CN109110800A - A kind of preparation method of zinc oxide micron/nano material - Google Patents
A kind of preparation method of zinc oxide micron/nano material Download PDFInfo
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- CN109110800A CN109110800A CN201811239127.3A CN201811239127A CN109110800A CN 109110800 A CN109110800 A CN 109110800A CN 201811239127 A CN201811239127 A CN 201811239127A CN 109110800 A CN109110800 A CN 109110800A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention discloses a kind of preparation method of zinc oxide micron/nano material, specifically includes the following steps: (1) is by ZnCl22:1 is configured to ZnCl in molar ratio with ChCl2/ ChCl eutectic solvent；(2) in ZnCl2The distilled water for being 1~2:1 with eutectic solvent volume ratio is added in/ChCl eutectic solvent, stirs evenly at room temperature, then adjusts pH value to 8~10 with ammonium hydroxide, obtains milky white solution；(3) milky white solution is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then is placed in 120~160 DEG C of progress hydro-thermal reactions in baking oven, by cooling, centrifugation, washed, be dried to obtain white powdery solids；(4) white powdery solids are transferred in tube furnace, 450~550 DEG C of calcinings in air atmosphere obtain white ZnO micro Nano material after cooling.The present invention has many advantages, such as that easy to operate, reaction condition is mild, ZnO micro Nano material morphology controllable.
Description
Technical field
The present invention relates to functional material preparation technical fields, more particularly to one kind with ZnCl2/ ChCl eutectic solvent is
The method that raw material prepares zinc oxide micron/nano material.
Background technique
Zinc oxide (ZnO) is commonly called as zinc white, as a kind of typical II-VI group direct band gap n-type semiconductor, in chemistry
Industry, medicine, the energy, photocatalytic degradation and environmental protection etc. are widely used.For example, ZnO micro Nano material
Under ultraviolet light of the wavelength lower than 387nm, it can excite and generate photo-generate electron-hole pair, generate hydroxyl radical free radical (OH)
With superoxide radical (O2 –) etc. with Strong oxdiative ability living radical, can be used for photocatalytically degradating organic dye etc. pollution
Object.Therefore, the preparation of ZnO micro Nano material causes the interest and concern of people.Currently, preparing the side of ZnO micro Nano material
Method mainly includes hydro-thermal method, chemical vapour deposition technique, sol-gal process and chemical precipitation method etc..Result of study shows different systems
The ZnO micro Nano material that Preparation Method obtains has biggish difference on pattern and microstructure, and finally influences the object of ZnO material
Physicochemical property and its application performance (A.Moezzi et al.Chemical Engineering Journal, 2012,185-
186:1-22).Therefore, the controllable preparation in relation to ZnO micro Nano material has become research hotspot.
Eutectic solvent (DESs) be by hydrogen bond receptor (HBA) (generally quaternary ammonium salt) and hydrogen bond donor (HBD) (generally
Carboxylic acid, polyalcohol, urea etc.) or mixed certain by certain mol proportion by quaternary ammonium salt and metallic salt substance, pass through hydrogen bond phase
A kind of congruent melting salt of interaction and self-association formation, freezing point are substantially less than the fusing point (E.L.Smith of each component pure material
Et al.Chemical reviews, 2014,114:11060-11082).The physicochemical properties and ionic liquid of eutectic solvent
Body is closely similar, therefore it is classified as a kind of novel ion liquid or ionic liquid analog by some scholars.For example, by urea
(Urea) and the Urea/ChCl eutectic solvent that forms according to molar ratio 2:1 of choline chloride (ChCl), fusing point are 12 DEG C (remote
Fusing point lower than Urea: 132~135 DEG C and ChCl of fusing point: 302~305 DEG C).Eutectic solvent, which has, prepares simple, dissolution
Property strong, good biocompatibility and the advantages that easily recycling uses, prepared as a kind of novel green solvent in micro Nano materials such as ZnO
Field has certain application.For example, Li Ao Qi etc. is spherical using the synthesis layering of Urea/ChCl eutectic solvent assisting alcohol-hydrothermal method
The Chemical Journal of Chinese Universities such as micro-/ nano ZnO crystal (Li Ao Qi, 2015,36:165-170).Reported at present using low
Then the method that congruent melting solvent prepares ZnO micro Nano material exists mainly first with the highly polar dissolution ZnO of eutectic solvent
Regulate and control the pattern of ZnO micro Nano material in the presence of anti-solvent by hydro-thermal reaction, and the related zinc salt that directlys adopt itself is formed
Eutectic solvent prepare ZnO micro Nano material, there is not yet open source literature is reported.Studies have shown that by ZnCl2One is pressed with ChCl
Determining molar ratio mixing can be obtained ZnCl2/ ChCl eutectic solvent (A.P.Abbott et al.Journal of
Electroanalytical Chemistry, 2007,599:288-294).If using ZnCl2/ ChCl eutectic solvent is
Zinc source prepares ZnO micro Nano material, utilizes ChCl and ZnCl2Between interaction make ZnCl2In structurally ordered state, from
And the pattern and microstructure of Effective Regulation ZnO micro Nano material, then this will be provided for the controllable preparation of ZnO micro Nano material
A kind of new method.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of preparation of zinc oxide micron/nano material is provided
Method has many advantages, such as that preparation process is simple, reaction condition is mild, ZnO micro Nano material morphology controllable.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of zinc oxide micron/nano material, this method specifically includes the following steps:
(1) by ZnCl2It is configured under 100 DEG C of constant temperatures with ChCl according to molar ratio 2:1 uniform, colorless and transparent
ZnCl2/ ChCl eutectic solvent；
(2) ZnCl made from step (1)2Being added in/ChCl eutectic solvent with eutectic solvent volume ratio is 1~2:
1 distilled water is stirred at room temperature and uniformly obtains colourless transparent solution, then adjusts the solution system pH value to 8~10 with ammonium hydroxide,
Obtain milky white solution；
(3) milky white solution made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will be anti-
Answer kettle to be placed in baking oven in 120~160 DEG C of progress hydro-thermal reactions, after reaction through cooling, centrifugation, wash, be dried to obtain white powder
Last shape solid；
(4) white powdery solids made from step (3) are transferred in tube furnace, 450~550 DEG C in air atmosphere
Calcining, natural cooling obtains white ZnO micro Nano material after calcining.
In the step (1), ZnCl21h is stirred to react in 100 DEG C of oil baths with ChCl, up to ZnCl after cooling2/ChCl
Eutectic solvent；
In the step (2), pH is adjusted using the ammonium hydroxide of 25% concentration.
In the step (3), the hydro-thermal reaction time is 10~12h.
In the step (3), reaction solution is cooling, centrifugation, obtains white solid after reaction, is handed over using ethyl alcohol and distilled water
For washing white solid 3~6 times, adopt be washed with distilled water for the last time, then 60~80 DEG C of 6~8h of vacuum drying to get
White powdery solids.
In the step (4), calcination time is 2~4h.
Further, ZnCl is formed in step (1)2/ ChCl eutectic solvent mechanism is as follows:
In the present invention, ZnCl2/ ChCl eutectic solvent is used as zinc source and solvent simultaneously；Fig. 1 is ZnCl2/ ChCl eutectic
The FT-IR spectrogram of solvent is shown in 3362cm in figure-1Nearby there is a wide absorption peak, belongs to ZnCl2/ ChCl is low total
- OH the stretching vibration absworption peak of ChCl in molten solvent；With the infrared stretching vibration absworption peak of-OH of ChCl pure material (according to SDBS:
The ChCl standard FT-IR spectrogram measured with KBr pressed-disc technique that the organic matter spectrogram library NIMC is announced) it compares, ZnCl2/ ChCl is low
Apparent red shift has occurred in the wave number of the infrared stretching vibration absworption peak of-OH of ChCl in congruent melting solvent, shows ZnCl2/ ChCl is low
- the OH and ZnCl of ChCl in congruent melting solvent2The Cl of/ChCl-Between can form ion interaction of hydrogen bond, so as to cause ChCl-
OH stretching vibration weakened, infrared absorption peak is mobile to lower wave number, this is conducive to ZnCl2ZnCl in/ChCl eutectic solvent2
Structural order, to preferably regulate and control the pattern and microstructure of subsequent ZnO micro Nano material.
Further, step (2) is mainly ZnCl2It reacts with ammonia water and generates ammonification basic zinc chloride and zinc ammonia complex
Process；Ammonium hydroxide is slowly added dropwise in reaction system during the preparation process as precipitating reagent, and the additional amount of ammonium hydroxide is relative to ZnCl2/
ChCl eutectic solvent is a small amount of, therefore will not destroy ZnCl2The hydrogen bond structure of/ChCl eutectic solvent, to make Zn2+Place
In structurally ordered state.
Further, it is to remove ChCl using the main purpose of ethyl alcohol and distillation water washing white solid in step (3)
Equal organic matters, obtained white powdery solids are ZnO and Zn (OH) in fact2Mixture.
Beneficial effects of the present invention are as follows:
(1) ZnCl is used2/ ChCl eutectic solvent no longer needs to additionally add during the preparation process other low as solvent
Congruent melting solvent, template or surfactant, have preparation process is simple, reaction condition is mild, ZnO micro Nano material pattern can
The features such as control；
(2) ZnCl is directlyed adopt2/ ChCl eutectic solvent is used as zinc source simultaneously, utilizes the hydroxyl (- OH) and ZnCl of ChCl2
Cl-Between ion interaction of hydrogen bond form fine and close hydrogen bond network structure, make ZnCl2Have in low cosolvent in structure
Sequence state, thus the pattern and microstructure of the subsequent ZnO micro Nano material of Effective Regulation；
(3) by changing hydrothermal temperature come the structure and morphology of Effective Regulation ZnO micro Nano material, there is operation letter
The features such as single, controllable.
Detailed description of the invention
Fig. 1 is ZnCl of the invention2The FT-IR spectrogram of/ChCl eutectic solvent；
Fig. 2 is the XRD spectra of the invention according to ZnO micro Nano material made from embodiment 1；
Fig. 3 is the XRD spectra of the invention according to ZnO micro Nano material made from embodiment 2；
Fig. 4 is the XRD spectra of the invention according to ZnO micro Nano material made from embodiment 3；
Fig. 5 is the SEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 1；
Fig. 6 is the SEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 2；
Fig. 7 is the SEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 3；
Fig. 8 is the TEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 1；
Fig. 9 is the TEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 2；
Figure 10 is the TEM spectrogram of the invention according to ZnO micro Nano material made from embodiment 3.
Specific embodiment
Present invention will be further described below with reference to the accompanying drawings and specific embodiments:
Embodiment 1
(1) (1) is by ZnCl22:1 is stirred to react 1h in 100 DEG C of constant temperature oil baths in molar ratio with ChCl, obtains after cooling
Uniformly, colorless and transparent ZnCl2/ ChCl eutectic solvent；
(2) ZnCl made from step (1)2Being added in/ChCl eutectic solvent with eutectic solvent volume ratio is 2:1's
Distilled water is stirred at room temperature and uniformly obtains colourless transparent solution, then with 25% concentration ammonium hydroxide adjust the solution system pH value to
8, obtain milky white solution；
(3) milky white solution made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will be anti-
Kettle is answered to be placed in baking oven in 120 DEG C of progress hydro-thermal reaction 12h, reaction solution is cooling, centrifugation, obtains white solid, adopt after reaction
Replace washing white solid 3 times with distilled water with ethyl alcohol, adopt be washed with distilled water for the last time, is then dried in vacuo at 80 DEG C
6h is to get white powdery solids；
(4) white powdery solids made from step (3) are transferred in tube furnace, 550 DEG C of calcinings in air atmosphere
2h, natural cooling obtains white ZnO micro Nano material after calcining.
Referring to the diffraction maximum comprising wurtzite structure in attached drawing 2,5,8, Fig. 2 and the diffraction maximum it is more sharp, show the production
Object is wurtzite-type zinc oxide and crystallinity is good, complete crystal form；In conjunction with Fig. 5, Fig. 8 it is found that sample shape made from the present embodiment
Looks are largely petal-shaped, are on a small quantity sheet, average grain diameter is about 50nm.
Embodiment 2
(1) by ZnCl22:1 is stirred to react 1h in 100 DEG C of constant temperature oil baths in molar ratio with ChCl, obtains after cooling
Even, colorless and transparent ZnCl2/ ChCl eutectic solvent；
(2) ZnCl made from step (1)2Being added in/ChCl eutectic solvent with eutectic solvent volume ratio is 2:1's
Distilled water is stirred at room temperature and uniformly obtains colourless transparent solution, then with 25% concentration ammonium hydroxide adjust the solution system pH value to
9, obtain milky white solution；
(3) milky white solution made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will be anti-
Kettle is answered to be placed in baking oven in 140 DEG C of progress hydro-thermal reaction 11h, reaction solution is cooling, centrifugation, obtains white solid, adopt after reaction
Replace washing white solid 5 times with distilled water with ethyl alcohol, adopt be washed with distilled water for the last time, is then dried in vacuo at 70 DEG C
7h is to get white powdery solids.
(4) white powdery solids made from step (3) are transferred in tube furnace, 500 DEG C of calcinings in air atmosphere
3h, natural cooling obtains white ZnO micro Nano material after calcining.
Referring to the diffraction maximum comprising wurtzite structure in attached drawing 3,6,9, Fig. 3 and the diffraction maximum it is more sharp, show the production
Object is wurtzite-type zinc oxide and crystallinity is good, complete crystal form；In conjunction with Fig. 6, Fig. 9 it is found that sample shape made from the present embodiment
Relatively regular petal-shaped is presented in looks, and average grain diameter is about 70nm.
Embodiment 3
(1) by ZnCl22:1 is stirred to react 1h in 100 DEG C of constant temperature oil baths in molar ratio with ChCl, obtains after cooling
Even, colorless and transparent ZnCl2/ ChCl eutectic solvent；
(2) ZnCl made from step (1)2Being added in/ChCl eutectic solvent with eutectic solvent volume ratio is 1:1's
Distilled water is stirred at room temperature and uniformly obtains colourless transparent solution, then with 25% concentration ammonium hydroxide adjust the solution system pH value to
10, obtain milky white solution；
(3) milky white solution made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will be anti-
Kettle is answered to be placed in baking oven in 160 DEG C of progress hydro-thermal reaction 10h, reaction solution is cooling, centrifugation, obtains white solid, adopt after reaction
Replace washing white solid 6 times with distilled water with ethyl alcohol, adopt be washed with distilled water for the last time, is then dried in vacuo at 60 DEG C
8h is to get white powdery solids.
(4) white powdery solids made from step (3) are transferred in tube furnace, 450 DEG C of calcinings in air atmosphere
4h, natural cooling obtains white ZnO micro Nano material after calcining.
Referring to the diffraction maximum comprising wurtzite structure in attached drawing 4,7,10, Fig. 4 and the diffraction maximum it is more sharp, show the production
Object is wurtzite-type zinc oxide and crystallinity is good, complete crystal form；In conjunction with Fig. 7, Figure 10 it is found that sample shape made from the present embodiment
Looks are reunited based on sheet and with a small amount of, and average grain diameter is about 100nm, according to the analysis, it is uneven that ammonium hydroxide is added dropwise when because adjusting pH
The unstable factors such as even, dry condition, the condition of centrifuge separation cause made sample to have part reunion to occur.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of zinc oxide micron/nano material, it is characterised in that: this method specifically includes the following steps:
(1) by ZnCl2Uniform, colorless and transparent ZnCl is configured under 100 DEG C of constant temperatures according to molar ratio 2:1 with ChCl2/
ChCl eutectic solvent；
(2) ZnCl made from step (1)2The steaming for being 1~2:1 with eutectic solvent volume ratio is added in/ChCl eutectic solvent
Distilled water is stirred at room temperature and uniformly obtains colourless transparent solution, then adjusts the solution system pH value to 8~10 with ammonium hydroxide, obtains
Milky white solution；
(3) milky white solution made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then by reaction kettle
Be placed in baking oven in 120~160 DEG C of progress hydro-thermal reactions, after reaction through cooling, centrifugation, wash, be dried to obtain white powder
Solid；
(4) white powdery solids made from step (3) are transferred in tube furnace, are forged for 450~550 DEG C in air atmosphere
It burns, natural cooling obtains white ZnO micro Nano material after calcining.
2. a kind of preparation method of zinc oxide micron/nano material as described in claim 1, it is characterised in that: in the step (1),
ZnCl21h is stirred to react in 100 DEG C of oil baths with ChCl, up to ZnCl after cooling2/ ChCl eutectic solvent.
3. a kind of preparation method of zinc oxide micron/nano material as described in claim 1, it is characterised in that: in the step (2),
PH is adjusted using the ammonium hydroxide of 25% concentration.
4. a kind of preparation method of zinc oxide micron/nano material as described in claim 1, it is characterised in that: in the step (3),
The hydro-thermal reaction time is 10~12h.
5. a kind of preparation method of zinc oxide micron/nano material as described in claim 1, it is characterised in that: in the step (3),
Reaction solution is cooling, centrifugation, obtains white solid after reaction, replaces washing white solid 3~6 times with distilled water using ethyl alcohol,
Last time, which is adopted, to be washed with distilled water, then in 60~80 DEG C of 6~8h of vacuum drying to get white powdery solids.
6. a kind of preparation method of zinc oxide micron/nano material as described in claim 1, it is characterised in that: in the step (4),
Calcination time is 2~4h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111204783A (en) * | 2020-01-17 | 2020-05-29 | 大连工业大学 | Porous gamma-Al prepared by using eutectic solvent as solvent and template agent2O3Method for preparing nano material |
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2018
- 2018-10-23 CN CN201811239127.3A patent/CN109110800B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111204783A (en) * | 2020-01-17 | 2020-05-29 | 大连工业大学 | Porous gamma-Al prepared by using eutectic solvent as solvent and template agent2O3Method for preparing nano material |
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