CN109110800B - Preparation method of zinc oxide micro-nano material - Google Patents

Preparation method of zinc oxide micro-nano material Download PDF

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CN109110800B
CN109110800B CN201811239127.3A CN201811239127A CN109110800B CN 109110800 B CN109110800 B CN 109110800B CN 201811239127 A CN201811239127 A CN 201811239127A CN 109110800 B CN109110800 B CN 109110800B
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CN109110800A (en
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许映杰
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University of Shaoxing
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a preparation method of a zinc oxide micro-nano material, which specifically comprises the following steps: (1) reacting ZnCl2And ChCl in a molar ratio of 2:1 preparation of ZnCl2a/ChCl eutectic solvent; (2) in ZnCl2Adding a solvent with a volume ratio of 1-2: 1, stirring uniformly at room temperature, and adjusting the pH value to 8-10 by using ammonia water to obtain a milky white solution; (3) transferring the milky white solution to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal synthesis reaction kettle in an oven at 120-160 ℃ for hydrothermal reaction, and then cooling, centrifuging, washing and drying to obtain white powdery solid; (4) and transferring the white powdery solid into a tubular furnace, calcining at 450-550 ℃ in an air atmosphere, and cooling to obtain the white ZnO micro-nano material. The method has the advantages of simple operation, mild reaction conditions, controllable morphology of the ZnO micro-nano material and the like.

Description

Preparation method of zinc oxide micro-nano material
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a ZnCl-based material2A method for preparing a zinc oxide micro-nano material by taking a/ChCl eutectic solvent as a raw material.
Background
Zinc oxide (ZnO), commonly known as zinc white, is widely used as a typical II-VI group direct band gap n-type semiconductor material in the chemical industry, medicine, energy, photocatalytic degradation, environmental protection, and the like. For example, the ZnO micro-nano material can be excited to generate photo-generated electron-hole pairs under the irradiation of ultraviolet light with the wavelength of less than 387nm to generate hydroxyl free radicals (OH) and superoxide free radicals (O)2 –) And the like, and active free radicals with strong oxidizing capability can be used for photocatalytic degradation of pollutants such as organic dyes and the like. Therefore, the preparation of the ZnO micro-nano material arouses interest and attention. At present, methods for preparing ZnO micro-nano materials mainly comprise a hydrothermal method, a chemical vapor deposition method, a sol-gel method, a chemical precipitation method and the like. Research results show that the ZnO micro-nano materials obtained by different preparation methods have larger differences in morphology and microstructure, and finally influence the physicochemical properties and application performance of the ZnO materials (A. Moezzi et al. chemical Engineering Journal, 2012, 185: 186: 1-22). Therefore, the controllable preparation of the ZnO micro-nano material becomes a research hotspot.
The eutectic solvent (DESS) is a eutectic salt formed by self-association of Hydrogen Bond Acceptor (HBA) (generally quaternary ammonium salt) and Hydrogen Bond Donor (HBD) (generally carboxylic acid, polyalcohol, urea and the like) or quaternary ammonium salt and metal salt substance in a certain molar ratio through hydrogen bond interaction, and the freezing point of the eutectic solvent is obviously lower than the melting point (E.L.Smith) of each component pure substanceal chemical reviews, 2014, 114: 11060-11082). The physical and chemical properties of the eutectic solvent are very similar to those of ionic liquids, so that the eutectic solvent is also classified as a novel ionic liquid or an ionic liquid analogue by scholars. For example, from Urea (Urea) and choline chloride (ChCl) in a molar ratio of 2:1, the melting point of the Urea/ChCl eutectic solvent is 12 ℃ (the melting point is far lower than that of Urea: 132-135 ℃ and that of ChCl: 302-305 ℃). The eutectic solvent has the advantages of simple preparation, strong solubility, good biocompatibility, easy recycling and the like, and has certain application in the field of preparation of micro-nano materials such as ZnO and the like as a novel green solvent. For example, plum 22881, qi et al adopt Urea/ChCl eutectic solvent assisted hydrothermal method to synthesize layered spherical micro/nano ZnO crystal (plum 22881, qi et al. advanced chemical bulletin, 2015, 36: 165-170). At present, the reported method for preparing the ZnO micro-nano material by using the eutectic solvent mainly dissolves ZnO by using the strong polarity of the eutectic solvent, and then regulates and controls the morphology of the ZnO micro-nano material through hydrothermal reaction in the presence of an anti-solvent, but no published literature report exists about directly preparing the ZnO micro-nano material by using the eutectic solvent formed by zinc salt. The research shows that the ZnCl is mixed with the zinc2Mixing with ChCl according to a certain mole ratio to obtain ZnCl2ChCl eutectic solvent (A.P.Abbott et al. journal of electroanalytical Chemistry, 2007, 599: 288-. If ZnCl is used2Preparing ZnO micro-nano material by using/ChCl eutectic solvent as zinc source and using ChCl and ZnCl2The interaction between them is ZnCl2The ZnO nano-material is in a structure ordered state, so that the morphology and microstructure of the ZnO micro-nano material are effectively regulated and controlled, and a new method is provided for the controllable preparation of the ZnO micro-nano material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the preparation method of the zinc oxide micro-nano material, which has the advantages of simple preparation process, mild reaction conditions, controllable appearance of the ZnO micro-nano material and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a zinc oxide micro-nano material specifically comprises the following steps:
(1) reacting ZnCl2And ChCl in a molar ratio of 2:1 preparing uniform, colorless and transparent ZnCl under the constant temperature condition of 100 DEG C2a/ChCl eutectic solvent;
(2) ZnCl produced in step (1)2Adding a solvent with a volume ratio of 1-2: 1, stirring the mixture evenly at room temperature to obtain a colorless transparent solution, and adjusting the pH value of the solution system to 8-10 by using ammonia water to obtain a milky white solution;
(3) transferring the milky white solution prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal reaction at 120-160 ℃, and cooling, centrifuging, washing and drying after the reaction to obtain a white powdery solid;
(4) and (4) transferring the white powdery solid prepared in the step (3) to a tubular furnace, calcining at 450-550 ℃ in an air atmosphere, and naturally cooling to obtain the white ZnO micro-nano material.
In the step (1), ZnCl is added2Stirring and reacting with ChCl in oil bath at 100 ℃ for 1h, and cooling to obtain ZnCl2a/ChCl eutectic solvent;
in the step (2), ammonia water with the concentration of 25% is adopted to adjust the pH.
In the step (3), the hydrothermal reaction time is 10-12 h.
And (3) after the reaction, cooling and centrifuging the reaction liquid to obtain a white solid, washing the white solid for 3-6 times by using ethanol and distilled water alternately, washing the white solid for the last time by using distilled water, and then drying the white solid for 6-8 hours in vacuum at the temperature of 60-80 ℃ to obtain a white powdery solid.
In the step (4), the calcination time is 2-4 h.
Further, ZnCl is formed in the step (1)2the/ChCl eutectic solvent mechanism is as follows:
in the present invention, ZnCl2the/ChCl eutectic solvent is used as a zinc source and a solvent at the same time; FIG. 1 is ZnCl2FT-IR spectrum of/ChCl eutectic solvent, shown at 3362cm-1A width appears nearbyAbsorption peaks ascribed to ZnCl2the-OH stretching vibration absorption peak of ChCl in the/ChCl eutectic solvent; compared with the-OH infrared stretching vibration absorption peak of the ChCl pure substance (according to the ChCl standard FT-IR spectrogram determined by KBr tabletting technology published by SDBS: NIMC organic matter spectrogram library)2The wave number of the-OH infrared stretching vibration absorption peak of the ChCl in the/ChCl eutectic solvent is obviously red-shifted, which shows that ZnCl2-OH and ZnCl of ChCl in/ChCl eutectic solvent2Cl of/ChCl-Can form ion hydrogen bond interaction, thereby leading the-OH stretching vibration intensity of the ChCl to be weakened and the infrared absorption peak to be moved to low wave number, which is beneficial to ZnCl2ZnCl in/ChCl eutectic solvent2The structure order of the ZnO nano-material is realized, so that the appearance and the microstructure of the subsequent ZnO micro-nano material are better regulated and controlled.
Further, step (2) is mainly ZnCl2Reacting with ammonia water to generate ammoniated basic zinc chloride and a zinc-ammonia complex; ammonia water is used as a precipitator and is slowly dripped into the reaction system in the preparation process, and the addition amount of the ammonia water is relative to that of ZnCl2the/ChCl eutectic solvent is small and therefore does not destroy ZnCl2Hydrogen bonding structure of/ChCl eutectic solvent, thereby leading Zn to be2+In a structurally ordered state.
Further, the main purpose of washing the white solid with ethanol and distilled water in the step (3) is to remove organic matters such as ChCl and the like, and the obtained white powdery solid is actually ZnO and Zn (OH)2A mixture of (a).
The invention has the following beneficial effects:
(1) by using ZnCl2the/ChCl eutectic solvent is used as a solvent, other eutectic solvents, templates or surfactants do not need to be additionally added in the preparation process, and the preparation method has the characteristics of simple preparation process, mild reaction conditions, controllable morphology of the ZnO micro-nano material and the like;
(2) directly using ZnCl2the/ChCl eutectic solvent is simultaneously used as a zinc source, and hydroxyl (-OH) of ChCl and ZnCl are utilized2Cl of-The ion hydrogen bond interaction between the ZnCl and the ZnCl forms a compact hydrogen bond network structure2In a structurally ordered state in a low co-solvent,thereby effectively regulating and controlling the appearance and microstructure of the subsequent ZnO micro-nano material;
(3) the structural morphology of the ZnO micro-nano material is effectively regulated and controlled by changing the hydrothermal reaction temperature, and the method has the characteristics of simplicity in operation, controllability and the like.
Drawings
FIG. 1 shows ZnCl of the present invention2FT-IR spectrum of/ChCl eutectic solvent;
fig. 2 is an XRD spectrogram of the ZnO micro-nano material prepared according to example 1 of the present invention;
fig. 3 is an XRD spectrogram of the ZnO micro-nano material prepared according to example 2 of the present invention;
fig. 4 is an XRD spectrogram of the ZnO micro-nano material prepared according to example 3 of the present invention;
FIG. 5 is a SEM spectrogram of the ZnO micro-nano material prepared according to example 1 of the present invention;
FIG. 6 is a SEM spectrogram of the ZnO micro-nano material prepared according to example 2;
FIG. 7 is a SEM spectrogram of the ZnO micro-nano material prepared according to example 3 of the present invention;
fig. 8 is a TEM spectrogram of the ZnO micro-nano material prepared according to example 1 of the present invention;
fig. 9 is a TEM spectrogram of the ZnO micro-nano material prepared according to example 2 of the present invention;
fig. 10 is a TEM spectrum of the ZnO micro/nano material prepared according to example 3 of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings and the detailed description below:
example 1
(1) (1) reacting ZnCl2And ChCl in a molar ratio of 2:1 are stirred and reacted for 1 hour in a constant temperature oil bath at 100 ℃, and uniform, colorless and transparent ZnCl is obtained after cooling2a/ChCl eutectic solvent;
(2) ZnCl produced in step (1)2Adding a solvent with a volume ratio of 2:1, stirring at room temperature to obtain colorless transparent solution, and adjusting with 25% ammonia waterThe pH value of the solution system is 8, and a milky white solution is obtained;
(3) transferring the milky white solution prepared in the step (2) into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a drying oven to perform hydrothermal reaction for 12 hours at 120 ℃, cooling and centrifuging reaction liquid after the reaction to obtain a white solid, alternately washing the white solid for 3 times by using ethanol and distilled water, washing the white solid by using distilled water for the last time, and then performing vacuum drying for 6 hours at 80 ℃ to obtain a white powdery solid;
(4) and (4) transferring the white powdery solid prepared in the step (3) to a tubular furnace, calcining for 2h at 550 ℃ in an air atmosphere, and naturally cooling to obtain the white ZnO micro-nano material.
Referring to fig. 2, 5 and 8, the diffraction peak of wurtzite structure is included in fig. 2 and is relatively sharp, which indicates that the product is wurtzite zinc oxide and has good crystallinity and complete crystal form; as can be seen from fig. 5 and 8, most of the samples prepared in this example have petal-shaped shapes, a small number of flake-shaped shapes, and an average particle size of about 50 nm.
Example 2
(1) Reacting ZnCl2And ChCl in a molar ratio of 2:1 are stirred and reacted for 1 hour in a constant temperature oil bath at 100 ℃, and uniform, colorless and transparent ZnCl is obtained after cooling2a/ChCl eutectic solvent;
(2) ZnCl produced in step (1)2Adding a solvent with a volume ratio of 2:1, stirring the mixture evenly at room temperature to obtain a colorless transparent solution, and adjusting the pH value of the solution system to 9 by using 25% ammonia water to obtain a milky white solution;
(3) transferring the milky white solution prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal reaction at 140 ℃ for 11 hours, cooling and centrifuging reaction liquid after the reaction to obtain a white solid, alternately washing the white solid for 5 times by using ethanol and distilled water, washing the white solid by using distilled water for the last time, and then drying the white solid for 7 hours in vacuum at 70 ℃ to obtain a white powdery solid.
(4) And (4) transferring the white powdery solid prepared in the step (3) to a tubular furnace, calcining for 3h at 500 ℃ in an air atmosphere, and naturally cooling to obtain the white ZnO micro-nano material.
Referring to fig. 3, 6 and 9, the diffraction peak of wurtzite structure is included in fig. 3 and is relatively sharp, which indicates that the product is wurtzite zinc oxide and has good crystallinity and complete crystal form; as can be seen from fig. 6 and 9, the morphology of the sample prepared in this example is more regular petal-shaped, and the average particle size is about 70 nm.
Example 3
(1) Reacting ZnCl2And ChCl in a molar ratio of 2:1 are stirred and reacted for 1 hour in a constant temperature oil bath at 100 ℃, and uniform, colorless and transparent ZnCl is obtained after cooling2a/ChCl eutectic solvent;
(2) ZnCl produced in step (1)2Adding a solvent with a volume ratio of 1: 1, stirring the mixture evenly at room temperature to obtain a colorless transparent solution, and adjusting the pH value of the solution system to 10 by using 25% ammonia water to obtain a milky white solution;
(3) transferring the milky white solution prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal reaction at 160 ℃ for 10 hours, cooling and centrifuging reaction liquid after the reaction to obtain a white solid, alternately washing the white solid for 6 times by using ethanol and distilled water, washing the white solid by using distilled water for the last time, and then drying the white solid for 8 hours in vacuum at 60 ℃ to obtain a white powdery solid.
(4) And (4) transferring the white powdery solid prepared in the step (3) to a tubular furnace, calcining for 4 hours at 450 ℃ in an air atmosphere, and naturally cooling to obtain the white ZnO micro-nano material.
Referring to fig. 4, 7 and 10, the diffraction peak of wurtzite structure is contained in fig. 4 and is relatively sharp, which indicates that the product is wurtzite zinc oxide and has good crystallinity and complete crystal form; as can be seen from fig. 7 and 10, the sample prepared in this example has a flaky shape mainly with a small amount of agglomeration, and the average particle size is about 100nm, and it is considered by analysis that the sample prepared has a part of agglomeration due to unstable factors such as non-uniformity of dropwise addition of ammonia water when adjusting the pH, drying conditions, and centrifugal separation conditions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A preparation method of a zinc oxide micro-nano material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) reacting ZnCl2And ChCl in a molar ratio of 2:1 preparing uniform, colorless and transparent ZnCl under the constant temperature condition of 100 DEG C2a/ChCl eutectic solvent;
(2) ZnCl produced in step (1)2Adding a solvent with a volume ratio of 1-2: 1, stirring the mixture evenly at room temperature to obtain a colorless transparent solution, and adjusting the pH value of the solution system to 8-10 by using ammonia water to obtain a milky white solution;
(3) transferring the milky white solution prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal reaction at 120-160 ℃, and cooling, centrifuging, washing and drying after the reaction to obtain a white powdery solid;
(4) and (4) transferring the white powdery solid prepared in the step (3) to a tubular furnace, calcining at 450-550 ℃ in an air atmosphere, and naturally cooling to obtain the white ZnO micro-nano material.
2. The preparation method of the zinc oxide micro-nano material according to claim 1, which is characterized by comprising the following steps: in the step (1), ZnCl is added2Stirring and reacting with ChCl in oil bath at 100 ℃ for 1h, and cooling to obtain ZnCl2a/ChCl eutectic solvent.
3. The preparation method of the zinc oxide micro-nano material according to claim 1, which is characterized by comprising the following steps: in the step (2), ammonia water with the concentration of 25% is adopted to adjust the pH.
4. The preparation method of the zinc oxide micro-nano material according to claim 1, which is characterized by comprising the following steps: in the step (3), the hydrothermal reaction time is 10-12 h.
5. The preparation method of the zinc oxide micro-nano material according to claim 1, which is characterized by comprising the following steps: and (3) after the reaction, cooling and centrifuging the reaction liquid to obtain a white solid, washing the white solid for 3-6 times by using ethanol and distilled water alternately, washing the white solid for the last time by using distilled water, and then drying the white solid for 6-8 hours in vacuum at the temperature of 60-80 ℃ to obtain a white powdery solid.
6. The preparation method of the zinc oxide micro-nano material according to claim 1, which is characterized by comprising the following steps: in the step (4), the calcination time is 2-4 h.
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"咪唑基离子液体及氯化胆碱低共熔溶剂中微/纳米ZnO晶体的调控合成";胡晓宇;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215(第S2期);第4、24、26页 *

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