CN103183372A - Solid-phase preparation method for nano zinc oxide through template - Google Patents
Solid-phase preparation method for nano zinc oxide through template Download PDFInfo
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- CN103183372A CN103183372A CN2013101177837A CN201310117783A CN103183372A CN 103183372 A CN103183372 A CN 103183372A CN 2013101177837 A CN2013101177837 A CN 2013101177837A CN 201310117783 A CN201310117783 A CN 201310117783A CN 103183372 A CN103183372 A CN 103183372A
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Abstract
The invention discloses a solid-phase preparation method for nano zinc oxide through a template and relates to a solid-phase preparation method for nano zinc oxide. The method comprises the following steps: first, synthesizing lignin into lignin amine; and then, performing solid-phase preparation for nano zinc oxide taking the lignin amine as the template. According to the invention, the reticular lignin amine is prepared from the lignin through Mannick reaction, the advantages of being low in cost, nontoxic, easy to get and the like can be achieved; some base groups of the lignin amine are removed through high-temperature roasting, a pore structure is left, so that the specific surface area of the nano zinc oxide obtained from the lignin amine as a template agent is increased. Therefore, the method provided by the invention has the advantages of simple synthesis process, uniform particle size, controllable dynamics, low cost, easiness in operation, high yield, and low pollution, and reduces the hard aggregation appearance. The product prepared from the method is ice-cream, and adopts the structure of lead zinc ore of hexagonal system, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of method of solid phase preparation nano zine oxide, particularly is the method that template molecule prepares nano zine oxide with the lignin amine.
Background technology
Characteristics such as that xylogen has is nontoxic, with low cost, environmental friendliness are effectively utilized xylogen not only can save natural resources, and are conducive to protect environment.The comprehensive utilization of xylogen is the key of straw pulp black liquor resource type treating.In preparation of nanomaterials, template can be controlled particle diameter, the pattern of nano material better, realizes synthetic and being assembled into one of nano material, can solve the dispersion stabilization problem of nano material simultaneously, and building-up process is simple relatively, and a lot of methods are fit to produce in batches.Template mainly contains the colloidal crystal of various types of tensio-active agents, segmented copolymer, on-surface-active organic molecule, microemulsion emulsion droplets and polymer microballoon formation etc., the lignin amine that forms behind the lignin modification is mesh-structured, does not appear in the newspapers with its pertinent literature as the template nano materials.
Nano zine oxide (ZnO) crystal is because its energy gap is big, and the exciton binding energy height is with a wide range of applications and receives much attention in fields such as short wavelength light electrical equipment, field-effect transistor, varistor, gas sensor, solar cell and catalysis.Its size of particles is little, and specific surface area is big, has characteristics such as tangible surface and interfacial effect, shows physicals and the chemical property of many uniquenesses at aspects such as chemistry, optics, biology and electricity.In recent years, along with industrial expansion and progress, the demand of zinc oxide is increased day by day, the photoluminescence of research nano zine oxide can be deeply to the understanding of nano zine oxide, and people pay close attention to its research more.
The solid state reaction legal system is equipped with nano-ZnO, compares than vapor phase process, liquid phase method, and synthesis technique is simple, and particle diameter is even, and dynamics is controlled, reduces the hard aggregation phenomenon, and cost is low, easy to operate, high yield, pollution are few.These characteristics meet the requirement of current social Green Chemistry development, have shown bigger advantage aspect nano material synthetic, just progressively develop into a little subbranch in synthetic field.In the present invention, use lignin amine to show excellent fluorescence as template solid phase synthesis nano zine oxide.
Summary of the invention
The objective of the invention is to adopt lignin amine is template, synthesizes and pass through to calcine under the differing temps by solid phase method to prepare nano zine oxide, and technology is simple, and raw material is easy to obtain, and is with low cost, of reduced contamination, is suitable for suitability for industrialized production.
Technical scheme of the present invention is: a kind of method of lignin amine template solid phase preparation nano zine oxide, earlier xylogen is synthesized lignin amine, and be template solid phase preparation nano zine oxide with prepared lignin amine then.
(1) synthesis step of lignin amine is as follows:
Take by weighing the xylogen of certain mass under A, the room temperature, add deionized water and 0.4 mol ﹒ L
-1NaOH solution, behind the magnetic agitation 10-20min, the formaldehyde that adds certain volume, stir 10-20min, add a certain amount of amine again, continue to stir 10-20min, described xylogen: deionized water is (4-8): (95-190) g/mL, xylogen: NaOH is (4-8): (5.5-10.0) g/mL, and xylogen: formaldehyde is (4-8): (0.5-2.5) g/mL, xylogen and amine mass ratio are (4-8): (2.6-7.0);
B, with the above-mentioned solution 3-5h that under 65-95 ℃ of temperature, refluxes, be cooled to room temperature, filter;
C, in filtrate, add 10% potassium ferricyanide solution, treat complete post precipitation, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into the dry 10-12h of thermostatic drying chamber, described loft drier temperature is 50-60 ℃.
(2) be that the reactions steps of template solid phase preparation nano zine oxide is as follows with prepared lignin amine:
A, solid-state zinc salt and the yellow soda ash of amount of substance such as getting grind 10-20 min respectively, transfer in the same mortar, the lignin amine that adds above-mentioned preparation continues to grind 20-30min in this mortar, get paste mixture, described zinc salt and lignin amine add the mixed of 1 ~ 3g lignin amine with the 0.05mol zinc salt;
B, with the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitate with deionized water is cleaned 2-3 time, cleans 3-5 time centrifugation again with dehydrated alcohol;
C, the solid after will separating are put into the dry 10-12h of thermostatic drying chamber, and the temperature of described thermostatic drying chamber is 50-60 ℃;
D, at last with dried solid in 300-600 ℃ of roasting temperature 2-4h.
In the more excellent open example of the present invention, described xylogen is alkali lignin.
In the more excellent open example of the present invention, described amine is ethylene diamine, diethylenetriamine, any in triethylene tetramine, tetraethylene pentamine, the hexanediamine.
In the more excellent open example of the present invention, described zinc salt is zinc nitrate.
According to the nano zine oxide that the method disclosed in the present prepares, the plumbous zinc ore structure of hexagonal system.
The used reagent of this experiment is all analytical pure, and alkali lignin is technical grade, is commercially available.
Beneficial effect
The present invention utilizes xylogen to make cancellated lignin amine by Mannich reaction, it has inexpensive, nontoxic, advantage such as be easy to get, and after high-temperature roasting, the part group of lignin amine is removed, stay pore texture, making is increased as the nano zine oxide specific surface area that template makes by lignin amine.Synthesis technique of the present invention is simple, and particle diameter is even, and dynamics is controlled, reduces the hard aggregation phenomenon, and cost is low, easy to operate, high yield, pollution are few.The product of preparation is oyster white, and the plumbous zinc ore structure of hexagonal system is fit to suitability for industrialized production.
Description of drawings
The X ray diffracting spectrum of Fig. 1 sample (XRD), a is the XRD figure spectrum of embodiment 1 sample among the figure, and b is the XRD figure spectrum of embodiment 2 samples among the figure, and c is the XRD figure spectrum of embodiment 3 samples among the figure, and d is the XRD figure spectrum of embodiment 7 samples among the figure.
The sem photograph of Fig. 2 sample (SEM), wherein, a is the sem photograph of embodiment 1 sample; B is the sem photograph of embodiment 2 samples; C is the sem photograph of embodiment 3 samples.
The fluorescence spectrum of Fig. 3 sample (PL), wherein a is the PL figure of embodiment 1 sample, excitation wavelength is 280nm; B is the PL figure of embodiment 3 samples, and excitation wavelength is 280nm; C is the PL figure of embodiment 7 samples, and excitation wavelength is 280nm.
Embodiment
The present invention will be further described below in conjunction with concrete embodiment, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
Lignin amine template solid phase preparation nano zinc oxide photocatalyst, the concrete step is poly-as follows:
1. get alkali lignin 4g under the room temperature and place the 250mL round-bottomed flask, add 95mL deionized water and 5.5 mL, 0.4 mol ﹒ L
-1NaOH solution, stir 10min, add the formaldehyde of 1.5 mL, stir 10min, add the 4.8g hexanediamine again, stir 10min, at 65 ℃ of following reflux 3h, be cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, the lignin amine of preparation is precipitated fully, decompress filter, repeatedly the unnecessary Tripotassium iron hexacyanide is removed in washing, and filter cake is put into 60 ℃ of dry 10h of thermostatic drying chamber;
2. with 0.05mol Zn (NO
3)
26H2O and 0.05molNa
2CO
3In different mortars, grind 15 min respectively, the two is transferred in the same mortar then, grind 20min together to wherein adding the lignin amine that 1.0g step 1 synthesized again, with the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitation is cleaned 3 times with dehydrated alcohol, uses washed with de-ionized water again 3 times, centrifugation; After the separation solid put into 60 ℃ of dry 10h of thermostatic drying chamber; Then with sample at 300 ℃ of following roasting 2h, namely obtain the oyster white nano zine oxide.Sample XRD such as Fig. 1 a, SEM such as Fig. 2 a, PL such as Fig. 3 a.
Embodiment 2
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is that the formaldehyde that adds in the 1st step is 2.5mL, and used amine is tetraethylene pentamine 3.2g, the 2nd the step at last with sample at 400 ℃ of following roasting 2h, namely obtain white nano zine oxide.Sample XRD such as Fig. 1 b, SEM such as Fig. 2 b.
Embodiment 3
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference be the 2nd the step at last with sample at 600 ℃ of following roasting 2h, get white nano zine oxide.Sample XRD such as Fig. 1 c, SEM such as Fig. 2 c, PL such as Fig. 3 b.
Embodiment 4
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is in the 1st step filter cake to be put into 50 ℃ of dry 12h of thermostatic drying chamber, and the lignin amine of being synthesized that adds in the 2nd step is 3g, at last with sample at 400 ℃ of following roasting 2h, get white nano zine oxide.
Embodiment 5
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is that the formaldehyde that adds in the 1st step is 2.5mL, used amine is triethylene tetramine 3.2g, 0.05mol Zn (NO in the 2nd step
3)
26H2O and 0.05molNa
2CO
3In different mortars, grind 20 min respectively, the two is transferred in the same mortar then, grind 30min together to wherein adding the lignin amine that 1.0g step 1 synthesized again, after the separation solid put into 50 ℃ of dry 12h of thermostatic drying chamber, at last with sample at 600 ℃ of following roasting 2h, get white nano zine oxide.
Embodiment 6
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is to add alkali lignin 8g in the 1st step, deionized water 190mL, NaOH solution 10mL, hexanediamine 7g is at 95 ℃ of following reflux 5h; 0.05mol Zn (NO in the 2nd step
3)
26H2O and 0.05molNa
2CO
3In different mortars, grind respectively 10 min at last with sample at 500 ℃ of following roasting 3h, get white nano zine oxide.
Embodiment 7
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference be at last with sample at 400 ℃ of following roasting 3h, get white nano zine oxide.Sample XRD such as Fig. 1 d, PL such as Fig. 3 c.
Embodiment 8
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is that the alkali lignin that adds in the 1st step is 8g, deionized water 190mL, 0.4 mol ﹒ L
-1NaOH solution be 10mL, formaldehyde is 2.5mL, used hexanediamine is that amine is 7g, condensing reflux 5 hours, the 2nd the step at last with sample at 600 ℃ of following roasting 4h, get white nano zine oxide.
Embodiment 9
Lignin amine template solid phase preparation nano zine oxide, with embodiment 1 step, difference is that the formaldehyde that adds in the 1st step is 0.5mL, used hexanediamine is 2.6g, in the 2nd step at last with sample at 400 ℃ of following roasting 2h, get white nano zine oxide.
Claims (8)
1. the method for a lignin amine template solid phase preparation nano zine oxide, undertaken by following step:
(1) synthesis step of lignin amine is as follows:
Take by weighing the xylogen of certain mass under A, the room temperature, add deionized water and 0.4 mol ﹒ L
-1NaOH solution, behind the magnetic agitation 10-20min, the formaldehyde that adds certain volume, stir 10-20min, add a certain amount of amine again, continue to stir 10-20min, described xylogen: deionized water is (4-8): (95-190) g/mL, xylogen: NaOH is (4-8): (5.5-10.0) g/mL, and xylogen: formaldehyde is (4-8): (0.5-2.5) g/mL, xylogen and amine mass ratio are (4-8): (2.6-7.0);
B, with the above-mentioned solution 3-5h that under 65-95 ℃ of temperature, refluxes, be cooled to room temperature, filter;
C, in filtrate, add 10% potassium ferricyanide solution, treat complete post precipitation, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into the dry 10-12h of thermostatic drying chamber, described loft drier temperature is 50-60 ℃;
(2) be that the reactions steps of template solid phase preparation nano zine oxide is as follows with prepared lignin amine:
A, solid-state zinc salt and the yellow soda ash of amount of substance such as getting grind 10-20 min respectively, transfer in the same mortar, the lignin amine that adds above-mentioned preparation continues to grind 20-30min in this mortar, get paste mixture, described zinc salt and lignin amine add the mixed of 1 ~ 3g lignin amine with the 0.05mol zinc salt;
B, with the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitate with deionized water is cleaned 2-3 time, cleans 3-5 time centrifugation again with dehydrated alcohol;
C, the solid after will separating are put into the dry 10-12h of thermostatic drying chamber, and the temperature of described thermostatic drying chamber is 50-60 ℃;
D, at last with dried solid in 300-600 ℃ of roasting temperature 2-4h.
2. according to the method for the lignin amine template solid phase preparation nano zine oxide described in the claim 1, it is characterized in that the xylogen described in the step (1) is alkali lignin.
3. according to the method for the lignin amine template solid phase preparation nano zine oxide described in the claim 1, it is characterized in that the amine described in the step (1) is ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or hexanediamine.
4. according to the method for the lignin amine template solid phase preparation nano zine oxide described in the claim 1, it is characterized in that the zinc salt described in the step (2) is zinc nitrate.
5. the nano zine oxide for preparing according to the described either party's method of claim 1 ~ 4, the plumbous zinc ore structure of hexagonal system.
6. the preparation method of a lignin amine, synthetic by following step:
Take by weighing the xylogen of certain mass under A, the room temperature, add deionized water and 0.4 mol ﹒ L
-1NaOH solution, behind the magnetic agitation 10-20min, the formaldehyde that adds certain volume, stir 10-20min, add a certain amount of amine again, continue to stir 10-20min, described xylogen: deionized water is (4-8): (95-190) g/mL, xylogen: NaOH is (4-8): (5.5-10.0) g/mL, and xylogen: formaldehyde is (4-8): (0.5-2.5) g/mL, xylogen and amine mass ratio are (4-8): (2.6-7.0);
B, with the above-mentioned solution 3-5h that under 65-95 ℃ of temperature, refluxes, be cooled to room temperature, filter;
C, in filtrate, add 10% potassium ferricyanide solution, treat complete post precipitation, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into the dry 10-12h of thermostatic drying chamber, described loft drier temperature is 50-60 ℃.
7. according to the method for the lignin amine template solid phase preparation nano zine oxide described in the claim 6, it is characterized in that the xylogen described in the steps A is alkali lignin.
8. according to the method for the lignin amine template solid phase preparation nano zine oxide described in the claim 6, it is characterized in that the amine described in the steps A is ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or hexanediamine.
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| CN106587019A (en) * | 2016-12-16 | 2017-04-26 | 武汉工程大学 | Preparation method for lignin-based biological carbon/graphene composite nanometer material |
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| CN108671906A (en) * | 2018-05-29 | 2018-10-19 | 江苏海川卓越密封材料有限公司 | Compound bismuth vanadate photocatalyst of high activity and preparation method thereof |
| CN111675238A (en) * | 2020-08-03 | 2020-09-18 | 安徽景成新材料有限公司 | Method for preparing multi-morphology nano zinc oxide by solid phase method |
| CN112072085A (en) * | 2020-08-20 | 2020-12-11 | 华南理工大学 | Nano lignin zinc oxycarbide composite material and preparation method and application thereof |
| CN112794324A (en) * | 2019-11-14 | 2021-05-14 | 华南理工大学 | High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof |
| US11059031B2 (en) | 2017-05-11 | 2021-07-13 | South China University Of Technology | Three-dimensional lignin porous carbon/zinc oxide composite material and its preparation and application in the field of photocatalysis |
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2013
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| CN106587019A (en) * | 2016-12-16 | 2017-04-26 | 武汉工程大学 | Preparation method for lignin-based biological carbon/graphene composite nanometer material |
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| US11059031B2 (en) | 2017-05-11 | 2021-07-13 | South China University Of Technology | Three-dimensional lignin porous carbon/zinc oxide composite material and its preparation and application in the field of photocatalysis |
| CN108554458A (en) * | 2018-05-29 | 2018-09-21 | 江苏海川卓越密封材料有限公司 | Core/membranous type composite bismuth vanadium photocatalyst and preparation method thereof |
| CN108671906A (en) * | 2018-05-29 | 2018-10-19 | 江苏海川卓越密封材料有限公司 | Compound bismuth vanadate photocatalyst of high activity and preparation method thereof |
| CN108671906B (en) * | 2018-05-29 | 2020-03-31 | 江苏海川卓越密封材料有限公司 | High-activity composite bismuth vanadate photocatalyst and preparation method thereof |
| CN108554458B (en) * | 2018-05-29 | 2020-03-31 | 江苏海川卓越密封材料有限公司 | Bismuth vanadate composite photocatalyst and preparation method thereof |
| CN112794324A (en) * | 2019-11-14 | 2021-05-14 | 华南理工大学 | High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof |
| CN112794324B (en) * | 2019-11-14 | 2022-10-25 | 华南理工大学 | High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof |
| CN111675238A (en) * | 2020-08-03 | 2020-09-18 | 安徽景成新材料有限公司 | Method for preparing multi-morphology nano zinc oxide by solid phase method |
| CN112072085A (en) * | 2020-08-20 | 2020-12-11 | 华南理工大学 | Nano lignin zinc oxycarbide composite material and preparation method and application thereof |
| CN112072085B (en) * | 2020-08-20 | 2021-06-25 | 华南理工大学 | Nano lignin zinc oxycarbide composite material and preparation method and application thereof |
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