CN103058263B - Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method - Google Patents
Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method Download PDFInfo
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- CN103058263B CN103058263B CN201210517113.XA CN201210517113A CN103058263B CN 103058263 B CN103058263 B CN 103058263B CN 201210517113 A CN201210517113 A CN 201210517113A CN 103058263 B CN103058263 B CN 103058263B
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Abstract
The invention belongs to the technical field of semiconductor photocatalysis materials, and relates to a method of preparing nanometer zinc oxide photocatalyst by using lignin amine as template molecule, especially to a method of a solid phase preparation of the nanometer zinc oxide photocatalyst by using a lignin amine template method. The method disclosed by the invention firstly synthesizes the lignin into the lignin amine, and then uses the prepared lignin amine as the template for the solid phase preparation of the nanometer zinc oxide photocatalyst. By using the lignin amine derived from the graft-modified lignin, the method is inexpensive, non-toxic, easy to get, etc. Part groups of the lignin amine can be removed after a high-temperature roasting, and pore structures are left, so that the nanometer zinc oxide photocatalyst prepared by using the lignin amine as the template is increased in specific surface area, and shows excellent photocatalysis performance. The method is easy to control, low in cost and simple in technology and flow; the lignin amine is recycled waste, and thus the method is low in cost; and prepared product is milky, has a hexagonal lead-zinc ore structure, and is good in photocatalysis effect and suitable for industrial production.
Description
Technical field
The invention belongs to conductor photocatalysis material technical field, relate to and take lignin amine and prepare the method for nano zinc oxide photocatalyst as template molecule, relate in particular to a kind of method that lignin amine template solid phase is prepared nano zinc oxide photocatalyst.
Background technology
Nano zine oxide (ZnO) is as a kind of new and effective conductor photocatalysis functional materials, aspect organic pollutant degradation, show very high quantum yield, the even mineralising of the toxic organic pollutant of some bio-refractory effectively can being degraded at normal temperatures and pressures, and it is with low cost, product non-secondary pollution, in photocatalysis field, shown fabulous application prospect.
Solid state reaction legal system, for nano-ZnO, is compared compared with vapor phase process, liquid phase method, and without solvent, technique is simple, with low cost, react controlled, and transformation efficiency is high, and energy consumption is lower, of reduced contamination, and powder granule is reunited less, output is larger.These features meet the requirement of society Green Chemistry development, aspect nano material synthetic, have shown larger advantage, just progressively develop into a little subbranch in synthetic field.
In the preparation of solid phase method porous material, conventional polyoxyethylene glycol, dodecyl alcohol, Triton X-100 etc. are as dispersion agent and the template of pioneer precipitate.Lignin amine is the preparation field at solid phase method nano inorganic material as template, there is not yet report.Xylogen is natural high moleculer eompound, is the main component of black liquid, and the comprehensive utilization of xylogen is the committed step of administration of papermaking black liquid.Derive from the lignin amine of xylogen graft modification, have inexpensive, nontoxic, the advantage such as be easy to get, the nano zinc oxide photocatalyst that uses in the present invention lignin amine to make as template has shown excellent photocatalysis performance.
Summary of the invention
The object of the invention is to adopt lignin amine is template, by solid phase method and through differing temps, calcines to prepare nano zinc oxide photocatalyst, and technique is simple, and raw material is easy to obtain, with low cost, is conducive to suitability for industrialized production.
Technical scheme of the present invention is: a kind of lignin amine template solid phase is prepared the method for nano zinc oxide photocatalyst, first xylogen is synthesized to lignin amine, and the prepared lignin amine of then take is prepared nano zinc oxide photocatalyst as template solid phase.
In a more excellent open example of the present invention, the synthesis step of described lignin amine is as follows:
Under A, room temperature, take the xylogen of certain mass, add deionized water and NaOH, after magnetic agitation 10-20min, the formaldehyde that adds certain volume, stir 10-20min, the amine that adds again certain volume, continues to stir 10-20min, described xylogen: deionized water: NaOH: formaldehyde: the ratio of amine is 4-10g:30-60ml:0.5-1.0g:0.5-2.5 mL:1.5-4.8mL;
B, 3-5h that above-mentioned solution is refluxed at 60-90 ℃ of temperature, be cooled to room temperature, filters;
C, in filtrate, add 10% potassium ferricyanide solution, after precipitating completely, decompress filter, repeatedly washs and removes after the unnecessary Tripotassium iron hexacyanide with deionized water, and filter cake is put into the dry 10-12h of thermostatic drying chamber, and described loft drier temperature is 50-60 ℃.
In a more excellent open example of the present invention, described to take the reactions steps that prepared lignin amine prepares nano zinc oxide photocatalyst as template solid phase as follows:
A, solid-state zinc salt and the sodium oxalate of the amount of substance such as getting grind respectively 10-20 min, transfer in same mortar, add the lignin amine of above-mentioned preparation in this mortar, to continue to grind 20-30min, obtain paste mixture, described zinc salt mixes with 0.1mol:1 ~ 3g ratio with lignin amine;
B, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, dehydrated alcohol cleans 2-3 time for precipitation, then uses washed with de-ionized water 3-5 time, centrifugation;
C, the solid after separation is put into the dry 10-12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 50-60 ℃;
D, finally by dried solid in 300-600 ℃ of roasting temperature 2-3h.
In a more excellent open example of the present invention, described xylogen is alkali lignin.
In a more excellent open example of the present invention, described amine is ethylene diamine, diethylenetriamine, any in triethylene tetramine, tetraethylene pentamine, hexanediamine.
In a more excellent open example of the present invention, described zinc salt is zinc nitrate.
The nano zinc oxide photocatalyst preparing according to the method disclosed in the present, median size is 18 ~ 60nm, the plumbous zinc ore structure of hexagonal system.
The nano zinc oxide photocatalyst preparing according to the method disclosed in the present, is applied to the processing of various dyeing waste waters, and energy exhaustive oxidation degraded organic pollutants has a good application prospect in processing organic wastewater.
This is tested reagent used and is all analytical pure, and alkali lignin (rugose wood element) is technical grade, is commercially available.
photocatalytic degradation experiment:
Preparation 1L 20mgL
-1methyl orange solution, getting the nano-ZnO photocatalyst that 0.1g makes adds wherein, supersound process 30min mixes it, be placed in SGY-1 multifunctional light chemical reaction instrument (Nanjing Si Dongke Electric Appliance Equipment Co., Ltd, UV-light predominant wavelength 365nm) in, unglazed whip attachment 20min reaches physical adsorption and desorption balance, open subsequently light source and carry out light-catalyzed reaction, reaction times 1h, every 10min, sample, sampling sample is carried out to high speed centrifugation separation, with 7220 spectrophotometers (Beijing Rayleigh Analytical Instrument Co.,Ltd), at 463nm place, measure the absorbancy of the upper strata stillness of night, according to the variation of absorbance, try to achieve the degradation rate of tropeolin-D.
Degradation rate: α=(A
0-A)/A
0* 100%
A wherein
0the initial absorbance of dye solution adsorption equilibrium, the absorbancy of dye solution after A degraded.
beneficial effect
The present invention adopts the lignin amine derive from xylogen graft modification, has inexpensive, nontoxic, the advantage such as be easy to get, and using it as template, in the preparation field of solid phase method nano inorganic material, there is not yet report.After high-temperature roasting, the part group of lignin amine is removed, and leaves pore texture, and the nano zinc oxide photocatalyst specific surface area being made as template by lignin amine is increased, and demonstrates excellent photocatalysis performance.This technique has the control of being easy to, and cost is low, the advantage of technique and simple flow, and the nano zinc oxide photocatalysis of preparation is effective, is applicable to suitability for industrialized production.
Accompanying drawing explanation
The X ray diffracting spectrum of Fig. 1 sample (XRD).
The scanning electron microscope (SEM) photograph of Fig. 2 sample (SEM), wherein, a is the scanning electron microscope (SEM) photograph of 400 ℃ of embodiment 2 sample calcinings; B is the scanning electron microscope (SEM) photograph of 500 ℃ of embodiment 3 sample calcinings; C is the scanning electron microscope (SEM) photograph of 600 ℃ of embodiment 4 sample calcinings.
The photocatalysis effect figure of Fig. 3 sample, is respectively pure zinc oxide prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, the lignin amine that undopes and the photocatalysis effect figure that does not add catalyzer.
embodiment
Below in conjunction with concrete embodiment, the present invention will be further described, 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 is prepared nano zinc oxide photocatalyst, and concrete step is poly-as follows:
1. the alkali lignin 5g that gets the degraded of purifying under room temperature is placed in 250mL round-bottomed flask, the NaOH that adds 30mL deionized water and 0.5g, stir 10min, the formaldehyde that adds 1.2 mL, stir 10min, the tetraethylene pentamine that adds again 1.50mL, stir 10min, at 75 ℃, reflux 3h, is cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, the lignin amine of preparation is precipitated completely, 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. by 14.87g Zn (NO
3)
26H
2o and 6.70gNaC
2o
4in different mortars, grind respectively 15 min, then the two is transferred in same mortar, add wherein again the lignin amine of 1.0g step 1 synthesized to grind together 20min, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, precipitation is cleaned 3 times with dehydrated alcohol, then uses washed with de-ionized water 3 times, centrifugation; After separation, solid is put into 60 ℃ of dry 10h of thermostatic drying chamber; Then by sample roasting 3h at 300 ℃, obtain oyster white nano zinc oxide photocatalyst, median size 60nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 68%.
embodiment 2
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is that amine used is triethylene tetramine, finally, by sample roasting 3h at 400 ℃, obtain oyster white nano zinc oxide photocatalyst, median size 34nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 81%.
embodiment 3
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is finally by sample roasting 2h at 500 ℃, obtain white nano zinc oxide photocatalyst, median size 18nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 96%.
embodiment 4
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is that amine used is diethylenetriamine, and the amount that adds formaldehyde is 0.5mL, finally by sample roasting 2h at 600 ℃, obtain white nano zinc oxide photocatalyst, median size 50nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 74%.
embodiment 5
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is to add 0.5g lignin amine in the 2nd step, finally, by sample roasting 2h at 500 ℃, obtain white nano zinc oxide photocatalyst, median size 30nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 84%.
embodiment 6
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is to get raw alkaline lignin 5g in the 1st step, and amine used is triethylene tetramine, in the 2nd step, add 3g lignin amine, finally, by sample roasting 2h at 500 ℃, obtain white nano zinc oxide photocatalyst, median size 40nm, gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 77%.
embodiment 7
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is in the 1st step, to get raw alkaline lignin 4g to be placed in 250mL round-bottomed flask, the NaOH that adds 30mL water and 0.5g, at room temperature stir 20min, the formaldehyde that adds 1.5 mL, at room temperature stir 20min, the hexanediamine that adds again 4.8mL, at room temperature stir 10min, reflux 3h at 65 ℃, be cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, the lignin amine of preparation is precipitated completely, decompress filter, repeatedly the unnecessary Tripotassium iron hexacyanide is removed in washing, filter cake is put into 50 ℃ of dry 10h of thermostatic drying chamber.The 2nd step is with embodiment 1, and difference is by sample roasting 3h at 500 ℃, obtains white nano zinc oxide photocatalyst, median size 23nm, and gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 94%.
embodiment 8
Lignin amine template solid phase is prepared nano zinc oxide photocatalyst, with embodiment 1 step, difference is in the 1st step, to get raw alkaline lignin 10g to be placed in 250mL round-bottomed flask, the NaOH that adds 60mL water and 1.0g, at room temperature stir 20min, the formaldehyde that adds 2.5 mL, at room temperature stir 10min, the tetraethylene pentamine that adds again 4.8mL, at room temperature stir 20min, reflux 5h at 90 ℃, be cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, the lignin amine of preparation is precipitated completely, decompress filter, repeatedly the unnecessary Tripotassium iron hexacyanide is removed in washing, filter cake is put into 50 ℃ of dry 12h of thermostatic drying chamber.The 2nd step is with example 1, and difference is by sample roasting 3h at 500 ℃, obtains white nano zinc oxide photocatalyst, median size 39nm, and gained sample carries out photocatalytic degradation test, take tropeolin-D as model, illumination 60min, degradation rate 80%.
Claims (4)
1. lignin amine template solid phase is prepared a method for nano zinc oxide photocatalyst, first xylogen is synthesized to lignin amine, and the prepared lignin amine of then take is prepared nano zinc oxide photocatalyst as template solid phase, it is characterized in that:
The synthesis step of described lignin amine is as follows:
Under A, room temperature, take the xylogen of certain mass, add deionized water and NaOH, after magnetic agitation 10-20min, the formaldehyde that adds certain volume, stir 10-20min, then add the amine of certain volume, continue to stir 10-20min, described xylogen: deionized water: NaOH: formaldehyde: the ratio of amine is 4-10g:30-60mL:0.5-1.0g:0.5-2.5 mL:1.5-4.8mL
B, 3-5h that above-mentioned solution is refluxed at 60-90 ℃ of temperature, be cooled to room temperature, filter,
C, in filtrate, add 10% potassium ferricyanide solution, after precipitating completely, decompress filter, repeatedly washs and removes after the unnecessary Tripotassium iron hexacyanide with deionized water, and filter cake is put into the dry 10-12h of thermostatic drying chamber, and described loft drier temperature is 50-60 ℃;
It is described that to take the reactions steps that prepared lignin amine prepares nano zinc oxide photocatalyst as template solid phase as follows:
A, solid-state zinc salt and the sodium oxalate of the amount of substance such as getting grind respectively 10-20 min, transfer in same mortar, add the lignin amine of above-mentioned preparation in this mortar, to continue to grind 20-30min, obtain paste mixture, described zinc salt mixes with 0.1mol:1 ~ 3g ratio with lignin amine
B, by the deionized water ultrasonic cleaning of gained paste mixture, centrifugation, dehydrated alcohol cleans 2-3 time for precipitation, then uses washed with de-ionized water 3-5 time, centrifugation,
C, the solid after separation is put into the dry 10-12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 50-60 ℃,
D, finally by dried solid in 300-600 ℃ of roasting temperature 2-3h.
2. lignin amine template solid phase according to claim 1 is prepared the method for nano zinc oxide photocatalyst, it is characterized in that, described xylogen is alkali lignin.
3. lignin amine template solid phase according to claim 1 is prepared the method for nano zinc oxide photocatalyst, it is characterized in that, described amine is ethylene diamine, diethylenetriamine, any in triethylene tetramine, tetraethylene pentamine, hexanediamine.
4. lignin amine template solid phase according to claim 1 is prepared the method for nano zinc oxide photocatalyst, it is characterized in that, described zinc salt is zinc nitrate.
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| CN103303962B (en) * | 2013-06-05 | 2015-04-22 | 江苏大学 | Method for preparing nanometre copper oxide by solid-phase template method |
| 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 |
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| 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 |
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