CN103183372B - A kind of template solid phase prepares the method for nano zine oxide - Google Patents
A kind of template solid phase prepares the method for nano zine oxide Download PDFInfo
- Publication number
- CN103183372B CN103183372B CN201310117783.7A CN201310117783A CN103183372B CN 103183372 B CN103183372 B CN 103183372B CN 201310117783 A CN201310117783 A CN 201310117783A CN 103183372 B CN103183372 B CN 103183372B
- Authority
- CN
- China
- Prior art keywords
- amine
- zine oxide
- lignin
- nano zine
- lignin amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of method that template solid phase prepares nano zine oxide, relates to the method that solid phase prepares nano zine oxide, and step is: be first lignin amine by lignin synthesis, then with prepared lignin amine for template solid phase prepares nano zine oxide.Xylogen is utilized to obtain cancellated lignin amine by Mannich reaction, its have inexpensive, nontoxic, the advantage such as be easy to get, after high-temperature roasting, the moieties of lignin amine is removed, leaving pore gap structure, making to make the obtained nano zine oxide specific surface area of template by lignin amine increases.Synthesis technique of the present invention is simple, uniform particle sizes, and dynamics is controlled, reduces hard aggregation phenomenon, and cost is low, easy to operate, high yield, pollution are few.The product of preparation is oyster white, hexagonal system Pb-Zn deposits structure, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of method that solid phase prepares nano zine oxide, is particularly the method that template molecule prepares nano zine oxide with lignin amine.
Background technology
Xylogen has the features such as nontoxic, with low cost, environmental friendliness, effectively utilizes xylogen not only can save natural resources, and is conducive to protection of the environment.The comprehensive utilization of xylogen is the key of straw pulp black liquor resource type treating.In the preparation method of nano material, template can control particle diameter, the pattern of nano material better, realizes nano material synthesis and being assembled into one, can solve the stably dispersing sex chromosome mosaicism of nano material simultaneously, and building-up process is relatively simple, a lot of method is applicable to batch production.Template mainly contains the colloidal crystal etc. that various types of tensio-active agent, segmented copolymer, on-surface-active organic molecule, microemulsion emulsion droplets and polymer microballoon are formed, the lignin amine formed after lignin modification is mesh-structured, has no report with its pertinent literature as template nano materials.
Nano zine oxide (ZnO) crystal due to its energy gap large, exciton binding energy is high, 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 large, has the features such as obvious surface and interface effect, shows physicals and the chemical property of many uniquenesses in chemistry, optics, biology and electricity etc.In recent years, along with industrial expansion and progress, day by day increase the demand of zinc oxide, the photoluminescence of research nano zine oxide can deeply to the understanding of nano zine oxide, and people pay close attention to its research more.
Solid state reaction legal system is for nano-ZnO, and comparatively vapor phase process, liquid phase method are compared, and synthesis technique is simple, uniform particle sizes, and dynamics is controlled, reduces hard aggregation phenomenon, and cost is low, easy to operate, high yield, pollution are few.These features meet the requirement of society green chemistry, in the synthesis of nano material, show larger advantage, just progressively develop into a little subbranch in synthesis field.In the present invention, the fluorescence property that lignin amine is excellent for template solid-state Synthesis zinc oxide shows is used.
Summary of the invention
The object of the invention is to adopt lignin amine to be template, nano zine oxide is prepared in calcining by Solid phase synthesis and under differing temps, and technique is simple, and raw material is easy to obtain, with low cost, of reduced contamination, is suitable for suitability for industrialized production.
Technical scheme of the present invention is: a kind of lignin amine template solid phase prepares the method for nano zine oxide, is first lignin amine by lignin synthesis, then with prepared lignin amine for template solid phase prepares nano zine oxide.
(1) synthesis step of lignin amine is as follows:
Take the xylogen of certain mass under A, room temperature, add deionized water and 0.4 mol ﹒ L
-1naOH solution, after magnetic agitation 10-20min, add the formaldehyde of certain volume, stir 10-20min, then add a certain amount of amine, 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, xylogen: formaldehyde is (4-8): (0.5-2.5) g/mL, and xylogen and amine mass ratio are (4-8): (2.6-7.0);
B, reflux above-mentioned solution at 65-95 DEG C of temperature 3-5h, is cooled to room temperature, filters;
C, add in filtrate 10% potassium ferricyanide solution, after precipitating completely, decompress filter, after repeatedly washing the unnecessary Tripotassium iron hexacyanide of removing with deionized water, filter cake is put into the dry 10-12h of thermostatic drying chamber, described loft drier temperature is 50-60 DEG C.
(2) reactions steps preparing nano zine oxide for template solid phase with prepared lignin amine is as follows:
A, the solid-state zinc salt amount of substance such as getting and sodium carbonate grind 10-20 min respectively, transfer in same mortar, the lignin amine adding above-mentioned preparation continues to grind 20-30min in this mortar, obtain paste mixture, the ratio that described zinc salt adds 1 ~ 3g lignin amine with lignin amine with 0.05mol zinc salt mixes;
B, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitate with deionized water cleaning 2-3 time, then uses washes of absolute alcohol 3-5 time, centrifugation;
C, by be separated after solid put into the dry 10-12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 50-60 DEG C;
D, finally by dried solid in 300-600 DEG C of roasting temperature 2-4h.
In a more excellent disclosed example of the present invention, described xylogen is alkali lignin.
In a more excellent disclosed example of the present invention, described amine is ethylene diamine, diethylenetriamine, any one in triethylene tetramine, tetraethylene pentamine, hexanediamine.
In a more excellent disclosed 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, hexagonal system Pb-Zn deposits structure.
This is tested reagent used and is all analytical pure, and alkali lignin is technical grade, is commercially available.
beneficial effect
The present invention utilizes xylogen to obtain cancellated lignin amine by Mannich reaction, its have inexpensive, nontoxic, the advantage such as be easy to get, after high-temperature roasting, the moieties of lignin amine is removed, leaving pore gap structure, making to make the obtained nano zine oxide specific surface area of template by lignin amine increases.Synthesis technique of the present invention is simple, uniform particle sizes, and dynamics is controlled, reduces hard aggregation phenomenon, and cost is low, easy to operate, high yield, pollution are few.The product of preparation is oyster white, hexagonal system Pb-Zn deposits structure, is applicable to suitability for industrialized production.
Accompanying drawing explanation
The X ray diffracting spectrum (XRD) of Fig. 1 sample, in figure, a is the XRD figure spectrum of embodiment 1 sample, and in figure, b is the XRD figure spectrum of embodiment 2 sample, and in figure, c is the XRD figure spectrum of embodiment 3 sample, and in figure, d is the XRD figure spectrum of embodiment 7 sample.
The scanning electron microscope (SEM) photograph (SEM) of Fig. 2 sample, wherein, a is the scanning electron microscope (SEM) photograph of embodiment 1 sample; B is the scanning electron microscope (SEM) photograph of embodiment 2 sample; C is the scanning electron microscope (SEM) photograph of embodiment 3 sample.
The fluorescence spectrum (PL) of Fig. 3 sample, wherein a is the PL figure of embodiment 1 sample, and excitation wavelength is 280nm; B is the PL figure of embodiment 3 sample, and excitation wavelength is 280nm; C is the PL figure of embodiment 7 sample, and excitation wavelength is 280nm.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described, and to make 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 prepares nano zinc oxide photocatalyst, and concrete step is poly-as follows:
1. get alkali lignin 4g under room temperature and be placed in 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, then add 4.8g hexanediamine, stir 10min, reflux 3h at 65 DEG C, be cooled to room temperature, filter, in filtrate, add the potassium ferricyanide solution of 10%, the lignin amine of preparation is precipitated completely, decompress filter, the Tripotassium iron hexacyanide that repeatedly washing removing is unnecessary, puts into thermostatic drying chamber 60 DEG C of dry 10h by filter cake;
2. by 0.05mol Zn (NO
3)
26H2O and 0.05molNa
2cO
315 min are ground respectively in different mortar, then the two is transferred in same mortar, the lignin amine added wherein synthesized by 1.0g step 1 grinds 20min together again, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitation washes of absolute alcohol 3 times, then use washed with de-ionized water 3 times, centrifugation; After separation, solid is put into thermostatic drying chamber 60 DEG C of dry 10h; Then by sample roasting 2h at 300 DEG C, oyster white nano zine oxide is namely obtained.Sample XRD is if Fig. 1 a, SEM are if Fig. 2 a, PL are as Fig. 3 a.
embodiment 2
Lignin amine template solid phase prepares nano zine oxide, with embodiment 1 step, difference is the formaldehyde added in the 1st step is 2.5mL, and amine used is tetraethylene pentamine 3.2g, last by sample roasting 2h at 400 DEG C in 2nd step, namely obtain white nano zine oxide.Sample XRD is if Fig. 1 b, SEM are as Fig. 2 b.
embodiment 3
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference is last by sample roasting 2h at 600 DEG C in the 2nd step, obtains white nano zine oxide.Sample XRD is if Fig. 1 c, SEM are if Fig. 2 c, PL are as Fig. 3 b.
embodiment 4
Lignin amine template solid phase prepares nano zine oxide, with embodiment 1 step, difference in the 1st step, filter cake is put into thermostatic drying chamber 50 DEG C of dry 12h, and the synthesized lignin amine added in the 2nd step is 3g, finally by sample roasting 2h at 400 DEG C, obtain white nano zine oxide.
embodiment 5
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference is the formaldehyde added in the 1st step is 2.5mL, and amine used is triethylene tetramine 3.2g, 0.05mol Zn (NO in the 2nd step
3)
26H2O and 0.05molNa
2cO
320 min are ground respectively in different mortar, then the two is transferred in same mortar, the lignin amine added wherein synthesized by 1.0g step 1 grinds 30min together again, after separation, solid is put into thermostatic drying chamber 50 DEG C of dry 12h, finally by sample roasting 2h at 600 DEG C, obtain white nano zine oxide.
embodiment 6
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference adds alkali lignin 8g, deionized water 190mL, NaOH solution 10mL, hexanediamine 7g, reflux 5h at 95 DEG C in the 1st step; 0.05mol Zn (NO in 2nd step
3)
26H2O and 0.05molNa
2cO
3in different mortar, grind 10 min respectively finally by sample roasting 3h at 500 DEG C, obtain white nano zine oxide.
embodiment 7
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference is last by sample roasting 3h at 400 DEG C, obtains white nano zine oxide.Sample XRD is if Fig. 1 d, PL are as Fig. 3 c.
embodiment 8
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference is the alkali lignin added in the 1st step is 8g, deionized water 190mL, 0.4 mol ﹒ L
-1naOH solution be 10mL, formaldehyde is 2.5mL, and hexanediamine used is amine is 7g, condensing reflux 5 hours, last by sample roasting 4h at 600 DEG C in the 2nd step, obtains white nano zine oxide.
embodiment 9
Lignin amine template solid phase prepares nano zine oxide, and with embodiment 1 step, difference is the formaldehyde added in the 1st step is 0.5mL, and hexanediamine used is 2.6g, last by sample roasting 2h at 400 DEG C in the 2nd step, obtains white nano zine oxide.
Claims (1)
1. lignin amine template solid phase prepares a method for nano zine oxide, carries out in the steps below:
(1) synthesis step of lignin amine is as follows:
Take the xylogen of certain mass under A, room temperature, add deionized water and 0.4 mol ﹒ L
-1naOH solution, after magnetic agitation 10-20min, add the formaldehyde of certain volume, stir 10-20min, then add a certain amount of amine, 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, xylogen: formaldehyde is (4-8): (0.5-2.5) g/mL, and xylogen and amine mass ratio are (4-8): (2.6-7.0);
B, reflux above-mentioned solution at 65-95 DEG C of temperature 3-5h, is cooled to room temperature, filters;
C, add in filtrate 10% potassium ferricyanide solution, after precipitating completely, decompress filter, after repeatedly washing the unnecessary Tripotassium iron hexacyanide of removing with deionized water, filter cake is put into the dry 10-12h of thermostatic drying chamber, described loft drier temperature is 50-60 DEG C;
(2) reactions steps preparing nano zine oxide for template solid phase with prepared lignin amine is as follows:
A, the solid-state zinc salt amount of substance such as getting and sodium carbonate grind 10-20 min respectively, transfer in same mortar, the lignin amine adding above-mentioned preparation continues to grind 20-30min in this mortar, obtain paste mixture, the ratio that described zinc salt adds 1 ~ 3g lignin amine with lignin amine with 0.05mol zinc salt mixes;
B, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitate with deionized water cleaning 2-3 time, then uses washes of absolute alcohol 3-5 time, centrifugation;
C, by be separated after solid put into the dry 10-12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 50-60 DEG C;
D, finally by dried solid in 300-600 DEG C of roasting temperature 2-4h;
Xylogen described in step (1) is alkali lignin;
Amine described in step (1) is ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or hexanediamine;
Zinc salt described in step (2) is zinc nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310117783.7A CN103183372B (en) | 2013-04-07 | 2013-04-07 | A kind of template solid phase prepares the method for nano zine oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310117783.7A CN103183372B (en) | 2013-04-07 | 2013-04-07 | A kind of template solid phase prepares the method for nano zine oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183372A CN103183372A (en) | 2013-07-03 |
| CN103183372B true CN103183372B (en) | 2015-08-05 |
Family
ID=48674863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310117783.7A Expired - Fee Related CN103183372B (en) | 2013-04-07 | 2013-04-07 | A kind of template solid phase prepares the method for nano zine oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103183372B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587019B (en) * | 2016-12-16 | 2018-07-17 | 武汉工程大学 | A kind of preparation method of lignin-base biological carbon/graphene composite nano material |
| CN107282030B (en) | 2017-05-11 | 2019-12-10 | 华南理工大学 | Three-dimensional lignin porous carbon/zinc oxide composite material, preparation thereof and application thereof in photocatalysis field |
| 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 |
| 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 |
| 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 |
-
2013
- 2013-04-07 CN CN201310117783.7A patent/CN103183372B/en not_active Expired - Fee Related
Non-Patent Citations (5)
| Title |
|---|
| 二乙烯三胺/甲醛改性木质素胺的制备及应用性能;刘祖广等;《中国造纸学报纸》;20051231;第75-79页 * |
| 以木质素基磷酸酯季铵盐为模板剂直接沉淀法制备纳米氧化锌的研究;余方丹等;《纳米科技》;20111031;第14页第1.2节 * |
| 木质素的胺化改性;王晓红等;《中国造纸》;20101203;第43页第1.2-1.4节 * |
| 白青龙等.木质素为模板合成多孔材料.《内蒙古民族大学学报(自然科学版)》.2005,第510-512页. * |
| 纳米氧化锌的固相合成;黄志明等;《纳米氧化锌的固相合成》;20031231;第35页第1.1-1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103183372A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103183372B (en) | A kind of template solid phase prepares the method for nano zine oxide | |
| CN102897724B (en) | Tin selenide nano-flowers and preparation method thereof | |
| CN106732668A (en) | A kind of hydrothermal preparing process of flower-shaped molybdenum bisuphide/cupric oxide composite nano materials | |
| CN102923791B (en) | Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method | |
| CN103523824B (en) | The preparation method of nano-sheet ferroelectric material for a kind of photocatalysis | |
| CN101613121A (en) | A kind of preparation method of ellipsoid-shaped zinc oxide | |
| CN103991896A (en) | Spherical zinc oxide nanometer material preparation method | |
| CN105727925A (en) | Preparation and application of porous structure ZnO/ZnGa2O4 visible-light-induced photocatalyst with high specific surface area | |
| CN107649153A (en) | A kind of method that solvent-thermal method prepares BiOCl photochemical catalysts | |
| CN103058263B (en) | Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method | |
| CN110203976A (en) | Rapid synthesis flakes ZnCo2O4The preparation method of-ZnO compound electric grade material | |
| CN103274441A (en) | Method for preparing nanoscale sheet cerium oxide by hydrothermal method | |
| CN108675339A (en) | A kind of preparation method of the glomerate zinc cadmium sulphur solid-solution material of rodlike self assembly | |
| CN105731518B (en) | Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN106830024B (en) | A kind of red mud prepares hydro-thermal-thermal conversion process of active boehmite and aluminum oxide porous microballoon for raw material | |
| CN106517299B (en) | A kind of sheet self assembly basic copper carbonate bouquet and its simple method for preparing | |
| CN105271443A (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN103303962B (en) | Method for preparing nanometre copper oxide by solid-phase template method | |
| CN103570031A (en) | Method for preparing BaCuSi2O6 and BaCu2Si2O7 pigments through hydrothermal technology | |
| CN102275973A (en) | Preparation method of basic copper carbonate microspheres | |
| CN103771492B (en) | Simple preparation method of flaky zinc oxide nano material | |
| CN102627316A (en) | Preparation method for SnO2 three-dimensional hollow sphere nano material | |
| CN102259872B (en) | Method for preparing white carbon black by utilizing vanadium ore waste residue | |
| CN107381618A (en) | A kind of preparation method of club shaped structure nano zine oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150805 Termination date: 20160407 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |