CN103303962B - Method for preparing nanometre copper oxide by solid-phase template method - Google Patents
Method for preparing nanometre copper oxide by solid-phase template method Download PDFInfo
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- CN103303962B CN103303962B CN201310224700.4A CN201310224700A CN103303962B CN 103303962 B CN103303962 B CN 103303962B CN 201310224700 A CN201310224700 A CN 201310224700A CN 103303962 B CN103303962 B CN 103303962B
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- xylogen
- amine
- deionized water
- lignin
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Abstract
The invention discloses a method for preparing nanometre copper oxide by a solid-phase template method. The method comprises the following steps of: purifying and degrading lignin at first; then synthesising lignin-amine via amination modification; and finally using the prepared lignin-amine as a template for preparing nanometre copper oxide in a solid phase. Lignin is difficult to dissolve in general solvents, therefore, the template agent is removed by a roasting method. The method disclosed by the invention is simple in synthesis process, low in cost, easily-available in raw materials, high in productivity, and less in environmental pollution; the prepared product is black, various in shape, and wide in application.
Description
Technical field
The present invention relates to a kind of method that solid phase prepares nano cupric oxide, is particularly the method that template molecule prepares nano cupric oxide with lignin amine.
Background technology
The quantity that xylogen exists at nature is quite huge, containing a large amount of xylogen in pulping and paper-making waste liquid, if do not returned
Receive and utilize, directly enter water body with black liquor, not only waste resource, and cause serious environmental pollution damage.In the technical study prepared in nano material in recent years, the utilization of mould plate technique attract attention, as long as prepare the size and shape that suitable template just can control nano material hole, the employing of new type formwork agent has greatly enriched the type of nano material.Have the features such as nontoxic, with low cost, environmental friendliness according to xylogen, the xylogen after amination modifying is mesh-structured, is that template application prospect is extensive with it.
Nano cupric oxide has unique electricity, magnetic, catalysis characteristics, is a kind of multifunctional inorganic material having broad prospect of application.The preparation of nano cupric oxide, properties and application become a study hotspot at home and abroad.Traditional chemosynthesis is carried out often in solution or gas phase.Owing to being subject to that energy consumption is high, the time is long, environmental pollution is serious and the feature impact such as complex process, and modern solid phase synthesis chemistry becomes an important research field prepared by nano material.Xylogen after the present invention's amination modifying is template, low-temperature solid-phase method synthesizing nano copper oxide, and pattern is various, is widely used.
summary of the invention
The object of the invention is to adopt lignin amine to be template, nano cupric 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.
Technical scheme of the present invention is: lignin amine template solid phase prepares the method for nano cupric oxide, is first degraded by Lignin pufification, then is synthesized lignin amine, then with prepared lignin amine for template solid phase prepares nano cupric oxide.
(1) Lignin pufification degradation step is as follows:
A, get xylogen, add deionized water, instill the mixture of concentrated hydrochloric acid and dioxane while stirring, by every 6-10g xylogen, add 30mL deionized water, 1mL concentrated hydrochloric acid and 7mL dioxane;
B, by above-mentioned solution reflux 5h at 75 DEG C of temperature, be cooled to room temperature, filter, washing precipitation is filtered;
The xylogen that C, above-mentioned steps of learning from else's experience are purified, adds dehydrated alcohol, instills concentrated hydrochloric acid while stirring, add 20-30mL dehydrated alcohol by the xylogen that every 6-10g is purified, 0.75-1.0mL concentrated hydrochloric acid;
D, by above-mentioned solution reflux 4h at 50-75 DEG C of temperature, filter, washing for several times, obtains brown fine powder, air-dry, for subsequent use.
(2) synthesis step of lignin amine is as follows:
Take the xylogen after the purification degraded prepared by certain mass step 1 under A, room temperature, add deionized water and 0.4 mol ﹒ L
-1naOH solution, after magnetic agitation 10min, add the formaldehyde of certain volume, stir 10min, add a certain amount of amine again, continue to stir 10min, the consumption of the xylogen after above-described degraded of purifying and deionized water, NaOH, formaldehyde, amine is respectively: xylogen: deionized water is for (4-8): (92-184) g/mL, xylogen: NaOH is (4-8): (5.5-11.0) g/mL, xylogen: formaldehyde is (4-8): (2.5-5) g/mL, xylogen and amine mass ratio are (4-8): (2.8-5.6) g/mL;
B, by above-mentioned solution reflux 3-5h at 60-90 DEG C of temperature, be cooled to room temperature, filter;
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 12h of thermostatic drying chamber, described loft drier temperature is 60 DEG C.
(3) reactions steps preparing nano cupric oxide for template solid phase with prepared lignin amine is as follows:
A, the mantoquita amount of substance such as getting and sodium carbonate grind 20 min respectively, transfer in same mortar, the lignin amine added prepared by step 2 continues to grind 20min in this mortar, and obtain mixture, the ratio that described mantoquita adds 0.5 ~ 3g lignin amine with lignin amine with every 0.05mol mantoquita mixes;
B, by the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water cleans 3 times, then uses washes of absolute alcohol 3 times, centrifugation;
C, by be separated after solid put into the dry 12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 60 DEG C;
D, finally by dried solid in 300-700 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 tetraethylene pentamine.
In a more excellent disclosed example of the present invention, described mantoquita is copper sulfate.
This is tested reagent used and is all analytical pure, and alkali lignin is technical grade, is commercially available.
Beneficial effect
Xylogen after the present invention utilizes degraded of purifying obtains cancellated lignin amine by Mannich reaction, and it has nontoxic, with low cost, advantages of environment protection, with it as template solid-state Synthesis cupric oxide.Because xylogen is insoluble in general solvent, therefore have employed roasting method removing template.Synthesis technique of the present invention is simple, with low cost, and raw material is easy to get, and productive rate is high, low in the pollution of the environment.The product of preparation is black, and pattern is various, is widely used.
Accompanying drawing explanation
The X ray diffracting spectrum (XRD) of Fig. 1 sample, in Fig. 1, a is the XRD figure spectrum of embodiment 1 sample, and in Fig. 1, b is the XRD figure spectrum of embodiment 3 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.
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 cupric oxide, and concrete step is poly-as follows:
1. get 10g xylogen, add 30mL deionized water, instill the mixture of 1mL concentrated hydrochloric acid and 7mL dioxane while stirring, reflux 5h at 75 DEG C of temperature, is cooled to room temperature, filters, washing precipitation is filtered, and gets 10g through the purified xylogen of above-mentioned steps, adds 30mL dehydrated alcohol, instill 0.75mL concentrated hydrochloric acid while stirring, reflux 4h at 75 DEG C of temperature, filter, washing for several times, obtain brown fine powder, air-dry, for subsequent use.
2. take the xylogen 8g after the purification degraded prepared by step 1 under room temperature, add deionized water 184mL and 0.4 mol ﹒ L
-1naOH solution 11mL, after magnetic agitation 10min, adds formaldehyde 5mL, stir 10min, then add tetraethylene pentamine 5.6mL, continue to stir 10min, solution is reflux 3h at 75 DEG C of temperature, be cooled to room temperature, filter, in filtrate, add the potassium ferricyanide solution of 10%, after precipitating completely, decompress filter, after repeatedly washing the unnecessary Tripotassium iron hexacyanide of removing, puts into 60 DEG C of dry 12h of thermostatic drying chamber with deionized water by filter cake.
3. by 0.05molCuSO
45H
2o and 0.05mol Na
2cO
3grind 20 min respectively, then transfer in same mortar, the lignin amine 1g added prepared by step 2 continues to grind 20min in this mortar, by the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water cleans 3 times, use washes of absolute alcohol again 3 times, centrifugation, by be separated after solid put into 60 DEG C of dry 12h of thermostatic drying chamber, finally by dried solid in 400 DEG C of roasting temperature 2h.Sample XRD is if Fig. 1 a, SEM are as Fig. 2 a.
embodiment 2
Lignin amine template solid phase prepares nano cupric oxide, and with embodiment 1 step, difference is in the 3rd step, finally by dried solid in 700 DEG C of roasting temperature 2h.Sample SEM is as Fig. 2 b.
embodiment 3
Lignin amine template solid phase prepares nano cupric oxide, and with embodiment 1 step, difference is in the 2nd step, takes the xylogen 4g after the purification degraded prepared by step 1, adds deionized water 92mL and 0.4 mol ﹒ L
-1naOH solution 5.5mL, the formaldehyde added is 2.5mL, and the tetraethylene pentamine added is 2.8mL.In 3rd step, finally by dried solid in 300 DEG C of roasting temperature 2h.Sample XRD is as Fig. 1 b.
embodiment 4
Lignin amine template solid phase prepares nano cupric oxide, with embodiment 1 step, difference is in the 2nd step, solution is reflux 5h at 60 DEG C of temperature, the lignin amine 0.5g added in 3rd step prepared by step 2 continue in this mortar grind 20min, finally by dried solid in 500 DEG C of roasting temperature 4h.
embodiment 5
Lignin amine template solid phase prepares nano cupric oxide, with embodiment 1 step, difference is in the 2nd step, solution is reflux 4h at 90 DEG C of temperature, the lignin amine 3g added in 3rd step prepared by step 2 continue in this mortar grind 20min, finally by dried solid in 600 DEG C of roasting temperature 3h.
embodiment 6
Lignin amine template solid phase prepares nano cupric oxide, with embodiment 1 step, the lignin amine 2g added in the 3rd step prepared by step 2 continue in this mortar grind 20min, finally by dried solid in 500 DEG C of roasting temperature 2h.
embodiment 7
1. get 6g xylogen, add 30mL deionized water, instill the mixture of 1mL concentrated hydrochloric acid and 7mL dioxane while stirring, reflux 5h at 75 DEG C of temperature, is cooled to room temperature, filters, washing precipitation is filtered, and gets 6g through the purified xylogen of above-mentioned steps, adds 20mL dehydrated alcohol, instill 1.0mL concentrated hydrochloric acid while stirring, reflux 4h at 50 DEG C of temperature, filter, washing for several times, obtain brown fine powder, air-dry, for subsequent use.
2. take the xylogen 6g after the purification degraded prepared by step 1 under room temperature, add deionized water 138mL and 0.4 mol ﹒ L
-1naOH solution 8.25mL, after magnetic agitation 10min, adds formaldehyde 3.75mL, stir 10min, then add tetraethylene pentamine 4.2mL, continue to stir 10min, solution is reflux 3h at 75 DEG C of temperature, be cooled to room temperature, filter, in filtrate, add the potassium ferricyanide solution of 10%, after precipitating completely, decompress filter, after repeatedly washing the unnecessary Tripotassium iron hexacyanide of removing, puts into 60 DEG C of dry 12h of thermostatic drying chamber with deionized water by filter cake.
3. by 0.05molCuSO
45H
2o and 0.05mol Na
2cO
3grind 20 min respectively, then transfer in same mortar, the lignin amine 1g added prepared by step 2 continues to grind 20min in this mortar, by the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water cleans 3 times, use washes of absolute alcohol again 3 times, centrifugation, by be separated after solid put into 60 DEG C of dry 12h of thermostatic drying chamber, finally by dried solid in 400 DEG C of roasting temperature 2h.
Claims (1)
1. a method for solid phase template synthesis nano cupric oxide, carry out in the steps below:
A, the mantoquita amount of substance such as getting and sodium carbonate grind 20 min respectively, transfer in same mortar, add lignin amine to continue to grind 20min in this mortar, obtain mixture, the ratio that described mantoquita adds 0.5 ~ 3g lignin amine with lignin amine with every 0.05mol mantoquita mixes;
B, by the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water cleans 3 times, then uses washes of absolute alcohol 3 times, centrifugation;
C, by be separated after solid put into the dry 12h of thermostatic drying chamber, the temperature of described thermostatic drying chamber is 60 DEG C;
D, finally by dried solid in 300-700 DEG C of roasting temperature 2-4h;
Mantoquita wherein described in steps A is copper sulfate;
Described lignin amine is prepared in the steps below:
(1) Lignin pufification degraded
A, get xylogen, add deionized water, instill the mixture of concentrated hydrochloric acid and dioxane while stirring, by every 6-10g xylogen, add 30mL deionized water, 1mL concentrated hydrochloric acid and 7mL dioxane;
B, by above-mentioned solution reflux 5h at 75 DEG C of temperature, be cooled to room temperature, filter, washing precipitation is filtered;
The xylogen that C, above-mentioned steps of learning from else's experience are purified, adds dehydrated alcohol, instills concentrated hydrochloric acid while stirring, add 20-30mL dehydrated alcohol by the xylogen that every 6-10g is purified, 0.75-1.0mL concentrated hydrochloric acid;
D, by above-mentioned solution reflux 4h at 50-75 DEG C of temperature, filter, washing for several times, obtains brown fine powder, air-dry, for subsequent use;
(2) synthesis of lignin amine
Take the xylogen after the purification degraded prepared by certain mass step 1 under A, room temperature, add deionized water and 0.4 mol ﹒ L
-1naOH solution, after magnetic agitation 10min, add the formaldehyde of certain volume, stir 10min, add a certain amount of amine again, continue to stir 10min, the consumption of the xylogen after above-described degraded of purifying and deionized water, NaOH, formaldehyde, amine is respectively: xylogen: deionized water is for (4-8): (92-184) g/mL, xylogen: NaOH is (4-8): (5.5-11.0) g/mL, xylogen: formaldehyde is (4-8): (2.5-5) g/mL, xylogen and amine mass ratio are (4-8): (2.8-5.6) g/mL;
B, by above-mentioned solution reflux 3-5h at 60-90 DEG C of temperature, be cooled to room temperature, filter;
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 12h of thermostatic drying chamber, described loft drier temperature is 60 DEG C;
Xylogen described in step (1) is alkali lignin;
Amine described in step (2) is tetraethylene pentamine.
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| 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 |
| CN111330560B (en) * | 2019-12-31 | 2023-05-16 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
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| CN103058263B (en) * | 2012-12-06 | 2014-12-03 | 江苏大学 | Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method |
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