CN106279763B - A kind of hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids and application - Google Patents
A kind of hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids and application Download PDFInfo
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- CN106279763B CN106279763B CN201610652279.0A CN201610652279A CN106279763B CN 106279763 B CN106279763 B CN 106279763B CN 201610652279 A CN201610652279 A CN 201610652279A CN 106279763 B CN106279763 B CN 106279763B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The invention discloses a kind of hydrothermal preparing process of nano-ZnO cellulose composite material based on NaOH/ urea liquids and application, this method to be：In the cellulose solution of NaOH/ urea, nano-ZnO cellulose composite material is prepared using hydro-thermal method In-situ reaction.The hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids of the present invention, after cellulose dissolution, hydroxyl on its molecule is combined with zinc ion, overcome the shortcomings that zinc source is not easily penetrated into carrier, and solvent for use NaOH/ urea is cheap and easy to get, hydrothermal synthesis temperature is substantially reduced.The nano-ZnO cellulose composite material contains 47.5%ZnO；There is higher removal efficiency, ZnO cellulose composite materials prepared by the present invention, cheap environmental protection in terms of the processing of phenolic waste water, to have good practicability as Photodegradation catalyst the phenol in light degradation waste water.
Description
Technical field
The invention belongs to nano-ZnO cellulose composite material technical fields, and in particular to one kind being based on NaOH/ urea liquids
Nano-ZnO cellulose composite material hydrothermal preparing process and application.
Background technology
Zinc oxide (ZnO) is a kind of unique broad stopband direct band-gap semicondictor oxide, and energy gap is at room temperature
3.37eV, wide energy gap, high breakdown strength and saturated electrons mobility, makes it have excellent electrical property, is answered extensively
For fields such as the light anode material of solar cell and high-performance transistors.ZnO nano material is due to its nano effect, in power
The performance of, photoelectricity, piezoelectricity, air-sensitive, catalysis etc. is greatly improved, and shows that some new physics are special
Property, such as good photocatalysis performance, excellent field emission performance, superior absorbing property and the dilute magnetism of good doping etc.,
These characteristics make nano zine oxide in photochemical catalyst, optical device, electronic device, feds, photovoltaic device, piezoelectricity device
The application aspects such as part, absorbing material, bio-medical material show huge potentiality.
In materials science field, composite material is learnt from other's strong points to offset one's weaknesses in performance, synergistic effect is generated, in numerous areas such as work
Industry, biomedical sector etc. show great application prospect.Nano-ZnO micro mist has superior antibacterial, photocatalysis and suction
Attached performance, is combined with cellulose, can improve the application of cellulose in other respects, while ZnO can be overcome easily to reunite, hardly possible point
From the shortcomings of.Currently, there are two main classes for the preparation method of nano-ZnO/cellulose composite material：First, with cellulose or cellulose
Film is carrier, and zinc source (such as zinc nitrate, zinc acetate) is supported on carrier, zinc source is finally converted to nano zine oxide, is obtained
To nano-ZnO/cellulose composite material；Second is that nano-ZnO is first prepared, nano-ZnO is then dispersed in cellulose or fibre
In the solution of the plain derivative (such as cellulose acetate) of dimension, finally cellulose or cellulose derivative are precipitated, obtain out nanometer
ZnO/ cellulose composite materials.The above two classes method has its disadvantage：The first kind, using fiber or film as carrier, zinc source is not easy to ooze
It penetrates into carrier；Second class needs to select cellulose or the solvent of cellulose derivative, causes environmental pollution；And nano-ZnO
Grain be not easy to be dispersed in cellulose or solution of cellulose derivative, and spinned fiber or film forming procedure are caused it is unfavorable
It influences.Based on obtained composite material is generally applied with cellulose, ZnO content is less, based on the research of antibiotic property effect.
Bagheri etc. is by cellulose dissolution in 1- butyl -3- methylimidazole villaumites [C4Mim] in Cl, it is prepared by In-situ reaction
Cellulose-ZnO nano composite material, although overcoming the shortcomings that zinc source is not easily penetrated into carrier, ionic liquid cost
It is too high, it is difficult to apply.
Invention content
Goal of the invention：For deficiency existing for the above method, it is molten based on NaOH/ urea that the object of the present invention is to provide one kind
Zinc is added by cellulose dissolution in NaOH/ urea liquids in the hydrothermal preparing process of the nano-ZnO cellulose composite material of liquid
Source, hydro-thermal method In-situ reaction prepare ZnO cellulose nanocomposites, and nano-ZnO cellulose is prepared by controlling reaction condition
Composite material, and applied in Photocatalytic Degradation of Phenol.
Technical solution：In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is：
A kind of hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids is urinated in NaOH/
In the cellulose solution of element, nano-ZnO cellulose composite material is prepared using hydro-thermal method In-situ reaction.
The hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids, concrete operations
It is：It taking 50g to prepare the aqueous solution of the pre- NaOH/Urea for being cooled to -12 DEG C, microcrystalline cellulose is added, rapid stirring is extremely dissolved,
The zinc solution of 1mol/L is instilled, after stirring is aged 30min, with 2% H2SO4Solution adjusts pH value, is transferred to hydrothermal reaction kettle
Middle reaction, after take out with distillation washing 3 times, in 70 DEG C of baking ovens drying weigh to obtain nano-ZnO cellulose composite material.
The hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids, NaOH/
In the aqueous solution of Urea, NaOH ︰ Urea ︰ H2The mass ratio of O is 7 ︰, 12 ︰ 81.
The hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids, zinc solution
For ZnCl2Or Zn (CH3COO)2Solution.
The hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids, hydro-thermal reaction
In kettle, 100 DEG C of reaction 2h.
What the hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids was obtained receives
Rice ZnO cellulose composite materials.
Application of the ZnO celluloses nanocomposite as photochemical catalyst.
Application of the ZnO celluloses nanocomposite in Photocatalytic Degradation of Phenol.
Advantageous effect：Compared with prior art, the nano-ZnO cellulose of the invention based on NaOH/ urea liquids is compound
The hydrothermal preparing process of material, solvent NaOH/ urea is cheap and easy to get, and simultaneously as the reaction reagent for preparing ZnO, and cellulose is molten
Xie Hou, the hydroxyl on molecule are combined with zinc ion, are conducive to the generation of nano-ZnO, and hydrothermal synthesis temperature is substantially reduced, because
This, preparation process has the advantages that energy saving.Obtained material is irregular particle shape nano-ZnO/cellulose new material, is contained
47.5% ZnO.Have higher removal efficiency, ZnO cellulose composite materials prepared by the present invention honest and clean phenol in waste water
Valence environmental protection has good practicability as photochemical catalyst in terms of the wastewater treatment of phenol.
Description of the drawings
Fig. 1 is the electron microscope of 1 product of embodiment；
Fig. 2 is the FTIR figures of 1 product of embodiment；
Fig. 3 is the TG figures of 1 product of embodiment
Fig. 4 is the XRD diagram of 1 product of embodiment；
Fig. 5 is 2 light degradation phenolic waste water removal rate figure of embodiment；
Fig. 6 is the electron microscope of 3 product of embodiment；
Fig. 7 is the infrared figure of 3 product of embodiment；
Fig. 8 is the XRD diagram of 3 product of embodiment；
Fig. 9 is 4 light degradation phenolic waste water removal rate figure of embodiment；
Specific implementation mode
With reference to specific embodiment, the present invention is described further.
The preparation of embodiment 1ZnO cellulose nanocomposites (zinc acetate is zinc source)
50g is taken to prepare aqueous solution (the NaOH ︰ Urea ︰ H of the pre- NaOH/Urea for being cooled to -12 DEG C2The mass ratio of O is 7 ︰
12 ︰ 81), 2g microcrystalline celluloses are added, rapid stirring is added dropwise to the Zn (CH of the 1mol/L of 30mL to dissolving3COO)2Solution stirs
After mixing ageing 30min, with 2% H2SO4Solution adjusts pH value to 9, is transferred to 100 DEG C of reaction 2h in hydrothermal reaction kettle, takes out and use
Distillation is washed 3 times, is dried in 70 DEG C of baking ovens and is weighed to obtain nano-ZnO cellulose composite material.
Prepared ZnO cellulose nanocomposites are characterized, it is specific as follows：
The electron microscopes of prepared ZnO cellulose nanocomposites as shown in Figure 1, infrared figure as shown in Fig. 2, TG as schemed
Shown in 3, XRD diagram such as Fig. 4.It can be seen that ZnO is gathered in cellulose surface in the form of nano-sheet from electron microscope, in infrared figure
472cm-1It is the characteristic peak of ZnO at wave number, illustrates in the composite material prepared successful In-situ reaction ZnO.From TG figures
It can be seen that ZnO content is 47.5% in the composite material of preparation.From the XRD diagram of Fig. 4 as can be seen that 2 θ=31.7 ° of the angle of diffraction,
34.4 °, 36.2 °, (100) of 47.5 °, 56.6 ° corresponding ZnO structures, (002), (101), (102), (110) crystal face,
With zinc oxide standard card JCPDS：36-1451 matches.There are two characteristic peaks at 2 θ=20.63 ° and 23.06 °, corresponding to be
The diffraction maximum of cellulose illustrates that the product is the combination product of ZnO and cellulose.
The light degradation property of embodiment 2ZnO cellulose nanocomposite Pyrogentisinic Acid's waste water
It takes the phenol solution of 100mL 50mg/L in 250mL quartz beakers, it is fine that obtained ZnO/ in embodiment 1 is added
The plain composite material 0.1g of dimension, is stirring evenly and then adding into the hydrogen peroxide of 0.01g30%, in ultraviolet light and sunshine on magnetic stirring apparatus
Under light irradiation, every half an hour sampling analysis Phenol in Aqueous Solution concentration, 6h is stirred altogether, the removal rate of phenol is 66.36% after 6h.
The concentration of phenol is surveyed absorbance at 235nm with ultraviolet-uisible spectrophotometer and is obtained according to phenol Standard curve.
The removal rate calculating formula of phenol：
In formula, C0It is the concentration of phenol solution before and after light degradation respectively with C；
The removal rate effect of phenol is as shown in Figure 5.With the increase of light degradation time in figure, ZnO celluloses are nano combined
The removal rate of material Pyrogentisinic Acid's phenol in wastewater increases up to 66.36%, and under similarity condition, and ZnO blank (is not added in embodiment 1
The control sample that cellulose is prepared) and cellulose blanks sample (be not added with ZnCl in embodiment 12The control sample that solution is prepared)
The removal rate of Pyrogentisinic Acid does not change substantially after 180min, and the maximum material removal rate of Pyrogentisinic Acid is respectively 17.72% He
12.04%.
Embodiment 3
50g is taken to prepare aqueous solution (the NaOH ︰ Urea ︰ H of the pre- NaOH/Urea for being cooled to -12 DEG C2The mass ratio of O is 7 ︰
12 ︰ 81), 4g microcrystalline celluloses are added, rapid stirring is added dropwise to the ZnCl of 1mol/L to dissolving2, after stirring is aged 30min, use
2% H2SO4Solution adjusts pH value to 9, is transferred to 100 DEG C of reaction 2h in hydrothermal reaction kettle, takes out with distillation washing 3 times, 70 DEG C
Drying weighs to obtain nano-ZnO cellulose composite material in baking oven.
The electron microscopes of prepared ZnO cellulose nanocomposites as shown in fig. 6, infrared figure as shown in fig. 7, XRD diagram
As shown in figure 8, as can be seen from Figure 6 due to adding more cellulose, cellulose dissolution is simultaneously insufficient, has portion of cellulose micro-
Fibril exists, and the ZnO of generation is wrapped in cellulose microfibril surface.It is smaller to dissolve regenerated cellulose grain, puffy ZnO covers
It covers on surface.From the infrared it can be seen from the figure that 430cm of Fig. 7-1It is the characteristic peak of ZnO at wave number, illustrates in the composite material prepared
Successful In-situ reaction ZnO.From the XRD diagram of Fig. 8 as can be seen that 2 θ=31.7 ° of the angle of diffraction, 34.4 °, 36.2 °,
(100) of 47.5 °, 56.6 °, 62.8 °, 67.9 ° corresponding ZnO structures, (002), (101), (102), (110),
(103), (112) and zinc oxide standard card JCPDS：36-1451 matches.There are two special at 2 θ=20.63 ° and 23.06 °
Peak is levied, corresponding is the diffraction maximum of cellulose, illustrates that the product is the combination product of ZnO and cellulose.
The light degradation property of 4 nano-ZnO cellulose composite material Pyrogentisinic Acid's waste water of embodiment
It takes the phenol solution of 100mL50mg/L in 250mL quartz beakers, it is fine that obtained ZnO/ in embodiment 3 is added
The plain composite material 0.1g of dimension, is stirring evenly and then adding into the hydrogen peroxide of 0.01g30%, in ultraviolet light and sunshine on magnetic stirring apparatus
Under light irradiation, every half an hour sampling analysis Phenol in Aqueous Solution concentration, 6h is stirred altogether, the removal rate of phenol is 70.04% after 6h.
The concentration of phenol is surveyed absorbance at 235nm with ultraviolet-uisible spectrophotometer and is obtained according to phenol Standard curve.
The removal rate calculating formula of phenol：
In formula, C0It is the concentration of phenol solution before and after light degradation respectively with C；
The removal rate effect of phenol is as shown in Figure 9.With the increase of light degradation time in figure, ZnO celluloses are nano combined
The removal rate of material Pyrogentisinic Acid's phenol in wastewater increases up to 70.04%, and under similarity condition, and ZnO blank (is not added in embodiment 1
The control sample that cellulose is prepared) and cellulose blanks sample (be not added with ZnCl in embodiment 12The control sample that solution is prepared)
The removal rate of Pyrogentisinic Acid does not change substantially after 180min, and the maximum material removal rate of Pyrogentisinic Acid is respectively 17.72% He
12.04%.
Claims (7)
1. a kind of hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids, which is characterized in that
In the cellulose solution of NaOH/ urea, nano-ZnO cellulose composite material is prepared using hydro-thermal method In-situ reaction；Tool
Gymnastics is made：It takes 50g to prepare the aqueous solution of the pre- NaOH/Urea for being cooled to -12 DEG C, microcrystalline cellulose is added, rapid stirring is extremely
Dissolving instills the zinc solution of 1mol/L, after stirring is aged 30min, with 2% H2SO4Solution adjusts pH value, is transferred to hydro-thermal
Reacted in reaction kettle, after take out with distillation washing 3 times, in 70 DEG C of baking ovens drying weigh to obtain nano-ZnO cellulose compound
Material.
2. the hydro-thermal preparation side of the nano-ZnO cellulose composite material according to claim 1 based on NaOH/ urea liquids
Method, which is characterized in that in the aqueous solution of NaOH/Urea, NaOH ︰ Urea ︰ H2The mass ratio of O is 7 ︰, 12 ︰ 81.
3. the hydro-thermal preparation side of the nano-ZnO cellulose composite material according to claim 1 based on NaOH/ urea liquids
Method, which is characterized in that zinc solution ZnCl2Or Zn (CH3COO)2Solution.
4. the hydro-thermal preparation side of the nano-ZnO cellulose composite material according to claim 1 based on NaOH/ urea liquids
Method, which is characterized in that in hydrothermal reaction kettle, 100 DEG C of reaction 2h.
5. the hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids described in claim 1 is obtained
The nano-ZnO cellulose composite material obtained.
6. application of the ZnO celluloses nanocomposite as photochemical catalyst described in claim 5.
7. ZnO celluloses nanocomposite described in claim 5 is in the application of Photocatalytic Degradation of Phenol.
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| CN110041564A (en) * | 2019-03-29 | 2019-07-23 | 北京林业大学 | The in-situ preparation method of cellulose antibacterial film, the cellulose antibacterial film by this method preparation and its application |
| CN109939745A (en) * | 2019-04-22 | 2019-06-28 | 南京林业大学 | A kind of nano-titanium dioxide/wood flour composite material and its preparation method and application |
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| CN101011656A (en) * | 2007-01-26 | 2007-08-08 | 福建师范大学 | Preparing method of zinc oxide nano fiber film used as photocatalyst |
| CN104018235A (en) * | 2014-06-09 | 2014-09-03 | 浙江理工大学 | Method for manufacturing zinc oxide-cellulose nanocrystalline composite fiber film with antibacterial characteristic and photocatalytic degradation characteristic at same time |
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| CN101011656A (en) * | 2007-01-26 | 2007-08-08 | 福建师范大学 | Preparing method of zinc oxide nano fiber film used as photocatalyst |
| CN104018235A (en) * | 2014-06-09 | 2014-09-03 | 浙江理工大学 | Method for manufacturing zinc oxide-cellulose nanocrystalline composite fiber film with antibacterial characteristic and photocatalytic degradation characteristic at same time |
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