CN102976344A - Preparation method of zinc silicate nanometer material - Google Patents
Preparation method of zinc silicate nanometer material Download PDFInfo
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- CN102976344A CN102976344A CN2012105881976A CN201210588197A CN102976344A CN 102976344 A CN102976344 A CN 102976344A CN 2012105881976 A CN2012105881976 A CN 2012105881976A CN 201210588197 A CN201210588197 A CN 201210588197A CN 102976344 A CN102976344 A CN 102976344A
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Abstract
The invention discloses a preparation method of a zinc silicate nanometer material. Amorphous nanometer silicon dioxide and soluble zinc salt are used as raw materials. The preparation method comprises the following steps: (A) weighing the amorphous nanometer silicon dioxide and the soluble zinc salt according to a stoichiometric ratio so as to prepare a suspended aqueous solution, regulating pH value of the suspended aqueous solution to 5-13, and stirring the suspended aqueous solution; (B) transferring the suspended aqueous solution in the step A into a hydrothermal reaction kettle and reacting the suspended aqueous solution at 160-230 DEG C for 2-24 hours; and (C) cooling a reaction system after the reaction is finished, and washing and drying a reaction product so as to obtain the zinc silicate nanometer material. The preparation method disclosed by the invention has the advantages of mild reaction, good reproducibility, simplicity in operation and the like; and the prepared Zn2SiO4 can be widely applied to the fields of fluorescent materials, catalytic degradation, adsorbing materials and so on.
Description
Technical field
The present invention relates to the synthetic field of inorganic functional nano material, a kind of zinc silicate preparations of nanomaterials method particularly, it adopts one step of hydrothermal method to form nano material, and technique is simple, flow process is short.
Background technology
Zinc silicate (Zn
2SiO
4) be a kind of important inorganic materials, be widely used in the fields such as fluorescent material, sorbent material, glass additive, coating.Especially zinc silicate has the advantages such as environmental compatibility is strong, chemical stability good, moisture resistance is strong, be easy to prepare, cheap as the luminous host material, receives much attention in luminescent material research.
At present, the synthetic method of zinc silicate material mainly is high-temperature solid phase reaction method, is about to ZnO and SiO
2Mix afterwards roasting acquisition (Y. Wang, Y. Hao, L. H. Yuwen, J. Alloy. Compd. 2006,425,339-342 in the hot environment more than 1000 ℃ by stoichiometric ratio; A. Morell, N. Elkhiati, J. Electrochem. Soc. 1993,140,2019-2022); Also have adopt sol-gel method obtain behind the precursor again through high-temperature heat treatment obtain (M. S. Kwon, C. J. Kim, H. L. Park, T. W. Kim, H. S. Lee, J. Mater. Sci. 2005,40,4089-4091).These methods all need hot environment, and reaction process exists the energy consumption height, fires long shortcoming of cycle; In addition, through the product that high-temperature heat treatment obtains, its moiety and particle size are wayward, and pattern is also irregular, and these shortcomings have restricted the performance of material to a certain extent.
In recent years, along with the development of Materials science and nanotechnology, nano material is because its unique microtexture demonstrates impayable advantage on its performance gradually.Compare with traditional bulk material, the particle diameter of nano material is little, specific surface area is large, in use can show better properties, and is of great advantage to the application of material.At present, the research for preparing the aspect about hydrothermal method acquisition zinc silicate nano material is also very limited at home and abroad, mostly needs to introduce tensio-active agent (X. Yu, Y. H. Wang, J. Nanosci. Nanotechno. 2010,10,1-4; J. X. Wan, Z. H. Wang, X. Y. Chen, L. Mu, W. C. Yu, Y. T. Qian, J. Lumin. 2006,121,32-38), organic formwork agent (G. Q. Xu, J. Q. Liu, Z. X. Zheng, Y. C. Wu, Chin. J. Lumin. 2011,32, the additive such as 550-554), or under 280 ℃ high temperature, could obtain (H. F. Wang through long-time reaction, Y. Q. Ma, G. S. Yi, D. P. Chen, Mater. Chem. Phys. 2003,82,414-418), these methods have increased preparation cost greatly, also are unfavorable for industrial production simultaneously.Therefore: explore the low temperature controllable preparation method of zinc silicate nano material, be of great significance for the application tool of zinc silicate material.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of zinc silicate preparations of nanomaterials method, and it adopts hydrothermal method one-step synthesis nanometer zinc silicate, and the method temperature of reaction is low, technique is simple, product pattern and size are easy to control.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is:
A kind of zinc silicate preparations of nanomaterials method, take the amorphous nano silicon-dioxide of stoichiometric ratio and soluble zinc salt as raw material, regulate the aqueous suspension pH to 5-13 of above-mentioned raw materials, then adopt hydrothermal method at 150-230 ℃ of reaction 2-24h, get the zinc silicate nano material.
Particularly, above-mentioned preparation method comprises the steps:
Steps A, take by weighing amorphous nano silicon-dioxide and the soluble zinc salt of stoichiometric ratio, be mixed with aqueous suspension, and adjust pH stirs to 5-13;
Step B, the aqueous suspension in the steps A is changed in the hydrothermal reaction kettle, in 150-230 ℃ of reaction 2-24 hour;
Step C, the reaction system that will react complete are cooled off, and reaction product gets the zinc silicate nano material through washing, drying.
Preferably, described soluble zinc salt is zinc nitrate, zinc sulfate or zinc chloride.
Soluble zinc salt is zinc nitrate, zinc sulfate or zinc chloride.
In the steps A in the aqueous suspension concentration of soluble zinc salt be 0.1-1mol/L.Zinc salt dissolves, and silicon-dioxide is non-water-soluble, has formed the aqueous suspension that contains 0.1-1 mol/L soluble zinc salt.
Preferably, regulate the pH value with NaOH or the KOH aqueous solution, stir 20-40min.Can not regulate the pH value with ammoniacal liquor among the present invention, can generate Zn (OH)
2Precipitation.
The preferred 200-220 of temperature of reaction ℃, when temperature of reaction was lower than 150 ℃, the product of generation was tested through XRD, and it is more to contain impurity.
Difference water and absolute ethanol washing are 3-5 time among the step C.Remaining foreign ion in the washing reaction system.
In the technique scheme, take stoichiometric amorphous nano silicon-dioxide and soluble zinc salt as raw material, take water as medium, adopt one step hydro thermal method can make grain size as the zinc silicate nano material of 20-300nm, need not use any tensio-active agent or organic formwork agent in the reaction process, operation is simple, experiment condition is controlled, good reproducibility.
The beneficial effect that adopts technique scheme to produce is: the advantage that (1) temperature of reaction of the present invention is low, reaction conditions is gentle, and technique is simple, good reproducibility, product crystal property are excellent, energy consumption of reaction is low, and environmental protection is suitable for industrialized scale production; (2) the present invention adopts one step hydro thermal method to realize the controlled preparation of low temperature of zinc silicate, adopts wet method synthetic, has realized the mixing on molecular level of zinc, silicon, oxygen, and product composition is controlled easily, even size distribution; (3) can control pattern and the size of zinc silicate Nano/micron material by reaction conditionss such as control temperature of reaction, reaction times, system pH and raw materials.
Description of drawings
Fig. 1 and Fig. 2 are respectively the Zn that embodiment 1 makes
2SiO
4The X-ray powder diffraction of nano particle (XRD) figure and scanning electron microscope analysis (SEM) figure;
Fig. 3 and Fig. 4 are respectively the Zn that embodiment 2 makes
2SiO
4The XRD figure of nanometer rod and SEM figure;
Fig. 5 and Fig. 6 are respectively the Zn that embodiment 3 makes
2SiO
4The XRD figure of nanometer rod and SEM figure;
Fig. 7 and Fig. 8 are respectively the Zn that embodiment 4 makes
2SiO
4The XRD figure of nanometer stub and SEM figure;
Fig. 9 and Figure 10 are respectively the Zn that embodiment 5 makes
2SiO
4The XRD figure of nanometer stub and SEM figure.
Embodiment
Embodiment 1
A kind of zinc silicate preparations of nanomaterials method take amorphous nano silicon-dioxide and soluble zinc salt as raw material, specifically comprises the steps:
Under steps A, the room temperature, take by weighing the amorphous nano SiO that the 2mmol diameter is about 200nm
2Add to the Zn (NO of 10mL 0.4mol/L
3)
26H
2In the O solution, stir 10 min, form aqueous suspension, then with the NaOH solution of 1mol/L the pH value of reaction system is transferred to 5, continuation stirring 30min;
Step B, the aqueous suspension in the steps A is changed in the 25 mL hydrothermal reaction kettles, be placed on after the sealing in the thermostat container, 220 ℃ of hydro-thermal reactions 24 hours;
Step C, reaction are cooled to room temperature with reaction system after complete, with the reaction product centrifugation, then use respectively deionized water and dehydrated alcohol difference washing reaction product each 5 times, remove foreign ion, then the product after will washing is 60 ℃ of vacuum-drying 4h in vacuum drying oven, obtain Zn
2SiO
4Nano particle.
The Zn that present embodiment makes
2SiO
4The XRD spectra of nano particle as shown in Figure 1, the intensity of its diffraction peak and position and Zn2SiO4 standard card (JCPDS-ICDD No. 37-1485) match, and do not have the dephasign diffraction peak, illustrate to have obtained the higher Zn of purity
2SiO
4Nano particle.
Zn
2SiO
4The scanning electron microscope analysis of nano particle (Fig. 2) shows: the Zn of present embodiment preparation
2SiO
4Be comprised of the uniform nano particle of a large amount of diameters, particle diameter is about 50nm.
Present embodiment has prepared the Zn that particle diameter is about 50nm with lower temperature, simple technique
2SiO
4, do not add any tensio-active agent or other dispersion agents in the reaction process, simple to operate, impurity is few, condition be easy to control.
Embodiment 2
Under steps A, the room temperature, take by weighing the amorphous nano SiO that the 2mmol diameter is about 200nm
2Add to the Zn (NO of 10 mL, 0.4 mol/L
3)
26H
2In the O solution, stir 10min, form aqueous suspension, then with the NaOH solution of 1mol/L the pH value of reaction system is transferred to 9 after, continuation stirring 30min;
Step B, the aqueous suspension in the steps A is changed in the 25 mL hydrothermal reaction kettles, be placed on after the sealing in the thermostat container, 220 ℃ of hydro-thermal reactions 24 hours;
Step C, reaction are cooled to room temperature with reaction system after complete, with the reaction product centrifugation, then use respectively deionized water and dehydrated alcohol difference washing reaction product each 5 times, remove foreign ion, then the product after will washing is 60 ℃ of vacuum-drying 4h in vacuum drying oven, obtain Zn
2SiO
4Nanometer rod.
The Zn that present embodiment makes
2SiO
4The XRD spectra of nanometer rod as shown in Figure 3, the intensity of its diffraction peak and position and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches; Scanning electron microscope analysis (Fig. 4) shows: product is to be made of a large amount of nanometer rod, and the diameter of single nanometer rod is about 100 nm, and length is about 500nm, and length-to-diameter ratio is about 5, and the size of nanometer rod is more even.
Embodiment 3
Under steps A, the room temperature, take by weighing the amorphous nano SiO that the 2mmol diameter is about 200nm
2Add to the Zn (NO of 10mL 0.4 mol/L
3)
26H
2In the O solution, stir 20 min, form aqueous suspension, then with the NaOH solution of 2mol/L the pH value of reaction system is transferred to 13 after, continuation stirring 30min;
Step B, the aqueous suspension in the steps A is changed in the 25 mL hydrothermal reaction kettles, be placed on after the sealing in the thermostat container, 220 ℃ of hydro-thermal reactions 24 hours;
Step C, reaction are cooled to room temperature with reaction system after complete, with the reaction product centrifugation, then use respectively deionized water and dehydrated alcohol difference washing reaction product repeatedly, remove foreign ion, then the product after will washing is 60 ℃ of vacuum-drying 4h in vacuum drying oven, obtain Zn
2SiO
4Sub-micrometer rod.
The Zn of present embodiment preparation
2SiO
4The XRD spectra of sub-micrometer rod as shown in Figure 5.The intensity of its diffraction peak and position and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches; Scanning electron microscope analysis (Fig. 6) shows: product is to be made of a large amount of finely disseminated sub-micrometer rods, and the surface of sub-micrometer rod is more smooth, and the diameter of single sub-micrometer rod is about 200 nm, and length is about 2-4 μ m, and length-to-diameter ratio is 10-20, and size is more even.
Embodiment 4
Under steps A, the room temperature, claim the 2mmol diameter to be about the amorphous nano SiO of 200nm
2Add to the Zn (NO of 5mL 0.8mol/L
3)
26H
2In the O solution, stir 10 min, form aqueous suspension, then with the NaOH solution of 1mol/L the pH value of reaction system is transferred to 9 after, continuation stirring 30min;
Step B, the aqueous suspension in the steps A is changed in the 25 mL hydrothermal reaction kettles, be placed on after the sealing in the thermostat container, 220 ℃ of hydro-thermal reactions 2 hours;
Step C, reaction are cooled to room temperature with reaction system after complete, with the reaction product centrifugation, then use respectively deionized water and dehydrated alcohol difference washing reaction product repeatedly, remove foreign ion, then the product after will washing is 60 ℃ of vacuum-drying 4h in vacuum drying oven, obtain Zn
2SiO
4The nanometer stub.
The Zn that present embodiment is prepared
2SiO
4The XRD spectra of nanometer stub as shown in Figure 7.The intensity of its diffraction peak and position and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches; Scanning electron microscope analysis (Fig. 8) shows: product is to be made of a large amount of nanometer stubs, and the surface of nanometer stub is more smooth, and the diameter of single nanometer rod is about 100 nm, and length is about 200 nm, and length-to-diameter ratio is about 2, size uniform, favorable dispersity.
Embodiment 5
Under steps A, the room temperature, take by weighing the amorphous nano SiO that the 2mmol diameter is about 200nm
2Add to the Zn (NO of 10mL 0.4mol/L
3)
26H
2In the O solution, stir 10 min, form aqueous suspension, then with the NaOH solution of 1mol/L the pH value of reaction system is transferred to 9 after, continuation stirring 30min;
Step B, the aqueous suspension in the steps A is changed in the 25 mL hydrothermal reaction kettles, be placed on after the sealing in the thermostat container, 160 ℃ of hydro-thermal reactions 24 hours;
Step C, reaction are cooled to room temperature with reaction system after complete, with the reaction product centrifugation, then use respectively deionized water and dehydrated alcohol difference washing reaction product repeatedly, remove foreign ion, then the product after will washing is 60 ℃ of vacuum-drying 4h in vacuum drying oven, obtain Zn
2SiO
4The nanometer stub.
The Zn of present embodiment preparation
2SiO
4The XRD spectra of nanometer stub as shown in Figure 9.The intensity of its diffraction peak and position and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches; Scanning electron microscope analysis (Figure 10) shows: product is to be made of a large amount of nanometer stubs, and the surface of nanometer stub is more smooth, and the diameter of single nanometer rod is about 100 nm, and length is about 200 nm, and length-to-diameter ratio is about 2, size uniform, favorable dispersity.
Embodiment 6
With reference to the synthetic Zn of the method steps of embodiment 1
2SiO
4Material, different is:
Raw material is the ZnSO of 10mL0.4mol/L
4, reaction conditions is: at 200 ℃ of reaction 10h, transfer pH to 10.
The Zn of present embodiment preparation
2SiO
4Be the nano particle of diameter at 80 ~ 120nm, size uniform.XRD figure spectrum and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches.
Embodiment 7
With reference to the synthetic Zn of the method steps of embodiment 1
2SiO
4Material, different is:
Raw material is the ZnCl of 10mL0.4mol/L
2, reaction conditions is: at 180 ℃ of reaction 12h, transfer pH to 9.
The Zn of present embodiment preparation
2SiO
4For diameter is about 120nm, length is about 250nm, and length-to-diameter ratio is about 2 nanometer rod, size uniform, favorable dispersity.XRD figure spectrum and Zn
2SiO
4Standard card (JCPDS-ICDD No. 37-1485) matches.
In sum, the present invention adopts simple technique, lower reaction conditions to prepare size uniform, nano material that pattern is good, is suitable for suitability for industrialized production.
Claims (9)
1. zinc silicate preparations of nanomaterials method, it is characterized in that take the amorphous nano silicon-dioxide of stoichiometric ratio and soluble zinc salt as raw material, regulate the aqueous suspension pH to 5-13 of above-mentioned raw materials, then adopt hydrothermal method at 150-230 ℃ of reaction 2-24h, get the zinc silicate nano material.
2. zinc silicate preparations of nanomaterials method according to claim 1 is characterized in that described method comprises the steps:
Steps A, take by weighing amorphous nano silicon-dioxide and the soluble zinc salt of stoichiometric ratio, be mixed with aqueous suspension, and adjust pH stirs to 5-13;
Step B, the aqueous suspension in the steps A is changed in the hydrothermal reaction kettle, in 150-230 ℃ of reaction 2-24 hour;
Step C, the reaction system that will react complete are cooled off, and reaction product gets the zinc silicate nano material through washing, drying.
3. zinc silicate preparations of nanomaterials method according to claim 1 and 2 is characterized in that described soluble zinc salt is zinc nitrate, zinc sulfate or zinc chloride.
4. zinc silicate preparations of nanomaterials method according to claim 1 and 2, the concentration that it is characterized in that soluble zinc salt in the aqueous suspension is 0.1-1mol/L.
5. zinc silicate preparations of nanomaterials method according to claim 1 and 2 is characterized in that regulating the pH value with NaOH or the KOH aqueous solution, stirs 20-40min.
6. zinc silicate preparations of nanomaterials method according to claim 1 and 2 is characterized in that temperature of reaction is 200-220 ℃.
7. zinc silicate preparations of nanomaterials method according to claim 1 is characterized in that distinguishing among the step C water and absolute ethanol washing 3-5 time.
8. zinc silicate preparations of nanomaterials method according to claim 1 is characterized in that the drying conditions among the step C is: 60-80 ℃ vacuum-drying 2-4 hour.
9. zinc silicate preparations of nanomaterials method according to claim 1, the particle size range that it is characterized in that the zinc silicate nano material is 20-300nm.
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CN104383873A (en) * | 2014-11-13 | 2015-03-04 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing composite adsorbent by utilizing low-grade attapulgite clay |
CN104447834A (en) * | 2014-11-25 | 2015-03-25 | 廊坊师范学院 | Preparation method for nano methyl zinc silicate |
CN108047795A (en) * | 2018-01-02 | 2018-05-18 | 华东理工大学 | A kind of zinc silicate anti-corrosion paint with warning function |
IT201700122793A1 (en) * | 2017-10-27 | 2019-04-27 | Bridgestone Corp | NANOMATERIALS BASED ON SILICA AS SUBSTITUTES OF THE ZNO IN RUBBER COMPOUNDS AND THEIR PREPARATION |
CN109796021A (en) * | 2019-04-04 | 2019-05-24 | 河北工业大学 | Utilize the method for iron tailings preparation ellipsoid zinc silicate compound adsorbent |
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CN117003253A (en) * | 2023-07-26 | 2023-11-07 | 上海师范大学 | Zinc silicate flower-shaped porous microsphere and preparation method thereof |
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CN104383873B (en) * | 2014-11-13 | 2016-08-24 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing composite adsorbent by using low-grade attapulgite clay |
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CN109796021B (en) * | 2019-04-04 | 2022-04-05 | 河北工业大学 | Method for preparing ellipsoidal zinc silicate composite adsorbent by using iron tailings |
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