CN103911150A - Hydro-thermal synthesis method based on pH value control for zinc tungstate nano wire luminescent material - Google Patents
Hydro-thermal synthesis method based on pH value control for zinc tungstate nano wire luminescent material Download PDFInfo
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- CN103911150A CN103911150A CN201410098375.6A CN201410098375A CN103911150A CN 103911150 A CN103911150 A CN 103911150A CN 201410098375 A CN201410098375 A CN 201410098375A CN 103911150 A CN103911150 A CN 103911150A
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Abstract
The invention relates to a hydro-thermal synthesis method based on pH value control for a zinc tungstate nano wire luminescent material. According to the method, sodium tungstate and zinc sulfate are adopted as raw materials, distilled water is adopted as a solvent, glacial acetic acid is adopted as a complexing agent, the pH value of a precursor solution is adjusted by utilization of HCl or NaOH, and a zinc tungstate nano wire with a luminescence property is prepared by hydro-thermal synthesis. The length of the nano wire is 700-800 nm, and the diameter is about 30 nm. Under excitation of light having a wavelength of 291 nm, the zinc tungstate nano wire can generate strong emission peaks in 400-550 nm and the strongest peak value is around 457 nm. The e zinc tungstate nano wire is a good down-conversion luminescent material from ultraviolet light to visible light.
Description
Technical field
The invention belongs to inorganic functional micro Nano material preparation field, relate generally to the hydrothermal synthesis method of zinc tungstate nano wire luminescent material, particularly relate to a kind of method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material.
Background technology
Metal tungstates is nanocrystalline is the important inorganic materials of a class, has a good application prospect at aspects such as scintillation material, photoconductive fiber, photoluminescence material, catalyzer and inhibiter.The pattern of the synthetic better zinc tungstate of luminescent properties of microwave-hydrothermal method mostly is nanometer rod, at present report [reaction conditions is to ZnWO
4the pattern of nanometer rod and the impact of photoluminescence performance, Acta PhySico-Chimica Sinica [J], 2007,23 (7): 1123-1126] and [a kind of ZnWO
4the preparation method CN:201210458736.4 of nanometer rod photocatalyst material] respectively pH value be 5 ~ 9 and pH value be that the zinc tungstate nanometer rod length of 6 ~ 8 o'clock synthesizeds is respectively 200 ~ 400 nm and 50 nm.The advantages such as hydrothermal method is because of mild condition, simple to operate, and composition and purity are controlled are one of people's important method of being widely used in the synthetic micro-nano crystalline substance of zinc tungstate.In the Hydrothermal Synthesis of zinc tungstate nano material, precursor solution pH value has important impact to its pattern, size and microstructure, and then affects the photoluminescence performance of the micro-nano crystalline substance of zinc tungstate.
It is smaller that document is less than the 9 zinc tungstate nanometer rod length major diameters that make in pH value, and 291 nm wavelength excite down, 400 ~ 550 nm emission peak intensity a little less than.
Summary of the invention
Goal of the invention:
The present invention proposes a kind of method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material, its objective is in order to solve the synthetic zinc tungstate of the existing hydrothermal method nanocrystalline lower problem of luminous intensity slightly.
Technical scheme:
The present invention implements by the following technical programs:
Based on a method of controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material, it is characterized in that: step is as follows:
(1), under room temperature, 0.1 mol/L solution of zinc sulfate is mixed than the ratio that is 1:1 ~ 1:2 according to amount of substance with Glacial acetic acid;
(2) under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 ~ 0.55 mol/L identical with 0.1 mol/L solution of zinc sulfate volume, and be 9 ~ 11 constant by the rare HCl of 2.5 mol/L or rare NaOH regulator solution pH value, continue to stir, obtain precursor solution;
(3) described step (2) precursor solution is moved in hydrothermal reaction kettle, compactedness is 80%, 180
oc hydro-thermal 24 h;
(4) hydrothermal reaction kettle is cooled to room temperature, and the precipitation obtaining is washed respectively 3 times with distilled water and dehydrated alcohol, then in 60
oc is dried, and obtains zinc tungstate nano wire.
Continue to stir 40 min, obtain precursor solution.
The length of zinc tungstate nano wire is 700 ~ 800 nm, and diameter is 25 ~ 35 nm.
Advantage and effect:
The invention provides a kind of method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material, tool has the following advantages and beneficial effect:
(1) in reaction system, introduce complexing agent Glacial acetic acid, it can regulate and control the ordering growth of zinc tungstate micro Nano material;
(2) advantage such as hydrothermal method mild condition, simple to operate, composition and purity is controlled, meets the new approaches of Green Chemistry.
Brief description of the drawings
Fig. 1 is the X-ray diffraction analysis figure of synthetic sample;
Fig. 2 is zinc tungstate nano wire scanning electronic microscope (SEM) figure;
Fig. 3 is the fluorescence spectrum figure of zinc tungstate nano wire.
Embodiment
The present invention adopts simple hydrothermal method, using Glacial acetic acid as complexing agent, be that 9 ~ 11 to prepare length be 700 ~ 800 nm by regulating the pH value of precursor solution, diameter is about 30 nm, 291 nm wavelength excite down, have the ZnWO of stronger emission peak at 400 ~ 550 nm
4nano wire, and luminescent properties is good, is the down-conversion luminescent material of better UV-light to visible ray.
Below in conjunction with specific embodiment, the present invention is specifically described:
The invention provides a kind of method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material, taking sodium wolframate and zinc sulfate as raw material, using distilled water as solvent, Glacial acetic acid is as complexing agent, it is 9 ~ 11,180 that the rare HCl of 2.5 mol/L or rare NaOH regulate precursor solution pH value
othe synthetic zinc tungstate nano wire with luminescent properties of C hydro-thermal 24 h; Concrete steps are as follows:
(1), under room temperature, 0.1 mol/L solution of zinc sulfate is mixed than the ratio that is 1:1 ~ 1:2 according to amount of substance with Glacial acetic acid;
(2) under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 ~ 0.55 mol/L identical with 0.1 mol/L solution of zinc sulfate volume, and be 9 ~ 11 constant by the rare HCl of 2.5 mol/L or rare NaOH regulator solution pH value, continue to stir 40 min, obtain precursor solution;
(3) described step (2) precursor solution is moved in hydrothermal reaction kettle, compactedness is 80%, 180
oc hydro-thermal 24 h;
(4) hydrothermal reaction kettle is cooled to room temperature, and the precipitation obtaining is washed respectively 3 times with distilled water and dehydrated alcohol, then in 60
oc is dried, and obtains zinc tungstate nano wire.
The zinc tungstate nano wire obtaining, shows that through X-ray diffraction analysis the thing of products therefrom is ZnWO mutually
4, there is pattern regular, degree of crystallinity high, the length of measuring zinc tungstate nano wire through scanning electronic microscope is 700 ~ 800 nm, diameter is 30nm left and right (25 ~ 35 nm).
Under 291 nm wavelength excite, zinc tungstate nano wire produces and is positioned at emission peak stronger between 400 ~ 550 nm, and highest peak value is positioned near 457 nm, is the down-conversion luminescent material of better UV-light to visible ray.
embodiment 1
Zinc tungstate the fabricate of nanowires method and structural characterization
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1200 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 mol/L of 20 mL, and be 9 constant by the rare HCl of 2.5 mol/L or rare NaOH regulator solution pH value, continue to stir 40 min, obtain precursor solution;
Above-mentioned precursor solution is moved in hydrothermal reaction kettle, and compactedness is 80%, 180
oc hydro-thermal 24 h.Hydrothermal reaction kettle is cooled to room temperature, and the precipitation obtaining is washed respectively 3 times with distilled water and dehydrated alcohol, then in 60
oc is dried, and obtains zinc tungstate nano wire.
Show that through X-ray diffraction analysis the thing of products therefrom is ZnWO mutually
4, it is regular that it has pattern, degree of crystallinity high, and the length of nano wire is that 700 ~ 800 nm, diameter are 30 nm left and right (25 ~ 35 nm).Under 291 nm wavelength light excite, nano wire produces the stronger emission peak being positioned between 400 ~ 550 nm, and highest peak value is positioned near 457 nm, is the down-conversion luminescent material of better UV-light to visible ray.
embodiment 2
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1800 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1.5 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.50 mol/L of 20 mL, and be 9 constant by the rare HCl of 2.5 mol/L or rare NaOH regulator solution pH value, other conditions are with embodiment 1.
embodiment 3
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.2400 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:2 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.55 mol/L of 20 mL, and be 9 constant by the rare HCl regulator solution of 2.5 mol/L pH value, other conditions are with embodiment 1.
embodiment 4
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1200 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 mol/L of 20 mL, and be 10 constant by the rare NaOH regulator solution of 2.5 mol/L pH value, other conditions are with embodiment 1.
embodiment 5
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1200 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.50 mol/L of 20 mL, and be 11 constant by the rare NaOH regulator solution of 2.5mol/L pH value, other conditions are with embodiment 1.
embodiment 6
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1800 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1.5 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.55 mol/L of 20 mL, and be 10 constant by the rare NaOH regulator solution of 2.5 mol/L pH value, other conditions are with embodiment 1.
embodiment 7
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.1800 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:1.5 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 mol/L of 20mL, and be 11 constant by the rare NaOH regulator solution of 2.5mol/L pH value, other conditions are with embodiment 1.
embodiment 8
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.2400 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:2 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.50 mol/L of 20 mL, and be 10 constant by the rare NaOH regulator solution of 2.5 mol/L pH value, other conditions are with embodiment 1.
embodiment 9
20 mL 0.1 mol/L solution of zinc sulfate are mixed with 0.2400 g Glacial acetic acid, obtain zinc sulfate and compare the mixed solution for 1:2 with Glacial acetic acid amount of substance; Under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.55 mol/L of 20 mL, and be 11 constant by the rare NaOH regulator solution of 2.5 mol/L pH value, other conditions are with embodiment 1.
Claims (3)
1. the method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material, is characterized in that: step is as follows:
(1), under room temperature, 0.1 mol/L solution of zinc sulfate is mixed than the ratio that is 1:1 ~ 1:2 according to amount of substance with Glacial acetic acid;
(2) under room temperature, stir, above-mentioned mixed solution is dropwise joined in the sodium tungstate solution of 0.45 ~ 0.55 mol/L identical with 0.1 mol/L solution of zinc sulfate volume, and be 9 ~ 11 constant by the rare HCl of 2.5 mol/L or rare NaOH regulator solution pH value, continue to stir, obtain precursor solution;
(3) described step (2) precursor solution is moved in hydrothermal reaction kettle, compactedness is 80%, 180
oc hydro-thermal 24 h;
(4) hydrothermal reaction kettle is cooled to room temperature, and the precipitation obtaining is washed respectively 3 times with distilled water and dehydrated alcohol, then in 60
oc is dried, and obtains zinc tungstate nano wire.
2. the method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material according to claim 1, is characterized in that: continue to stir 40 min, obtain precursor solution.
3. the method based on controlling pH value Hydrothermal Synthesis zinc tungstate nano wire luminescent material according to claim 1, is characterized in that: the length of zinc tungstate nano wire is 700 ~ 800 nm, and diameter is 25 ~ 35 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111105934A (en) * | 2019-12-25 | 2020-05-05 | 青岛科技大学 | ZnWO4Preparation of nano-rod and application thereof in super capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111105934A (en) * | 2019-12-25 | 2020-05-05 | 青岛科技大学 | ZnWO4Preparation of nano-rod and application thereof in super capacitor |
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