CN102121038A - Method for preparing cuprous oxide/ bacterial cellulose nano composite material - Google Patents
Method for preparing cuprous oxide/ bacterial cellulose nano composite material Download PDFInfo
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- CN102121038A CN102121038A CN2010105784271A CN201010578427A CN102121038A CN 102121038 A CN102121038 A CN 102121038A CN 2010105784271 A CN2010105784271 A CN 2010105784271A CN 201010578427 A CN201010578427 A CN 201010578427A CN 102121038 A CN102121038 A CN 102121038A
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Abstract
The invention relates to a method for preparing a cuprous oxide/ bacterial cellulose nano composite material. The preparing method comprises the following steps of: obliquely inoculating acetobacter xylinum strains into culture solution, and culturing the strains to obtain a bacterial cellulose gel film; performing surface activation treatment on the bacterial cellulose gel film in sulfuric acid solution and sodium hypochlorite solution respectively; and sequentially soaking the surface activated bacterial cellulose gel film into Cu(NO3)2 solution and hydroquinone solution to perform reduction reaction to obtain the cuprous oxide/ bacterial cellulose nano composite material. The method has the advantages that: the preparation process is simple; and the prepared composite material keeps the nano structure of cuprous oxide particles, simultaneously has good strength performance, and has wide application prospect on the aspects of electrode devices, catalysts, gas sensitive sensors and the like.
Description
Technical field
The present invention relates to is the preparation method of a kind of Red copper oxide/bacteria cellulose nano composite material, belongs to the Red copper oxide/bacteria cellulose nano composite material technology of three-dimensional space network structure.
Background technology
Red copper oxide (Cu
2O) belong to p N-type semiconductorN material, have some properties aspect light, electricity and the catalytic performance, therefore solar cell, electrode device, catalyzer, and aspect such as gas sensor obtain more and more widely application.At present, the method for preparing nano cuprous oxide has a lot, comprises chemical deposition, electrochemical process, irradiation method, polyvalent alcohol method etc.But the catalysis of nano cuprous oxide particulate, electricity and optical activity, often owing to the caused reunion of the high surface energy of nano particle is subjected to a certain degree restriction, when the cuprous nano particle of simultaneous oxidation is used for sewage disposal as catalyzer, play katalysis in the water by being suspended in, but because of floating can't sedimentation, therefore be difficult to recycling.
By template cuprous oxide nano particle is fixed in the three-dimensional structure template, forms nano composite material and then can well address this problem with three-dimensional space network structure.Bacteria cellulose has excellent mechanical property, very high chemical purity and degree of crystallinity and excellent biological compatibility and biological degradability, is widely used in fields such as medicine, biological support, papermaking, environmental pollution improvement and foodstuffs industry.Simultaneously, bacteria cellulose itself has the three-dimensional space network structure, is the ideal template material.Given this, be template with the modified bacteria cellulose, the Red copper oxide/bacteria cellulose nano composite material that adopts the redox reaction preparation to have spacial framework has important application value.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of Red copper oxide/bacteria cellulose nano composite material.This procedure is simple, and prepared Red copper oxide/bacteria cellulose nano composite material has the performance of good intensity and wide application prospect.
The present invention is realized that by the following technical programs the preparation method of a kind of Red copper oxide/bacteria cellulose nano composite material is characterized in that may further comprise the steps:
1) be 10: 3: 4 with glucose, yeast powder, peptone, Sodium phosphate dibasic and deionized water by mass ratio at room temperature: 4: 400 uniform mixing are also used Glacial acetic acid regulator solution pH to 4.5~5.0, obtain culture medium solution, culture medium solution is carried out steam sterilizing 30~50min under 110 ℃~130 ℃ of temperature; After sterilising medium solution is cooled to room temperature, utilize inclined-plane inoculation method inoculation acetobacter xylinum bacterial classification (Acetobacter xylinum), place shaking table then, under the condition of 30 ℃~37 ℃ of temperature and rotating speed r=150~80r/min, stir, churning time is 48~50h, then culture medium solution is filled in the culture dish that volume is 40~50mL by the transfer pipet branch, and put into 30 ℃ of biochemical incubators of constant temperature and continue to cultivate, incubation time is 5~7 days, promptly obtains the bacterial cellulose gel film.
2) the bacterial cellulose gel film that step 1) is made is put into deionized water and is boiled cleaning, and boiling time is 20min, and then is placed in the NaOH solution that concentration is 0.3~0.7mol/L and boils cleaning, and boiling time is 15min~20min; Use washed with de-ionized water bacterial cellulose gel film then, clean to rinse water pH be 7.
3) to step 2) the bacterial cellulose gel film of cleaning out that obtains carries out surface activation process, soak 48~50h in the sulphuric acid soln that at first immerse pH and be 1, concentration is 0.04~0.06mol/L, put into pH then and be 1, concentration is the NaIO of 0.20~0.25mol/L
4In the solution, under being 50~55 ℃ and stirring condition, lucifuge, temperature react 1~4h, be ethylene glycol solution and the washed with de-ionized water sample of 1.0~3.0mol/L with concentration successively afterwards, being immersed in subsequently with pH is that the concentration that 3.14 Glacial acetic acid are regulated is the NaClO of 0.20-0.25mom/L
248~50h in the solution is ethylene glycol solution and the washed with de-ionized water sample of 1.0~3.0mol/L with concentration more successively after finishing, and promptly obtains the bacteria cellulose film of surface activation process.
4) the bacteria cellulose film of the surface activation process that step 3) is made immersion concentration is the Cu (NO of 0.15~0.20mol/L
3)
246~50h in the solution, the Resorcinol solution of putting into concentration subsequently and be 0.016~0.018mol/L carries out reduction reaction 1-3h, keeping pH value of solution by the dropping triethylamine in the reaction process is 9, promptly obtains Red copper oxide/bacteria cellulose nano composite material after reaction is finished.
The invention has the advantages that, adopt simple and gentle relatively method to prepare Red copper oxide/bacteria cellulose nano composite material.This matrix material has not only kept Red copper oxide particulate nanostructure, simultaneously with the bacteria cellulose of mechanical property excellence as support, therefore make this matrix material keep Red copper oxide simultaneously also in some properties of aspects such as light, electricity and catalysis, also overcome the shortcoming of the recovery difficulty that cuprous oxide nano particle causes because of suspension, therefore be expected to be widely used at aspects such as electrode device, catalyzer and gas sensors.
Description of drawings
Fig. 1 for the carrying out of example 1 preparation Red copper oxide/bacteria cellulose nano composite material microscopic appearance photo of surface activation process 1h.
Fig. 2 for the carrying out of example 2 preparation Red copper oxide/bacteria cellulose nano composite material microscopic appearance photo of surface activation process 2h.
Embodiment
Example 1
It is as follows to prepare the required bacteria cellulose cultural method of matrix material: with glucose (12.5g), yeast powder (3.75g), peptone (5.00g) and Sodium phosphate dibasic (5.00g) are dissolved in the distilled water of 500mL, with Glacial acetic acid regulator solution pH to 4.7, obtain the culture medium solution of acetobacter xylinum.The nutrient solution branch is filled in the Erlenmeyer flask at 115 ℃ of steam sterilizing 30min, treats to utilize the inclined-plane inoculation method to inoculate after it is cooled to room temperature, then stir 48h (stirring velocity r=160r/min) down at 30 ℃.Again nutrient solution is moved in the culture dish and at last and cultivate, can obtain the gel film of BC after 5 days at biochemical incubator (30 ℃).Subsequently BC is cleared up, its scale removal process is as follows: the bacterial cellulose gel film is boiled in distilled water twice, each soaking time time is 20min, and then is placed in the NaOH solution that concentration is 0.5mol/L and boils three times, and each soaking time is 20min.With distilled water film is cleaned to neutral (pH=7) at last.
Then the bacteria cellulose film cleaned out is immersed pH=1, concentration is 48h in the sulphuric acid soln of 0.04mol/L, and then puts it into pH=1 (massfraction is that 98% sulphuric acid soln is regulated), and concentration is the NaIO of 0.20mol/L
4In the solution, in lucifuge, temperature is 50 ℃ and constantly reacts 1h under the stirring condition, is 1.0mol/L ethylene glycol solution cleaning sample with concentration subsequently, more repeatedly with washed with de-ionized water, after it is immersed in pH=3.14, concentration is the NaClO of 0.20mom/L
248h in the solution is ethylene glycol solution and the washed with de-ionized water sample of 2.0mol/L with concentration then successively, and immersing concentration subsequently at ambient temperature is the Cu (NO of 0.15mol/L
3)
246h in the solution, take out with deionized water rinsing repeatedly the back, puts into pH=9 again, and concentration is to react 1h in the Resorcinol solution of 0.016mol/L.Constantly stir in the reaction process, and constant with triethylamine regulator solution pH=9.Take out sample and clean up with deionized water, can obtain Red copper oxide/bacteria cellulose nano composite material of carboxylated processing 1h, its microtexture as shown in Figure 1.
Example 2
The bacteria cellulose film (preparation method is with example 1) for preparing and clean out is immersed pH=1, concentration is 49h in the sulphuric acid soln of 0.05mol/L, and then putting it into pH=1 (massfraction is that 98% sulphuric acid soln is regulated), concentration is the NaIO of 0.22mol/L
4In the solution, in lucifuge, temperature is 52 ℃ and constantly reacts 2h under the stirring condition, is 2.0mol/L ethylene glycol solution cleaning sample with concentration subsequently, more repeatedly with washed with de-ionized water, after it is immersed in pH=3.14, concentration is the NaClO of 0.22mom/L
249h in the solution is ethylene glycol solution and the washed with de-ionized water sample of 2.0mol/L with concentration then successively, and immersing concentration subsequently at ambient temperature is the Cu (NO of 0.17mol/L
3)
248h in the solution, take out with deionized water rinsing repeatedly the back, puts into pH=9 again, and concentration is to react 2h in the Resorcinol solution of 0.017mol/L.Constantly stir in the reaction process, and constant with triethylamine regulator solution pH=9.Take out sample and clean up with deionized water, can obtain Red copper oxide/bacteria cellulose nano composite material of carboxylated processing 2h, its microtexture as shown in Figure 2.
Example 3
The bacteria cellulose film (preparation method is with example 1) for preparing and clean out is immersed pH=1, concentration is 50h in the sulphuric acid soln of 0.06mol/L, and then putting it into pH=1 (massfraction is that 98% sulphuric acid soln is regulated), concentration is the NaIO of 0.25mol/L
4In the solution, in lucifuge, temperature is 55 ℃ and constantly reacts 3h under the stirring condition, is 3.0mol/L ethylene glycol solution cleaning sample with concentration subsequently, more repeatedly with washed with de-ionized water, after it is immersed in pH=3.14, concentration is the NaClO of 0.25mom/L
250h in the solution is ethylene glycol solution and the washed with de-ionized water sample of 3.0mol/L with concentration then successively, and immersing concentration subsequently at ambient temperature is the Cu (NO of 0.20mol/L
3)
250h in the solution, take out with deionized water rinsing repeatedly the back, puts into pH=9 again, and concentration is to react 3h in the Resorcinol solution of 0.018mol/L.Constantly stir in the reaction process, and constant with triethylamine regulator solution pH=9.Take out sample and clean up, can obtain Red copper oxide/bacteria cellulose nano composite material of carboxylated processing 3h with deionized water.
Claims (1)
1. the preparation method of Red copper oxide/bacteria cellulose nano composite material is characterized in that may further comprise the steps:
1) be 10: 3: 4 with glucose, yeast powder, peptone, Sodium phosphate dibasic and deionized water by mass ratio at room temperature: 4: 400 uniform mixing are also used Glacial acetic acid regulator solution pH to 4.5~5.0, obtain culture medium solution, culture medium solution is carried out steam sterilizing 30~50min under 110 ℃~130 ℃ of temperature; After sterilising medium solution is cooled to room temperature, utilize inclined-plane inoculation method inoculation acetobacter xylinum bacterial classification, place shaking table then, under the condition of 30 ℃~37 ℃ of temperature and rotating speed r=150~80r/min, stir, churning time is 48~50h, then culture medium solution is filled in the culture dish that volume is 40~50mL by the transfer pipet branch, and puts into 30 ℃ of biochemical incubators of constant temperature and continue to cultivate, incubation time is 5~7 days, promptly obtains the bacterial cellulose gel film;
2) the bacterial cellulose gel film that step 1) is made is put into deionized water and is boiled cleaning, and boiling time is 20min, and then is placed in the NaOH solution that concentration is 0.3~0.7mol/L and boils cleaning, and boiling time is 15min~20min; Use washed with de-ionized water bacterial cellulose gel film then, clean to rinse water pH be 7;
3) to step 2) the bacterial cellulose gel film of cleaning out that obtains carries out surface activation process, soak 48~50h in the sulphuric acid soln that at first immerse pH and be 1, concentration is 0.04~0.06mol/L, put into pH then and be 1, concentration is the NaIO of 0.20~0.25mol/L
4In the solution, under being 50~55 ℃ and stirring condition, lucifuge, temperature react 1~4h, be ethylene glycol solution and the washed with de-ionized water sample of 1.0~3.0mol/L with concentration successively afterwards, being immersed in subsequently with pH is that the concentration that 3.14 Glacial acetic acid are regulated is the NaClO of 0.20-0.25mom/L
248~50h in the solution is ethylene glycol solution and the washed with de-ionized water sample of 1.0~3.0mol/L with concentration more successively after finishing, and promptly obtains the bacteria cellulose film of surface activation process;
4) the bacteria cellulose film of the surface activation process that step 3) is made immersion concentration is the Cu (NO of 0.15~0.20mol/L
3)
246~50h in the solution, the Resorcinol solution of putting into concentration subsequently and be 0.016~0.018mol/L carries out reduction reaction 1-3h, keeping pH value of solution by the dropping triethylamine in the reaction process is 9, promptly obtains Red copper oxide/bacteria cellulose nano composite material after reaction is finished.
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CN103028117A (en) * | 2012-12-24 | 2013-04-10 | 深圳先进技术研究院 | Method for preparing bacterial cellulose gel composite material |
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