wet product in a vacuum drying oven.
Preferably, the washing liquid is a mixture of deionized water and anhydrous methanol, and the volume ratio of the two is as follows: 1:1-2.
Preferably, the concentration of the 2-methylimidazole aqueous solution is 0.28-1.12 mol/L, and the concentration of the zinc acetate aqueous solution is 0.1-0.4 mol/L.
Preferably, the ratio of tungsten trioxide to the amount of 2-methylimidazole in step (1), 2-methylimidazole in step (2) and zinc acetate added is: 1:(3-6):(2.7-5.4):(11-44).
Preferably, the mass ratio of the acetic acid, the sodium tungstate dihydrate, the polyvinylpyrrolidone and the deionized water is as follows: 1:660:100:12.
Preferably, the autoclave is coated with a polytetrafluoroethylene lining, and the polyvinylpyrrolidone has a relative molecular weight of 58000.
Compared with the prior art, the invention has the following advantages: the tungsten trioxide/ZIF-8 composite catalyst is prepared, ZIF-8 has rich pore structure and larger specific surface area, and is beneficial to enrichment of substrate molecules on the one hand, and can provide a large number of active sites on the other hand, reduce the adsorption energy of the substrate molecules and improve the adsorption/activation capacity of the substrate molecules on the other hand; the tungsten trioxide is beneficial to accelerating the migration of carriers from the catalyst body to the surface of the catalyst, so that more photo-generated carriers migrate to active sites on the surface of the catalyst to perform oxidation-reduction reaction with adsorbed substrate molecules; a heterogeneous interface is formed by ZIF-8 and tungsten trioxide, so that separation of photo-generated electrons and holes in space is realized, and the recombination efficiency of carriers is reduced; defects are constructed on the surfaces of tungsten trioxide and ZIF-8, defect sites are used as electron local centers, a channel for transferring electrons to substrate molecules is provided, and the substrate molecules are activated to promote a photocatalytic reaction. Therefore, the tungsten trioxide/ZIF-8 composite catalyst can be used as a photocatalyst to improve the performance of the material from the aspects of thermodynamics and kinetics, and finally improve the solar energy conversion efficiency.
Drawings
FIG. 1 is an SEM photograph of tungsten trioxide in accordance with example 1 of the present invention;
FIG. 2 is an SEM photograph of the tungsten trioxide/ZIF-8 composite catalyst of example 1 of the present invention;
FIG. 3 is a graph showing a comparison of the yields of nitrate radicals, which are reaction products of photocatalytic fixation of nitrogen by tungsten trioxide and a tungsten trioxide/ZIF-8 composite catalyst in example 2 of the present invention.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included therein, and unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and in the case of contradiction, the definitions in the present specification shall control. The term "prepared from … …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "meaning," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, this phrase is intended to claim as closed, meaning that it does not include materials other than those described, except in connection with the common journal of usage. When the phrase "consisting of … …" appears in a clause of the claimed subject matter rather than immediately following the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of values, with an upper limit preferred value and a lower limit preferred value, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
A synthetic method of a tungsten trioxide/ZIF-8 composite catalyst at least comprises the following steps:
(1) dispersing tungsten trioxide nano sheets in deionized water, adding a 2-methylimidazole water solution into the tungsten trioxide nano sheets, and carrying out ultrasonic treatment for 5-15 min;
(2) dropwise adding 2-methylimidazole water solution, and stirring for 8-15 min;
(3) adding the prepared zinc acetate aqueous solution, and stirring at room temperature for 1.5-2.5 h;
(4) washing with a washing solution and drying to obtain the target product.
Preferably, the preparation method of the tungsten trioxide nanosheet comprises the following steps: dissolving sodium tungstate dihydrate and polyvinylpyrrolidone in deionized water; and then dropwise adding acetic acid to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, then placing the mixed solution into an autoclave for reaction for 7-9 hours, wherein the reaction temperature is 180-220 ℃, naturally cooling to room temperature to obtain a crude product, and carrying out post-treatment on the crude product to obtain the tungsten trioxide nanosheet.
Preferably, the work-up of the crude product comprises at least the following steps: centrifuging the crude product to collect powder, washing the powder with deionized water and absolute ethyl alcohol for 6-8 times to obtain a wet product, and drying the wet product in a vacuum drying oven.
Preferably, the washing liquid is a mixture of deionized water and anhydrous methanol, and the volume ratio of the two is as follows: 1:1-2.
Preferably, the concentration of the 2-methylimidazole aqueous solution is 0.28-1.12 mol/L, and the concentration of the zinc acetate aqueous solution is 0.1-0.4 mol/L.
Preferably, the ratio of tungsten trioxide to the amount of 2-methylimidazole in step (1), 2-methylimidazole in step (2) and zinc acetate added is: 1:(3-6):(2.7-5.4):(11-44).
Preferably, the mass ratio of the acetic acid, the sodium tungstate dihydrate, the polyvinylpyrrolidone and the deionized water is as follows: 1:660:100:12.
Preferably, the autoclave is coated with a polytetrafluoroethylene lining, and the polyvinylpyrrolidone has a relative molecular weight of 58000.
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention. Many non-essential modifications and adaptations of the present invention will occur to those skilled in the art in view of the foregoing description, and are intended to be within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
A synthesis method of a tungsten trioxide/ZIF-8 composite catalyst comprises the steps of dissolving 660mg of sodium tungstate dihydrate and 100mg of polyvinylpyrrolidone (Fw = 58000) in 12mL of deionized water; and then dropwise adding 1ml of acetic acid to obtain a yellow-green mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave coated with a polytetrafluoroethylene lining, reacting for 7 hours at the reaction temperature of 180 ℃, naturally cooling to room temperature to obtain a crude product, centrifuging the crude product to collect powder, washing the powder for 6 times by using deionized water and absolute ethyl alcohol to obtain a wet product, and drying the wet product in a vacuum drying oven to obtain the tungsten trioxide nanosheet. Dispersing 2.2mg of tungsten trioxide nanosheets in 8ml of deionized water, and adding 0.1ml of 2-methylimidazole water solution (0.28 mol/L) thereto and performing ultrasound for 5 min; then dropwise adding 0.9ml of 2-methylimidazole water solution (0.28 mol/L), stirring for 8-15min, adding the prepared zinc acetate water solution with the concentration of 0.1mol/L, and stirring for 1.5h at room temperature; the volume ratio is as follows: and washing the generated white suspension by using a mixture of deionized water and anhydrous methanol in a ratio of 1:1, and drying to obtain the target product.
Example 2
A synthesis method of a tungsten trioxide/ZIF-8 composite catalyst comprises the steps of dissolving 660mg of sodium tungstate dihydrate and 100mg of polyvinylpyrrolidone (Fw = 58000) in 12mL of deionized water; and then dropwise adding 1ml of acetic acid to obtain a yellow-green mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave coated with a polytetrafluoroethylene lining, reacting for 8 hours at the reaction temperature of 200 ℃, naturally cooling to room temperature to obtain a crude product, centrifuging the crude product to collect powder, washing the powder for 7 times by using deionized water and absolute ethyl alcohol to obtain a wet product, and drying the wet product in a vacuum drying oven to obtain the tungsten trioxide nanosheet. Dispersing 2.2mg of tungsten trioxide nanosheets in 8ml of deionized water, and adding 0.1ml of 2-methylimidazole water solution (1.12 mol/L) thereto and performing ultrasound for 10 min; dropwise adding 0.9ml of 2-methylimidazole water solution (1.12 mol/L), and stirring for 10 min; adding the prepared zinc acetate aqueous solution with the concentration of 0.4mol/L, stirring at room temperature for 2.5h, cleaning the generated white suspension by using a mixture of deionized water and anhydrous methanol with the volume ratio of 1:2, and drying to obtain the target product.
Example 3
A synthesis method of a tungsten trioxide/ZIF-8 composite catalyst comprises the steps of dissolving 660mg of sodium tungstate dihydrate and 100mg of polyvinylpyrrolidone (Fw = 58000) in 12mL of deionized water; and then dropwise adding 1ml of acetic acid to obtain a yellow-green mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave coated with a polytetrafluoroethylene lining, reacting for 9 hours at the reaction temperature of 220 ℃, naturally cooling to room temperature to obtain a crude product, centrifuging the crude product to collect powder, washing the powder for 8 times by using deionized water and absolute ethyl alcohol to obtain a wet product, and drying the wet product in a vacuum drying oven to obtain the tungsten trioxide nanosheet. Dispersing 2.2mg of tungsten trioxide nanosheets in 8ml of deionized water, and adding 0.1ml of 2-methylimidazole water solution (0.56 mol/L) thereto and performing ultrasonic treatment for 15 min; dropwise adding 0.9ml of 2-methylimidazole water solution (0.56 mol/L), and stirring for 15 min; adding the prepared zinc acetate aqueous solution with the concentration of 0.2mol/L, and stirring for 2 hours at room temperature; washing the white suspension with a mixture of deionized water and anhydrous methanol at a volume ratio of 1:1.5, and drying to obtain the target product.
Example 4
A synthesis method of a tungsten trioxide/ZIF-8 composite catalyst comprises the steps of dissolving 660mg of sodium tungstate dihydrate and 100mg of polyvinylpyrrolidone (Fw = 58000) in 12mL of deionized water; and then dropwise adding 1ml of acetic acid to obtain a yellow-green mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave coated with a polytetrafluoroethylene lining, reacting for 7 hours at the reaction temperature of 190 ℃, naturally cooling to room temperature to obtain a crude product, centrifuging the crude product to collect powder, washing the powder for 8 times by using deionized water and absolute ethyl alcohol to obtain a wet product, and drying the wet product in a vacuum drying oven to obtain the tungsten trioxide nanosheet. Dispersing 2.2mg of tungsten trioxide nanosheets in 8ml of deionized water, adding 0.1ml of 2-methylimidazole water solution (0.84 mol/L) thereto, and performing ultrasonic treatment for 5-15 min; dropwise adding 0.9ml of 2-methylimidazole water solution (0.84 mol/L), and stirring for 12 min; adding the prepared zinc acetate aqueous solution with the concentration of 0.3mol/L, and stirring for 2 hours at room temperature; washing the white suspension with a mixture of deionized water and anhydrous methanol at a volume ratio of 1:1, and drying to obtain the target product.
Example 5
A synthesis method of a tungsten trioxide/ZIF-8 composite catalyst comprises the steps of dissolving 660mg of sodium tungstate dihydrate and 100mg of polyvinylpyrrolidone (Fw = 58000) in 12mL of deionized water; and then dropwise adding 1ml of acetic acid to obtain a yellow-green mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, putting the mixed solution into an autoclave coated with a polytetrafluoroethylene lining, reacting for 9 hours at the reaction temperature of 210 ℃, naturally cooling to room temperature to obtain a crude product, centrifuging the crude product to collect powder, washing the powder for 8 times by using deionized water and absolute ethyl alcohol to obtain a wet product, and drying the wet product in a vacuum drying oven to obtain the tungsten trioxide nanosheet. Dispersing 2.2mg of tungsten trioxide nanosheets in 8ml of deionized water, adding 0.1ml of 2-methylimidazole water solution (0.56 mol/L) thereto, and performing ultrasonic treatment for 5-15 min; dropwise adding 0.9ml of 2-methylimidazole water solution (0.56 mol/L), and stirring for 10 min; immediately adding the prepared zinc acetate aqueous solution with the concentration of 0.2mol/L, and stirring for 2 hours at room temperature; washing with a mixture of deionized water and anhydrous methanol in a volume ratio of 1:2, and drying to obtain the target product.
Sample characterization and results
The morphology of the prepared sample is observed by using a scanning electron microscope, the morphology of the tungsten trioxide nanosheet prepared by the method is shown in figure 1, and the morphology of the tungsten trioxide/ZIF-8 composite material prepared by the method is shown in figure 2. The tungsten trioxide/ZIF-8 composite material prepared in example 2 is subjected to catalytic fixation of nitrogen under ultraviolet irradiation, a photocatalytic reaction is performed for 60min, samples are sequentially taken every 15min and processed, then the absorbance of the samples is detected by a visible light photometer, the photocatalytic result is shown in FIG. 3, the tungsten trioxide is used as a catalyst to perform a comparative test, and the comparative result in FIG. 3 shows that the yield of nitrate radicals obtained by photocatalysis of the composite material is obviously superior to that of tungsten trioxide.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A synthetic method of a tungsten trioxide/ZIF-8 composite catalyst is characterized by at least comprising the following steps:
(1) dispersing tungsten trioxide nano sheets in deionized water, adding a 2-methylimidazole water solution into the tungsten trioxide nano sheets, and carrying out ultrasonic treatment for 5-15 min;
(2) dropwise adding 2-methylimidazole water solution, and stirring for 8-15 min;
(3) adding the prepared zinc acetate aqueous solution, and stirring at room temperature for 1.5-2.5 h;
(4) washing with a washing solution and drying to obtain the target product.
2. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 1, wherein the method comprises the steps of: the preparation method of the tungsten trioxide nanosheet comprises the following steps: dissolving sodium tungstate dihydrate and polyvinylpyrrolidone in deionized water; and then dropwise adding acetic acid to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30 minutes, then placing the mixed solution into an autoclave for reaction for 7-9 hours, wherein the reaction temperature is 180-220 ℃, naturally cooling to room temperature to obtain a crude product, and carrying out post-treatment on the crude product to obtain the tungsten trioxide nanosheet.
3. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 2, wherein: the work-up of the crude product comprises at least the following steps: centrifuging the crude product to collect powder, washing the powder with deionized water and absolute ethyl alcohol for 6-8 times to obtain a wet product, and drying the wet product in a vacuum drying oven.
4. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 1, wherein the method comprises the steps of: the washing liquid is a mixture of deionized water and anhydrous methanol, and the volume ratio of the deionized water to the anhydrous methanol is as follows: 1:1-2.
5. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 1, wherein the method comprises the steps of: the concentration of the 2-methylimidazole aqueous solution is 0.28-1.12 mol/L, and the concentration of the zinc acetate aqueous solution is 0.1-0.4 mol/L.
6. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 1, wherein the method comprises the steps of: the ratio of the tungsten trioxide to the amount of the 2-methylimidazole added in the step (1), the 2-methylimidazole added in the step (2), and the zinc acetate is as follows: 1:(3-6):(2.7-5.4):(11-44).
7. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 2, wherein: the mass ratio of acetic acid, sodium tungstate dihydrate, polyvinylpyrrolidone and deionized water is as follows: 1:660:100:12.
8. The method for synthesizing tungsten trioxide/ZIF-8 composite catalyst according to claim 2, wherein: the autoclave is coated with a polytetrafluoroethylene lining, and the relative molecular weight of the polyvinylpyrrolidone is 58000.
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