CN107541948A - A kind of cotton fiber of layered double hydroxide modification and its preparation method and application - Google Patents
A kind of cotton fiber of layered double hydroxide modification and its preparation method and application Download PDFInfo
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- CN107541948A CN107541948A CN201710737525.7A CN201710737525A CN107541948A CN 107541948 A CN107541948 A CN 107541948A CN 201710737525 A CN201710737525 A CN 201710737525A CN 107541948 A CN107541948 A CN 107541948A
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Abstract
The invention discloses cotton fiber of a kind of layered double hydroxide modification and its preparation method and application.Method is modified using poly-dopamine, cotton is immersed in the dopamine solution of pre-oxidation, the poly-dopamine layer with catechol structure is formed, coordinate bond is formed using the metal ion in catechol group and LDHs reaction solutions, by LDHs crystal fixation in situ on cotton fiber.Preparation method of the present invention is simple, and mild condition, decorative layer is evenly distributed, Stability Analysis of Structures, improves the adsorption capacity of LDHs crystal, solves the problems such as LDHs crystal directly applies in absorption the crystal reunion run into and reclaiming difficulty；It is not decreased obviously using rear absorption property for a long time, the absorption of anionic drugs and dyestuff contaminant suitable for environmental water sample.
Description
Technical field
The invention belongs to cotton fiber and its preparation field, and in particular to the cotton of layered double hydroxide modification is fine
Dimension and its preparation method and application.
Background technology
Layered double hydroxide（LDHs）, also commonly referred to as hydrotalcite-based compound.Wherein metal hydroxides structure
Into main layer board, anion and hydrone insertion interlayer form unique layer structure.Because LDHs crystal has porous, heat
Stability and extremely strong anion exchange capacity, so all having in fields such as absorption, catalysis, biology and drug deliveries extensive
Using.(Q. Wang, D. O'Hare. Chem. Rev. 112(2012), 4124-4155).
Based on the interchangeability of layered double hydroxide interlayer anion, LDHs crystal in polar compound especially
There is certain advantage in terms of the removal of anionic compound.But LDHs crystal is directly used in into absorption will face a lot
Problem, such as the aggregation of crystal itself will reduce adsorption avtive spot；Mass transfer between adsorbent and pending sample
Limited efficacy；Crystal is not easily recycled and crystal is filled into fixing device into the problems such as blocking often occurs.Therefore, select
Suitable crystal growth matrix just turns into the key to solve the above problems.As a kind of natural polymer, cotton fiber, which has, to be come
Source is enriched, and cost is low, it is environment-friendly the features such as.It can provide enough specific surface areas for crystal growth, short texture, be easy to
Compression, the problems such as will not bringing blocking is filled it into specific sample pre-treatments or wastewater treatment equipment, is fixed in crystal
And the application in practical laboratory and Industrial Wastewater Treatment has larger potentiality.Due to lacking suitable crystal fixation side
Method, had not been reported at present on crystal to be covalently fixed to the application on cotton fiber being used to adsorb.
The content of the invention
LDHs crystal is bonded by coordination based on poly-dopamine modification technique it is an object of the invention to provide one kind
The method that crystal fixation in situ is realized to cotton fiber surface, the crystal decorative layer Stability Analysis of Structures of formation is difficult for drop-off, will thus
The cotton fiber that method obtains is used for anionic pollutant in water（Medicine and dyestuff）Absorption.
Concrete technical scheme is as follows：
A kind of layered double hydroxide（LDHs）The preparation method of the cotton fiber of modification, is concretely comprised the following steps：Use first
Cotton fiber, i.e., be immersed in the dopamine solution of pre-oxidation by the method for poly-dopamine modification, and formation has catechol knot
The poly-dopamine layer of structure；Then, coordinate bond is formed using the metal ion in catechol group and LDHs reaction solutions, by LDHs
Crystal fixation in situ is on cotton fiber.
Preferably, described layered double hydroxide is NiAl-LDHs crystal, is concretely comprised the following steps：
1）1 ~ 2 mg/mL dopamine alkaline solution is prepared, the pH of the solution is 8.5 ~ 9, is placed in atmosphere, and pre-oxidation is extremely
Brown；
2）The cotton fiber for weighing 30 ~ 200 mg immerses step 1）In dopamine alkaline solution after the pre-oxidation of gained, add
4 ~ 12 h are stirred at room temperature in magneton, after being cleaned with deionized water, 3 h are dried under 60 °C, repeats the above steps 1 time, obtains dopamine
Cotton fiber after modification（PD@cotton）；
3）Prepare LDHs reaction solutions, 0.058 ~ 0.58 g Nickelous nitrate hexahydrates, 0.038 ~ 0.38 g ANN aluminium nitrate nonahydrates and 0.042
~ 0.42 g urea mixed dissolution adds PD@cotton, reacts 12 ~ 24 h under 70 ~ 100 °C in 10 ~ 50 mL deionized waters,
After cotton fiber after the modification of LDHs crystal is cleaned repeatedly with deionized water, 6 h are dried under 60 °C, after obtaining the modification of LDHs crystal
Cotton fiber（LDHs@PD@cotton）.
The process of the LDHs crystal modification reactions of the present invention is as shown in Figure 1.The principle of immobilization of the present invention is based on modification
Poly-dopamine to cotton fiber surface can provide catechol structure, with the Ni in LDHs2+、Al3+Atom forms coordination
Key, LDHs crystal are grown on cotton fiber by the method for chemical bonding while generation, formed one layer it is stable
LDHs crystal decorative layers, the cotton fiber of LDHs modifications can be realized to anionic drugs（Ketoprofen）And dyestuff（It is Congo red）
Effective quick adsorption.
On the other hand, it is fine to provide the cotton that a kind of layered double hydroxide prepared by the above method is modified by the present invention
Dimension.
Further, the present invention provide layered double hydroxide modification cotton fiber in environmental water sample the moon from
Application in sub- medicine or dyestuff contaminant absorption.
Preferably, the drug contamination thing in described environmental water sample is Ketoprofen, and dyestuff contaminant is Congo red.
The cotton fiber LDHs@PD@cotton after the modification of LDHs crystal in the present invention are used for adsorbing domain, have as follows
Advantage：
（1）Chemical coordination key is formed using the catechol structure and the metallic atom in LDHs crystal of poly-dopamine, by LDHs
Crystal is fixed on cotton fiber in the form of chemical bond, the crystal decorative layer Stability Analysis of Structures of formation, difficult for drop-off, is consolidated for crystal
Fixedization provides a kind of new method；
（2）The matrix that cotton fiber is fixed as a kind of crystal, make full use of cotton fiber specific surface area big, be easy to modify,
It is cheap and easy to get, the advantages that being easy to compress, the LDHs with fine sorption potential is fixed on cotton fiber, and is filled with
It is used for anionic drugs into a variety of matrix（Ketoprofen）And dyestuff（It is Congo red）Absorption, as a result prove adsorbent LDHs@PD@
Cotton adsorption rate and capacity relative to without fixed LDHs crystal have be obviously improved.
Brief description of the drawings
Fig. 1 is the cotton fiber preparation process schematic diagram of LDHs crystal modification；
Fig. 2 is that LDHs@PD@cotton contrast to the chromatogram before and after Ketoprofen and Congo red absorption；
Fig. 3 is LDHs@PD@cotton, LDHs-C and unmodified cotton fiber（Cotton）It is dynamic to Ketoprofen and Congo red absorption
Mechanics schematic diagram；
Fig. 4 is LDHs@PD@cotton and LDHs-C to Ketoprofen and Congo red saturated extent of adsorption schematic diagram；
Fig. 5 is that front and rear chromatogram contrast is adsorbed to Ketoprofen after LDHs@PD@cotton are filled into different device（Scheme A- chromatograms
Pre-column；B- syringe filters）；
Note：Fig. 3,4 LDHs-C represent LDHs crystal powders, and LDHs@PD@cotton represent to be consolidated based on poly-dopamine modification technique
Surely the cotton fiber of upper LDHs crystal.
Embodiment
By combination accompanying drawing described further below it will be further appreciated that the features and advantages of the invention.The implementation provided
Example is only explanation to the inventive method, remaining content without limiting the invention in any way announcement.
Nickelous nitrate hexahydrate, magnesium nitrate hexahydrate, ANN aluminium nitrate nonahydrate, Ketoprofen and Congo red examination used in embodiment
Agent is purchased from Aladdin reagent（Shanghai）Co., Ltd.
【Embodiment 1】
1）The mg/mL of 4 mL 2 dopamine alkaline solution is prepared, the pH of the solution is 8.5, is placed in atmosphere, and pre-oxidation is extremely
Brown；
2）The cotton fiber for weighing 30 mg immerses step 1）In dopamine alkaline solution after the pre-oxidation of gained, magneton is added
4 h are stirred at room temperature, after being cleaned with deionized water, 3 h is dried under 60 °C, are repeated the above steps 1 time, after acquisition DOPA is amine-modified
Cotton fiber（PD@cotton）；
3）Prepare NiAl-LDHs reaction solutions, 0.058 g Nickelous nitrate hexahydrates, 0.038 g ANN aluminium nitrate nonahydrates and 0.042 g urine
Plain mixed dissolution adds PD@cotton in 10 mL deionized waters, and 18 h, the cotton after the modification of LDHs crystal are reacted under 95 °C
After fiber is cleaned repeatedly with deionized water, 6 h are dried under 60 °C, obtain the cotton fiber after the modification of LDHs crystal（LDHs@PD@
cotton）；
4）LDHs@PD@cotton are filled in pipette tips；
5）10 mL syringes suck the mg/mL sample solutions of 5 mL 1（Ketoprofen and Congo red）, by peristaltic pump with 1 mL/
Raffinate is entered to analyze in high performance liquid chromatography and detected, absorption is front and rear such as Fig. 2 institutes by min speed by LDHs@PD@cotton
Show.
Figure it is seen that LDHs@PD@cotton can be realized to Ketoprofen and Congo red 100% under this condition
Absorption, adsorption effect are good.Illustrate LDHs crystal modification not influenceing the property of LDHs crystal inherently on cotton fiber
Matter, LDHs crystal can realize the good adsorption to anionic compound based on ion exchange.
【Embodiment 2】
1）The mg/mL of 20 mL 2 dopamine alkaline solution is prepared, the pH of the solution is 8.5, is placed in atmosphere, is pre-oxidized
To brown；
2）The cotton fiber for weighing 150 mg immerses step 1）In dopamine alkaline solution after the pre-oxidation of gained, magneton is added
4 h are stirred at room temperature, after being cleaned with deionized water, 6 h is dried under 60 °C, are repeated the above steps 1 time, after acquisition DOPA is amine-modified
Cotton fiber（PD@cotton）；
3）NiAl-LDHs reaction solutions are prepared, 0.58 g Nickelous nitrate hexahydrates, 0.38 g ANN aluminium nitrate nonahydrates and 0.42 g urea mix
Conjunction is dissolved in 10 mL deionized waters, adds PD@cotton, and 18 h are reacted under 95 °C, and the cotton fiber after LDHs modifications is spent
After ionized water cleans repeatedly, 6 h are dried under 60 °C, obtain the cotton fiber after LDHs modifications（LDHs@PD@cotton）；
4）Prepare 3 parts respectively and contain the mg/L Ketoprofens of 40 mL 200 and Congo red solution, corresponding addition LDHs@PD@cotton,
LDHs crystal powders（LDHs-C）And unmodified cotton fiber（Cotton）, the h of stirring and adsorbing 10,200 are taken out at regular intervals
μ L sample raffinates, are detected into liquid chromatogram, carry out adsorption dynamics adsorption kinetics analysis, as a result as shown in Figure 3.
5）The Ketoprofen of 2 parts of various concentrations of preparation and Congo red solution respectively（50~800 mg/L）, it is corresponding to add LDHs@
PD@cotton and LDHs-C, sample raffinate is taken out after stirring and adsorbing 10 h, 10 h, is detected into high performance liquid chromatography, carried out
Saturated extent of adsorption is analyzed, as a result as shown in Figure 4.
It is can be seen that from Fig. 3 and Fig. 4 compared with LDHs-C, LDHs@PD@cotton have faster adsorption rate and more
High adsorption capacity, illustrate, by LDHs crystal modification to cotton fiber, on the one hand to utilize the hygroscopicity and LDHs of cotton fiber
Advantage of the uniform crystal dispersion on cotton fiber surface increases the mass transfer velocity of adsorbent and sample solution, on the other hand increases
The adsorption site of LDHs planes of crystal exposure, improves LDHs crystal to Ketoprofen and Congo red adsorption capacity.
【Embodiment 3】
The difference of LDHs metallic atom species is added during crystal growth in situ by changing, variety classes can be prepared
The cotton fiber of LDHs modifications is used for the absorption of anionic pollutant.
1）The mg/mL of 4 mL 2 dopamine alkaline solution is prepared, the pH of the solution is 8.5, is placed in atmosphere, pre- oxygen
Change to brown；
2）The cotton fiber for weighing 30 mg immerses step 1）In dopamine alkaline solution after the pre-oxidation of gained, magneton is added
4 h are stirred at room temperature, after being cleaned with deionized water, 6 h is dried under 60 °C, are repeated the above steps 1 time, after acquisition DOPA is amine-modified
Cotton fiber（PD@cotton）；
3）Prepare MgAl-LDHs reaction solutions, 0.051 g magnesium nitrate hexahydrates, 0.038 g ANN aluminium nitrate nonahydrates and 0.042 g urine
Plain mixed dissolution adds PD@cotton in 10 mL deionized waters, and 18 h, the cotton after the modification of LDHs crystal are reacted under 95 °C
After fiber is cleaned repeatedly with deionized water, 6 h are dried under 60 °C, obtain the cotton fiber after different LDHs crystal modifications（MgAl-
LDHs@PD@cotton）.
【Embodiment 4】
1）LDHs@PD@cotton are filled into different fixing devices, in syringe filters, chromatogram pre-column；
2）10 mL syringes suck the mg/L sample solutions of 5 mL 1（Ketoprofen and Congo red）, by peristaltic pump with 1 mL/min
Speed by LDHs@PD@cotton, raffinate is entered in high performance liquid chromatography and analyzed, testing result is as shown in Figure 5.
Cotton fiber is easy to compress, and can fill it into different device and be used for the absorption of anionic drugs and dyestuff,
Expand its application in practice.
Claims (5)
- A kind of 1. layered double hydroxide（LDHs）The preparation method of the cotton fiber of modification, it is characterised in that adopt first Cotton fiber, i.e., be immersed in the dopamine solution of pre-oxidation by the method modified with poly-dopamine, and formation has catechol The poly-dopamine layer of structure；Then, coordinate bond is formed using the metal ion in catechol group and LDHs reaction solutions, will LDHs crystal fixation in situ is on cotton fiber.
- 2. according to the method for claim 1, it is characterised in that described layered double hydroxide is NiAl-LDHs Crystal, concretely comprise the following steps：1）1 ~ 2 mg/mL dopamine alkaline solution is prepared, the pH of the solution is 8.5 ~ 9, is placed in atmosphere, and pre-oxidation is extremely Brown；2）The cotton fiber for weighing 30 ~ 200 mg immerses step 1）In dopamine alkaline solution after the pre-oxidation of gained, add 4 ~ 12 h are stirred at room temperature in magneton, after being cleaned with deionized water, 3 h are dried under 60 °C, repeats the above steps 1 time, obtains dopamine Cotton fiber PD@cotton after modification；3）Prepare NiAl-LDHs reaction solutions, 0.058 ~ 0.58 g Nickelous nitrate hexahydrates, 0.038 ~ 0.38 g ANN aluminium nitrate nonahydrates and 0.042 ~ 0.42 g urea mixed dissolution adds PD@cotton in 10 ~ 50 mL deionized waters, and reaction 12 under 70 ~ 100 °C ~ After cotton after the modification of 24 h, LDHs crystal is cleaned repeatedly with deionized water, 6 h are dried under 60 °C, obtain the modification of LDHs crystal Cotton fiber LDHs@PD@cotton afterwards.
- 3. the cotton fiber that layered double hydroxide prepared by a kind of method by any one of claim 1 or 2 is modified.
- 4. the cotton fiber of the layered double hydroxide modification described in claim 3 anionic drugs in environmental water sample Or the application in dyestuff contaminant absorption.
- 5. application according to claim 4, it is characterised in that the pollutant in described environmental water sample is dirty for anion Contaminate thing, by Ketoprofen and it is Congo red exemplified by.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801818A (en) * | 2019-10-25 | 2020-02-18 | 南昌大学 | Composite functional material for removing radioactive iodine and application thereof |
| CN112342788A (en) * | 2020-11-21 | 2021-02-09 | 浙江理工大学 | Flame-retardant moisture-absorbing fabric and preparation method thereof |
| CN114920274A (en) * | 2022-05-23 | 2022-08-19 | 暨南大学 | Polylactic acid composite material with surface modified with drug-loaded layered double hydroxide, and preparation method and application thereof |
| CN117567062A (en) * | 2024-01-16 | 2024-02-20 | 广州市克来斯特建材科技有限公司 | Concrete targeting agent and preparation method thereof |
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| CN102872829A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing lead ions from natural water and preparation method for adsorption material |
| CN105148877A (en) * | 2015-09-21 | 2015-12-16 | 武汉大学 | Method for fixing layered double hydroxide on surface of polypropylene and application of method |
| CN106637956A (en) * | 2016-10-31 | 2017-05-10 | 武汉大学 | Phosphate radical containing cotton modification material and preparation method and application thereof |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872829A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing lead ions from natural water and preparation method for adsorption material |
| CN105148877A (en) * | 2015-09-21 | 2015-12-16 | 武汉大学 | Method for fixing layered double hydroxide on surface of polypropylene and application of method |
| CN106637956A (en) * | 2016-10-31 | 2017-05-10 | 武汉大学 | Phosphate radical containing cotton modification material and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801818A (en) * | 2019-10-25 | 2020-02-18 | 南昌大学 | Composite functional material for removing radioactive iodine and application thereof |
| CN112342788A (en) * | 2020-11-21 | 2021-02-09 | 浙江理工大学 | Flame-retardant moisture-absorbing fabric and preparation method thereof |
| CN114920274A (en) * | 2022-05-23 | 2022-08-19 | 暨南大学 | Polylactic acid composite material with surface modified with drug-loaded layered double hydroxide, and preparation method and application thereof |
| CN114920274B (en) * | 2022-05-23 | 2024-03-15 | 暨南大学 | Polylactic acid composite material of surface-modified drug-loaded layered double hydroxide, and preparation method and application thereof |
| CN117567062A (en) * | 2024-01-16 | 2024-02-20 | 广州市克来斯特建材科技有限公司 | Concrete targeting agent and preparation method thereof |
| CN117567062B (en) * | 2024-01-16 | 2024-03-22 | 广州市克来斯特建材科技有限公司 | Concrete targeting agent and preparation method thereof |
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