CN111841586A - Preparation method of nano zinc oxide composite material and nano zinc oxide composite material prepared by adopting method - Google Patents
Preparation method of nano zinc oxide composite material and nano zinc oxide composite material prepared by adopting method Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000005496 eutectics Effects 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 61
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003751 zinc Chemical class 0.000 claims abstract description 28
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 26
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 18
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 18
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229960003178 choline chloride Drugs 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- 239000012456 homogeneous solution Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 94
- 239000007787 solid Substances 0.000 description 19
- 239000004094 surface-active agent Substances 0.000 description 10
- 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 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000010981 drying operation Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a preparation method of a nano zinc oxide composite material, which comprises the following steps: mixing a certain amount of choline chloride and glycol, heating and stirring to obtain a eutectic solvent; adding a certain amount of zinc salt into the eutectic solvent, heating and stirring to obtain a first uniform solution; adding a certain amount of silver nitrate into the first uniform solution, heating and stirring to obtain a second uniform solution; adding a certain amount of alkali metal hydroxide solution into the second uniform solution, heating and stirring to obtain a solution after reaction; and adding the reacted solution into deionized water, and performing centrifugal separation, washing and drying to obtain the nano Ag/AgCl/ZnO composite material. The method adopts the eutectic solvent as the reaction solvent to prepare the nano Ag/AgCl/ZnO composite material, the preparation process is simple and environment-friendly, and the prepared nano composite material has good visible light photocatalysis performance.
Description
Technical Field
The invention relates to the field of preparation of nano zinc oxide materials, in particular to a preparation method of a nano zinc oxide composite material and the nano zinc oxide composite material prepared by the method.
Background
The nano zinc oxide material has better catalytic performance in the field of photocatalytic degradation of dye wastewater, but the application of the nano zinc oxide material in the visible light range is limited due to the characteristic of wider forbidden band width (3.37 eV). Therefore, many methods for modifying and preparing the zinc oxide are available, and the methods can be divided into precious metal deposition, ion doping, semiconductor heterojunction compounding and the like according to the principle of the modification method, and are specifically implemented into preparation methods, most of the methods are firstly used for preparing pure zinc oxide and then are used for modifying and preparing the pure zinc oxide, strong acid and strong base reagents are commonly used in the preparation process, the requirements on reaction conditions are strict, and a large amount of surfactants are added in the preparation process.
Chinese patent application CN201810834633.0 discloses ZnO/a-Fe2O3The preparation method of the nano heterostructure material has complex preparation process and uses surface active agents such as sodium dodecyl benzene sulfonate, ethylene diamine tetraacetic acid, silane coupling agent and the like.
Chinese patent application CN201910810632.7 discloses a preparation method of a composite nano cuprous oxide/zinc oxide material with photocatalytic performance, which firstly prepares a tetrakaidecahedron Cu 2O, then according to Cu2The mass ratio of the O powder to the zinc acetate to the dodecyl pyrrolidone is 0.2: 0.15: 0.5 preparation of Nano Cu2O/ZnO solution. It can be seen that a large amount of the surfactant dodecyl pyrrolidone is used.
The use of the surfactant is beneficial to preparing the nano material with controllable appearance and size, however, the discharge of the surfactant is easy to cause harm to water and soil, change the properties of the water and the soil and cause serious environmental pollution.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a green, environment-friendly and environment-friendly zinc oxide nano material. The invention adopts the eutectic solvent as the reaction solvent to prepare the nano Ag/AgCl/ZnO composite material which has good visible light photocatalysis performance.
The invention aims to provide a preparation method of a nano zinc oxide composite material, which comprises the following steps:
mixing a certain amount of choline chloride and glycol, heating and stirring to obtain a eutectic solvent;
adding a certain amount of zinc salt into the eutectic solvent, heating and stirring to obtain a first uniform solution;
adding a certain amount of silver nitrate into the first uniform solution, heating and stirring to obtain a second uniform solution;
Adding a certain amount of alkali metal hydroxide solution into the second uniform solution, heating and stirring to obtain a solution after reaction;
and adding the reacted solution into deionized water, and performing centrifugal separation, washing and drying to obtain the nano Ag/AgCl/ZnO composite material.
Preferably, the method for obtaining the eutectic solvent comprises: mixing choline chloride and ethylene glycol according to a molar ratio of 1:1-1:3, and stirring at a heating temperature of 60-100 ℃ for 1-3 h.
More preferably, the method for obtaining the eutectic solvent comprises: choline chloride and ethylene glycol are mixed according to the molar ratio of 1:2, and stirred for 2 hours at the heating temperature of 60 ℃.
Preferably, the method for obtaining the first homogeneous solution comprises: adding a certain amount of zinc salt into the eutectic solvent, and stirring at the heating temperature of 100-140 ℃ until the zinc salt and the eutectic solvent are uniformly mixed; wherein the ratio of the addition amount of the zinc salt to the volume of the eutectic solvent is 2-40mmol:30 ml.
More preferably, the heating temperature for obtaining the first homogeneous solution is 120-130 ℃, and the ratio of the addition amount of the zinc salt to the volume of the eutectic solvent is 10-30mmol:30 ml.
Preferably, the zinc salt comprises one or more of zinc acetate, zinc chloride, zinc nitrate.
More preferably, the zinc salt is zinc acetate.
Preferably, the method for obtaining the second homogeneous solution comprises: adding a certain amount of soluble silver salt into the first uniform solution, and stirring under the heating condition of 100-140 ℃ until the mixture is uniformly mixed; wherein the molar ratio of Ag to Zn is 0.1-2: 10.
More preferably, the heating temperature used to obtain the second homogeneous solution is 120-130 ℃, and the molar ratio of Ag to Zn is 0.5-1: 10.
Preferably, the method for obtaining the solution after the reaction comprises: adding a certain amount of alkali metal hydroxide solution into the second uniform solution, and stirring for 1-9h at the heating temperature of 100-140 ℃; wherein the volume ratio of water in the alkali metal hydroxide solution to the eutectic solution is 1:10, and OH in the alkali metal hydroxide solution-The molar ratio of the zinc salt to Zn in the zinc salt is 2-4: 1.
More preferably, the heating temperature for obtaining the solution after the reaction is 120-130 ℃, the heating time is 3-5h, and OH is-The molar ratio to Zn was 2: 1.
Preferably, the alkali metal hydroxide comprises sodium hydroxide and/or potassium hydroxide.
More preferably, the alkali metal hydroxide is sodium hydroxide.
In order to realize the purpose, the invention also provides a nano zinc oxide composite material which is prepared by the preparation method of the nano zinc oxide composite material.
Preferably, the nano zinc oxide composite material is a nano Ag/AgCl/ZnO composite material. The nano Ag/AgCl/ZnO composite material is a rod-shaped nano composite material with the particle size of 15-40 nm.
The invention adopts the eutectic solvent as the solvent for preparing the nano Ag/AgCl/ZnO composite material. The eutectic solvent is generally formed by combining a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio, wherein the hydrogen bond acceptor is choline chloride or betaine, and the hydrogen bond donor is urea, thiourea, polyalcohol, amino acid, saccharide and the like, is cheap and easily available, can be biodegraded, and is not easy to damage the environment. The hydrogen bond of the eutectic solvent can be broken by adding a large amount of water into the eutectic solvent to form an aqueous solution of the above substances, so that the separation operation can be conveniently carried out after the target product is prepared. The special hydrogen bond network structure in the eutectic solvent provides good dispersion effect for the material preparation process, and can also serve as a surfactant to a certain extent.
The technical scheme of the invention has the following beneficial effects:
(1) the eutectic solvent is adopted as the solvent, so that the synthesis is simple, the environment is protected, and the final separation of the product is easy;
(2) a large amount of surfactant is not required to be added in the preparation process, the processes of washing and dissolving the surfactant for many times and removing the residual surfactant by high-temperature calcination in the traditional preparation method for removing the surfactant in the product are omitted, the operation is simple, the consumption is low, and the environment is protected;
(3) The prepared nano Ag/AgCl/ZnO composite material has excellent catalytic degradation performance under visible light, and the degradation rate of methylene blue dye within 120min is more than 90%.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is an XRD characterization diagram of the nanomaterials prepared in example 1 of the present invention and comparative example 1;
FIG. 2 is a graph showing the evaluation of photocatalytic performance of the nanomaterials prepared in examples 1, 5 and 6 of the present invention and comparative example 1.
Detailed Description
The terms as used herein:
the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," 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.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, 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 "1-5" is disclosed, the described range should be interpreted to include the ranges "1-4", "1-3", "1-2 and 4-5", "1-3 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.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The invention provides a preparation method of a nano zinc oxide composite material, which comprises the following steps:
(1) mixing a certain amount of choline chloride and glycol, heating and stirring to obtain a eutectic solvent;
specifically, choline chloride and ethylene glycol are mixed according to the molar ratio of 1:1-1:3, and stirred for 1-3 hours at the heating temperature of 60-100 ℃ to obtain a colorless uniform eutectic solvent;
Preferably, choline chloride and ethylene glycol are mixed according to a molar ratio of 1:2, and stirred for 2 hours at a heating temperature of 60 ℃;
(2) adding a certain amount of zinc salt into the eutectic solvent obtained in the step (1), heating and stirring to obtain a first uniform solution;
specifically, adding 2-40mmol of zinc salt into 30ml of the eutectic solvent obtained in the step (1), and stirring at the heating temperature of 100-140 ℃ until the zinc salt and the eutectic solvent are uniformly mixed; wherein the zinc salt comprises one or more of zinc acetate, zinc chloride and zinc nitrate;
preferably, the heating temperature in the step is 120-130 ℃, and the ratio of the addition amount of the zinc salt to the volume of the eutectic solvent is 10-30mmol:30 ml; the zinc salt is preferably zinc acetate;
in the step, after the zinc salt is added into the eutectic solvent, the components of the eutectic solvent and the zinc salt generate interaction, on one hand, Cl in the eutectic solvent-Has strong electronegativity, and complex components can be formed after zinc salt molecules are added into a eutectic solventA seed; on the other hand, Cl-And attack of alkoxy groups in ethylene glycol, such that a portion of the acetate ions and water molecules are substituted. These results all lead to Zn2+Uniformly dispersed in a network structure formed by the components of the eutectic solvent;
(3) Adding a certain amount of silver nitrate into the first uniform solution obtained in the step (2), and heating and stirring to obtain a second uniform solution;
specifically, adding a certain amount of silver nitrate into the first uniform solution obtained in the step (2), and stirring under the heating condition of 100-140 ℃ until the silver nitrate and the first uniform solution are uniformly mixed; wherein the molar ratio of Ag to Zn is 0.1-2: 10;
preferably, the heating temperature in the step is 120-130 ℃, and the molar ratio of Ag to Zn is 0.5-1: 10;
in this step, silver nitrate added to the first homogeneous solution will react with Cl in the eutectic solvent-The reaction is carried out to form AgCl, meanwhile, the ethylene glycol component in the eutectic solvent serves as a reducing agent, and part of silver nitrate is reduced to generate silver simple substance;
(4) adding a certain amount of alkali metal hydroxide solution into the second uniform solution obtained in the step (3), heating and stirring to obtain a solution after reaction;
specifically, adding a certain amount of alkali metal hydroxide solution into the second uniform solution obtained in the step (3), and stirring for 1-9h at the heating temperature of 100-140 ℃; wherein the volume ratio of water in the alkali metal hydroxide solution to the eutectic solution is 1:10, and OH in the alkali metal hydroxide solution-The molar ratio of the zinc salt to Zn in the zinc salt is 2-4: 1; alkali metal hydroxides include sodium hydroxide and/or potassium hydroxide;
Preferably, the heating temperature in the step is 120-130 ℃, the heating time is 3-5h, OH-The molar ratio of Zn to Zn is 2: 1; the alkali metal hydroxide is preferably sodium hydroxide;
in this step, the hydroxide solution is added to the second homogeneous solution and the Zn is uniformly dispersed in the eutectic solvent system2+The zinc oxide is finally generated through gradual reaction, and the agglomeration effect of the product is reduced due to the high solubility of the eutectic solvent.
(5) Adding the reacted solution obtained in the step (4) into deionized water, and performing centrifugal separation, washing and drying to obtain a nano Ag/AgCl/ZnO composite material;
specifically, after the solution obtained in the step (4) after the reaction is cooled to normal temperature, adding a large amount of deionized water, destroying hydrogen bonds of the eutectic solvent to form an aqueous solution of choline chloride and ethylene glycol, and precipitating a product generated in the step; then, the rod-shaped nano Ag/AgCl/ZnO composite material with the grain diameter of 15-40nm is obtained after centrifugal separation, washing and drying.
The invention also provides a nano zinc oxide composite material, which is prepared by the preparation method of the nano zinc oxide composite material; the nano zinc oxide composite material comprises Ag/AgCl/ZnO, has a particle size of 15-40nm, and is rod-shaped.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, and stirring for 2 hours at a heating temperature of 60 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 10mmol of zinc acetate dihydrate into 30ml of eutectic solvent, and stirring at the heating temperature of 120 ℃ until a uniform solution is obtained;
3) adding 1mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 120 ℃ until the uniform solution is obtained;
4) dissolving 20mmol of sodium hydroxide solid in 3ml of deionized water, adding the sodium hydroxide solid into the uniform solution obtained in the step 3), and stirring the solution for 5 hours at 120 ℃ to obtain a solution after reaction;
5) Cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
The prepared nano Ag/AgCl/ZnO composite material is subjected to X-ray diffraction (XRD) analysis, the spectrum of the nano Ag/AgCl/ZnO composite material is shown as the upper curve in figure 1, and obvious diffraction peaks of three substances of Ag, AgCl and ZnO can be seen.
A500W long-arc xenon lamp is used as a reaction light source, after a visible light filter is added, 30ml of methylene blue solution with the concentration of 10mol/L is degraded by the nano Ag/AgCl/ZnO composite material prepared by 24mg, the photocatalytic performance test result is shown in figure 2, and the degradation rate of 120min methylene blue reaches 98%.
Example 2
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:1, and stirring for 3 hours at a heating temperature of 70 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 2mmol of zinc acetate dihydrate into 30ml of eutectic solvent, and stirring at the heating temperature of 100 ℃ until a uniform solution is obtained;
3) Adding 0.4mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 100 ℃ until the uniform solution is obtained;
4) dissolving 8mmol of sodium hydroxide solid in 3ml of deionized water, adding the solution into the uniform solution obtained in the step 3), and stirring the solution for 3 hours at 100 ℃ to obtain a solution after reaction;
5) cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
Example 3
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:3, and stirring for 1h at a heating temperature of 100 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 40mmol of zinc acetate dihydrate into 30ml of eutectic solvent, and stirring at the heating temperature of 140 ℃ until a uniform solution is obtained;
3) adding 0.4mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 140 ℃ until the uniform solution is obtained;
4) dissolving 80mmol of potassium hydroxide solid in 3ml of deionized water, adding the potassium hydroxide solid into the uniform solution obtained in the step 3), and stirring the solution for 1 hour at 140 ℃ to obtain a solution after reaction;
5) Cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
Example 4
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, and stirring at a heating temperature of 90 ℃ for 2 hours to obtain a colorless uniform eutectic solvent;
2) adding 30mmol of zinc acetate dihydrate into 30ml of eutectic solvent, and stirring at the heating temperature of 130 ℃ until a uniform solution is obtained;
3) adding 1.5mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 130 ℃ until the uniform solution is obtained;
4) dissolving 60mmol of sodium hydroxide solid in 3ml of deionized water, adding the sodium hydroxide solid into the uniform solution obtained in the step 3), and stirring the solution for 9 hours at 130 ℃ to obtain a solution after reaction;
5) cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
Example 5
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, and stirring for 2 hours at a heating temperature of 60 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 10mmol of zinc nitrate into 30ml of eutectic solvent, and stirring at the heating temperature of 120 ℃ until a uniform solution is obtained;
3) adding 1mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 120 ℃ until the uniform solution is obtained;
4) dissolving 20mmol of sodium hydroxide solid in 3ml of deionized water, adding the sodium hydroxide solid into the uniform solution obtained in the step 3), and stirring the solution for 5 hours at 120 ℃ to obtain a solution after reaction;
5) cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
A500W long-arc xenon lamp is used as a reaction light source, after a visible light filter is added, 30ml of methylene blue solution with the concentration of 10mol/L is degraded by the nano Ag/AgCl/ZnO composite material prepared by 24mg, the photocatalytic performance test result is shown in figure 2, and the degradation rate of the methylene blue reaches 92% in 120 min.
Example 6
The preparation method of the nano zinc oxide composite material comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, and stirring for 2 hours at a heating temperature of 60 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 10mmol of zinc chloride into 30ml of eutectic solvent, and stirring at the heating temperature of 120 ℃ until a uniform solution is obtained;
3) adding 1mmol of silver nitrate solid into the uniform solution obtained in the step 2), and stirring at the heating temperature of 120 ℃ until the uniform solution is obtained;
4) dissolving 20mmol of sodium hydroxide solid in 3ml of deionized water, adding the sodium hydroxide solid into the uniform solution obtained in the step 3), and stirring the solution for 5 hours at 120 ℃ to obtain a solution after reaction;
5) cooling the reacted solution obtained in the step 4) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the rod-shaped nano Ag/AgCl/ZnO composite material with the particle size of 15-40nm by centrifugal separation, washing and drying operations.
A500W long-arc xenon lamp is used as a reaction light source, after a visible light filter is added, 30ml of methylene blue solution with the concentration of 10mol/L is degraded by the nano Ag/AgCl/ZnO composite material prepared by 24mg, the photocatalytic performance test result is shown in figure 2, and the 120min methylene blue degradation rate reaches 90%.
Comparative example 1
The comparative example is different from example 1 in that pure zinc oxide nanomaterial is prepared by using eutectic solvent, and doping is not carried out.
The preparation method of the nano zinc oxide material of the comparative example comprises the following steps:
1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, and stirring for 2 hours at a heating temperature of 60 ℃ to obtain a colorless uniform eutectic solvent;
2) adding 10mmol of zinc acetate dihydrate into 30ml of eutectic solvent, and stirring at the heating temperature of 120 ℃ until a uniform solution is obtained;
3) dissolving 20mmol of sodium hydroxide solid in 3ml of deionized water, adding the sodium hydroxide solid into the uniform solution obtained in the step 2), and stirring the solution for 5 hours at 120 ℃ to obtain a solution after reaction;
4) cooling the reacted solution obtained in the step 3) to normal temperature, adding the solution into a large amount of deionized water to ensure that the eutectic solvent is destroyed by water molecules, and obtaining the final product of the rod-shaped nano ZnO material with the wurtzite structure and the particle size of 15-40nm through centrifugal separation, washing and drying operations.
The prepared nano ZnO material is subjected to X-ray diffraction (XRD) analysis, the spectrum of the nano ZnO material is shown as the lower curve in figure 1, and only obvious ZnO diffraction peaks are shown.
A500W long-arc xenon lamp is used as a reaction light source, after a visible light filter is added, 30ml of methylene blue solution with the concentration of 10mol/L is degraded by 24mg of the prepared nano ZnO material, and the result of the photocatalytic performance test is shown in figure 2, wherein the degradation rate of the methylene blue is only 10% in 120 min.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The preparation method of the nano zinc oxide composite material is characterized by comprising the following steps:
mixing a certain amount of choline chloride and glycol, heating and stirring to obtain a eutectic solvent;
adding a certain amount of zinc salt into the eutectic solvent, heating and stirring to obtain a first uniform solution;
adding a certain amount of silver nitrate into the first uniform solution, heating and stirring to obtain a second uniform solution;
adding a certain amount of alkali metal hydroxide solution into the second uniform solution, heating and stirring to obtain a solution after reaction;
and adding the reacted solution into deionized water, and performing centrifugal separation, washing and drying to obtain the nano Ag/AgCl/ZnO composite material.
2. The method for preparing nano zinc oxide composite material according to claim 1, wherein the method for obtaining the eutectic solvent comprises:
mixing choline chloride and ethylene glycol according to a molar ratio of 1:1-1:3, and stirring at a heating temperature of 60-100 ℃ for 1-3 h.
3. The method of preparing a nano zinc oxide composite material according to claim 1, wherein the obtaining of the first homogeneous solution comprises:
adding a certain amount of zinc salt into the eutectic solvent, and stirring at the heating temperature of 100-140 ℃ until the zinc salt and the eutectic solvent are uniformly mixed; wherein the ratio of the addition amount of the zinc salt to the volume of the eutectic solvent is 2-40mmol:30 ml.
4. The method for preparing the nano zinc oxide composite material according to claim 1, wherein the zinc salt comprises one or more of zinc acetate, zinc chloride and zinc nitrate.
5. The method of preparing a nano zinc oxide composite according to claim 1, wherein the second homogeneous solution is obtained by a method comprising:
adding a certain amount of soluble silver salt into the first uniform solution, and stirring at the heating temperature of 100-140 ℃ until the soluble silver salt and the first uniform solution are uniformly mixed; wherein the molar ratio of Ag to Zn is 0.1-2: 10.
6. The method of claim 5, wherein the molar ratio of Ag to Zn is 0.5-1: 10.
7. The method for preparing nano zinc oxide composite material according to claim 1, wherein the method for obtaining the solution after the reaction comprises:
adding a certain amount of alkali metal hydroxide solution into the second uniform solution, and stirring for 1-9h at the heating temperature of 100-140 ℃; wherein the volume ratio of water in the alkali metal hydroxide solution to the eutectic solution is 1:10, and OH in the alkali metal hydroxide solution-The molar ratio of the zinc salt to Zn in the zinc salt is 2-4: 1.
8. The method of preparing a nano zinc oxide composite according to claim 1, wherein the alkali metal hydroxide comprises sodium hydroxide and/or potassium hydroxide.
9. A nano zinc oxide composite material, characterized in that the nano zinc oxide composite material is prepared by the method for preparing the nano zinc oxide composite material according to any one of claims 1 to 8.
10. The nano-zinc oxide composite of claim 9, wherein the nano-zinc oxide composite is a nano-Ag/AgCl/ZnO composite.
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