CN103303962A - 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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- CN103303962A CN103303962A CN2013102247004A CN201310224700A CN103303962A CN 103303962 A CN103303962 A CN 103303962A CN 2013102247004 A CN2013102247004 A CN 2013102247004A CN 201310224700 A CN201310224700 A CN 201310224700A CN 103303962 A CN103303962 A CN 103303962A
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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 the method that a kind of solid phase prepares nano cupric oxide, particularly prepare the method for nano cupric oxide take lignin amine as template molecule.
Background technology
Xylogen is quite huge in the quantity that nature exists, and contains a large amount of xylogen in the pulping and paper-making waste liquid, as 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 of nano material preparation, the utilization of mould plate technique has caused people's attention in recent years, as long as the suitable template of preparation just can be controlled the size and shape in nano material hole, the employing of new type formwork agent has greatly enriched the type of nano material.Have the characteristics such as nontoxic, with low cost, environmental friendliness according to xylogen, the xylogen behind the amination modifying is mesh-structured, is that the template application prospect is extensive with it.
Nano cupric oxide has unique electricity, magnetic, catalysis characteristics, is a kind of multifunctional inorganic material that has broad prospect of application.The preparation of nano cupric oxide, performance and be applied in and become a study hotspot both at home and abroad.Traditional chemosynthesis is carried out in solution or gas phase often.Because be subject to that energy consumption is high, the time is long, environmental pollution is serious and the characteristics impact such as complex process, modern solid phase synthesis chemistry becomes an important research field of nano material preparation.The xylogen of the present invention after with amination modifying is template, the low-temperature solid-phase method synthesizing nano copper oxide, and pattern is various, is widely used.
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 cupric oxide, and technique is simple, and raw material is easy to obtain, and is 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, and the degraded of first xylogen being purified synthesizes lignin amine with it again, then prepares nano cupric oxide take prepared lignin amine as the template solid phase.
(1) xylogen purification degradation step is as follows:
A, get xylogen, add deionized water, splash into while stirring the mixture of concentrated hydrochloric acid and dioxane, by every 6-10g xylogen, add 30mL deionized water, 1mL concentrated hydrochloric acid and 7mL dioxane;
B, with mentioned solution reflux 5h under 75 ℃ of temperature, be cooled to room temperature, filter, washing precipitation is filtered;
The xylogen that C, the above-mentioned steps of learning from else's experience were purified adds dehydrated alcohol, splashes into while stirring concentrated hydrochloric acid, and the xylogen of purifying by every 6-10g adds 20-30mL dehydrated alcohol, 0.75-1.0mL concentrated hydrochloric acid;
D, with mentioned solution reflux 4h under 50-75 ℃ of temperature, filter, washing gets the brown fine powder for several times, and is air-dry, for subsequent use.
(2) synthesis step of lignin amine is as follows:
Take by weighing the xylogen after the prepared purification of certain mass step 1 is degraded under A, the room temperature, add deionized water and 0.4 mol ﹒ L
-1NaOH solution, behind the magnetic agitation 10min, the formaldehyde that adds certain volume, stir 10min, add again a certain amount of amine, continue to stir 10min, the consumption of the xylogen after the above-described purification degraded and deionized water, NaOH, formaldehyde, amine is respectively: xylogen: deionized water is (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, and xylogen and amine mass ratio are (4-8): (2.8-5.6) g/mL;
B, with mentioned solution reflux 3-5h under 60-90 ℃ of temperature, be cooled to room temperature, filter;
C, in filtrate, add 10% potassium ferricyanide solution, after precipitating fully, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into the dry 12h of thermostatic drying chamber, described loft drier temperature is 60 ℃.
(3) as follows take prepared lignin amine as the reactions steps that the template solid phase prepares nano cupric oxide:
A, the mantoquita of getting Isoequivalent weight and yellow soda ash grind respectively 20 min, transfer in the same mortar, add the prepared lignin amine of step 2 and continue to grind 20min in this mortar, get mixture, described mantoquita mixes with the ratio that every 0.05mol mantoquita adds 0.5 ~ 3g lignin amine with lignin amine;
B, with the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water is cleaned 3 times, cleans 3 times centrifugation with dehydrated alcohol again;
C, the solid after will separating are put into the dry 12h of thermostatic drying chamber, and the temperature of described thermostatic drying chamber is 60 ℃;
D, at last with dried solid in 300-700 ℃ 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 tetraethylene pentamine.
In the more excellent open example of the present invention, described mantoquita is copper sulfate.
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 the xylogen after the degraded of purifying to make 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 adopted roasting method to remove template.Synthesis technique of the present invention is simple, and is with low cost, and raw material is easy to get, and productive rate is high, and is low in the pollution of the environment.The product of preparation is black, and pattern is various, is widely used.
Description of drawings
The X ray diffracting spectrum of Fig. 1 sample (XRD), a is the XRD figure spectrum of embodiment 1 sample among Fig. 1, b is the XRD figure spectrum of embodiment 3 samples among Fig. 1.
The scanning electron microscope (SEM) photograph of Fig. 2 sample (SEM), wherein, a is the scanning electron microscope (SEM) photograph of embodiment 1 sample; B is the scanning electron microscope (SEM) photograph of embodiment 2 samples.
Embodiment
The present invention will be further described below in conjunction with the implementation example, 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 prepares nano cupric oxide, and the concrete step is poly-as follows:
1. get the 10g xylogen, add the 30mL deionized water, splash into while stirring the mixture of 1mL concentrated hydrochloric acid and 7mL dioxane, reflux 5h under 75 ℃ of temperature is cooled to room temperature, filters, washing precipitation is filtered, and gets the xylogen that 10g purified through above-mentioned steps, adds the 30mL dehydrated alcohol, splash into while stirring the 0.75mL concentrated hydrochloric acid, reflux 4h under 75 ℃ of temperature filters, washing for several times, get the brown fine powder, air-dry, for subsequent use.
2. take by weighing the xylogen 8g after the prepared purification of step 1 is degraded under the room temperature, add deionized water 184mL and 0.4 mol ﹒ L
-1NaOH solution 11mL behind the magnetic agitation 10min, adds formaldehyde 5mL, stir 10min, add again tetraethylene pentamine 5.6mL, continue to stir 10min, solution is reflux 3h under 75 ℃ of temperature, be cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, after precipitating fully, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into 60 ℃ of dry 12h of thermostatic drying chamber.
3. with 0.05molCuSO
45H
2O and 0.05mol Na
2CO
3Grind respectively 20 min, then transfer in the same mortar, add the prepared lignin amine 1g of step 2 and in this mortar, continue to grind 20min, with the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water is cleaned 3 times, clean 3 times with dehydrated alcohol again, centrifugation is put into 60 ℃ of dry 12h of thermostatic drying chamber with the solid after separating, at last with dried solid in 400 ℃ of roasting temperature 2h.Sample XRD such as Fig. 1 a, SEM such as Fig. 2 a.
Embodiment 2
Lignin amine template solid phase prepares nano cupric oxide, with embodiment 1 step, difference be the 3rd the step in, at last with dried solid in 700 ℃ of roasting temperature 2h.Sample SEM such 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 by weighing the xylogen 4g after the prepared purification of step 1 is degraded, and adds deionized water 92mL and 0.4 mol ﹒ L
-1NaOH solution 5.5mL, the formaldehyde of adding are 2.5mL, and the tetraethylene pentamine of adding is 2.8mL.The 3rd the step in, at last with dried solid in 300 ℃ of roasting temperature 2h.Sample XRD such 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 under 60 ℃ of temperature, add the prepared lignin amine 0.5g of step 2 in the 3rd step and in this mortar, continue grinding 20min, at last with dried solid in 500 ℃ 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 under 90 ℃ of temperature, add the prepared lignin amine 3g of step 2 in the 3rd step and in this mortar, continue grinding 20min, at last with dried solid in 600 ℃ of roasting temperature 3h.
Embodiment 6
Lignin amine template solid phase prepares nano cupric oxide, with embodiment 1 step, add the prepared lignin amine 2g of step 2 in the 3rd step and in this mortar, continue grinding 20min, at last with dried solid in 500 ℃ of roasting temperature 2h.
Embodiment 7
1. get the 6g xylogen, add the 30mL deionized water, splash into while stirring the mixture of 1mL concentrated hydrochloric acid and 7mL dioxane, reflux 5h under 75 ℃ of temperature is cooled to room temperature, filters, washing precipitation is filtered, and gets the xylogen that 6g purified through above-mentioned steps, adds the 20mL dehydrated alcohol, splash into while stirring the 1.0mL concentrated hydrochloric acid, reflux 4h under 50 ℃ of temperature filters, washing for several times, get the brown fine powder, air-dry, for subsequent use.
2. take by weighing the xylogen 6g after the prepared purification of step 1 is degraded under the room temperature, add deionized water 138mL and 0.4 mol ﹒ L
-1NaOH solution 8.25mL behind the magnetic agitation 10min, adds formaldehyde 3.75mL, stir 10min, add again tetraethylene pentamine 4.2mL, continue to stir 10min, solution is reflux 3h under 75 ℃ of temperature, be cooled to room temperature, filter, in filtrate, add 10% potassium ferricyanide solution, after precipitating fully, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into 60 ℃ of dry 12h of thermostatic drying chamber.
3. with 0.05molCuSO
45H
2O and 0.05mol Na
2CO
3Grind respectively 20 min, then transfer in the same mortar, add the prepared lignin amine 1g of step 2 and in this mortar, continue to grind 20min, with the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water is cleaned 3 times, clean 3 times with dehydrated alcohol again, centrifugation is put into 60 ℃ of dry 12h of thermostatic drying chamber with the solid after separating, at last with dried solid in 400 ℃ of roasting temperature 2h.
Claims (5)
1. the method for a solid phase template synthesis nano cupric oxide, carry out in the steps below:
A, the mantoquita of getting Isoequivalent weight and yellow soda ash grind respectively 20 min, transfer in the same mortar, add lignin amine and continue to grind 20min in this mortar, get mixture, described mantoquita mixes with the ratio that every 0.05mol mantoquita adds 0.5 ~ 3g lignin amine with lignin amine;
B, with the deionized water ultrasonic cleaning of gained mixture, centrifugation, precipitate with deionized water is cleaned 3 times, cleans 3 times centrifugation with dehydrated alcohol again;
C, the solid after will separating are put into the dry 12h of thermostatic drying chamber, and the temperature of described thermostatic drying chamber is 60 ℃;
D, at last with dried solid in 300-700 ℃ of roasting temperature 2-4h.
2. the method for a kind of solid phase template synthesis nano cupric oxide described in according to claim 1 is characterized in that wherein said lignin amine prepares in the steps below:
(1) xylogen is purified and is degraded
A, get xylogen, add deionized water, splash into while stirring the mixture of concentrated hydrochloric acid and dioxane, by every 6-10g xylogen, add 30mL deionized water, 1mL concentrated hydrochloric acid and 7mL dioxane;
B, with mentioned solution reflux 5h under 75 ℃ of temperature, be cooled to room temperature, filter, washing precipitation is filtered;
The xylogen that C, the above-mentioned steps of learning from else's experience were purified adds dehydrated alcohol, splashes into while stirring concentrated hydrochloric acid, and the xylogen of purifying by every 6-10g adds 20-30mL dehydrated alcohol, 0.75-1.0mL concentrated hydrochloric acid;
D, with mentioned solution reflux 4h under 50-75 ℃ of temperature, filter, washing gets the brown fine powder for several times, and is air-dry, for subsequent use;
(2) lignin amine is synthetic
Take by weighing the xylogen after the prepared purification of certain mass step 1 is degraded under A, the room temperature, add deionized water and 0.4 mol ﹒ L
-1NaOH solution, behind the magnetic agitation 10min, the formaldehyde that adds certain volume, stir 10min, add again a certain amount of amine, continue to stir 10min, the consumption of the xylogen after the above-described purification degraded and deionized water, NaOH, formaldehyde, amine is respectively: xylogen: deionized water is (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, and xylogen and amine mass ratio are (4-8): (2.8-5.6) g/mL;
B, with mentioned solution reflux 3-5h under 60-90 ℃ of temperature, be cooled to room temperature, filter;
C, in filtrate, add 10% potassium ferricyanide solution, after precipitating fully, decompress filter, with deionized water repeatedly wash remove the unnecessary Tripotassium iron hexacyanide after, filter cake is put into the dry 12h of thermostatic drying chamber, described loft drier temperature is 60 ℃.
3. the method for a kind of solid phase template synthesis nano cupric oxide described in according to claim 2 is characterized in that the xylogen described in the step (1) is alkali lignin.
4. the method for a kind of solid phase template synthesis nano cupric oxide described in according to claim 2 is characterized in that the amine described in the step (2) is tetraethylene pentamine.
5. the method for a kind of solid phase template synthesis nano cupric oxide described in according to claim 1 is characterized in that the mantoquita described in the steps A is copper sulfate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979600A (en) * | 2014-05-30 | 2014-08-13 | 上海沃凯生物技术有限公司 | Preparation method of ultrathin copper oxide powder |
| CN111330560A (en) * | 2019-12-31 | 2020-06-26 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058263A (en) * | 2012-12-06 | 2013-04-24 | 江苏大学 | Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method |
| JP2013108117A (en) * | 2011-11-18 | 2013-06-06 | Toshiba Corp | Method and apparatus for recovering copper from copper etching waste liquid |
-
2013
- 2013-06-05 CN CN201310224700.4A patent/CN103303962B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013108117A (en) * | 2011-11-18 | 2013-06-06 | Toshiba Corp | Method and apparatus for recovering copper from copper etching waste liquid |
| CN103058263A (en) * | 2012-12-06 | 2013-04-24 | 江苏大学 | Method of solid phase preparation of nanometer zinc oxide photocatalyst by using lignin amine template method |
Non-Patent Citations (3)
| Title |
|---|
| 李道华: "CuO纳米晶的一步超声室温固相合成及表征", 《西南民族大学学报·自然科学版》 * |
| 王晓红等: "木质素的胺化改性", 《中国造纸》 * |
| 陈玉等: "芦苇造纸黑液中木质素测定方法的优化", 《广西轻工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979600A (en) * | 2014-05-30 | 2014-08-13 | 上海沃凯生物技术有限公司 | Preparation method of ultrathin copper oxide powder |
| CN103979600B (en) * | 2014-05-30 | 2016-08-31 | 上海沃凯生物技术有限公司 | A kind of preparation method of ultrafine copper oxide powder |
| 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 |
| CN111330560A (en) * | 2019-12-31 | 2020-06-26 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
| 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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