CN106853363B - A kind of cyclodextrin supermolecule polymer/Fe3O4Magnetic nano-particle complex - Google Patents
A kind of cyclodextrin supermolecule polymer/Fe3O4Magnetic nano-particle complex Download PDFInfo
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- CN106853363B CN106853363B CN201710013546.4A CN201710013546A CN106853363B CN 106853363 B CN106853363 B CN 106853363B CN 201710013546 A CN201710013546 A CN 201710013546A CN 106853363 B CN106853363 B CN 106853363B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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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
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention provides a kind of cyclodextrin supermolecule polymer/Fe3O4Magnetic nano-particle complex, the complex are first to have synthesized a kind of cyclodextrin supermolecule polymer (β-CDSP) with beta-cyclodextrin and the crosslinking of Pyromellitic Acid dicarboxylic anhydride；β-CDSP and FeCl3·6H2O and FeCl2·4H2One kettle way is co-precipitated to obtain complex O under alkaline condition.It is characterized with X-ray diffraction (XRD), transmission electron microscope (TEM), infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) method, it was demonstrated that Fe3O4β-CDSP has been grafted on magnetic nano-particle.The complex synthesis cost is cheap, environment-protecting and non-poisonous, has hydroxyl abundant and free carboxyl and has preferable magnetic performance, can be used as a kind of adsorbent material of Liquidity limit type triphenylmethane dye pollutant.Study on adsorption properties is carried out using malachite green as Model Molecule, shows that complex has good adsorption effect to malachite green, and there is potential application foreground in terms of environmental contaminants adsorbent material.
Description
Technical field
The present invention relates to magnetic nanometer adsorbents and water-treatment technology field, and in particular to a kind of cyclodextrin supermolecule polymerization
Object/Fe3O4Magnetic nano-particle complex and its preparation method and application.
Background technique
Cationic triphenylmethane dye is the dyestuff that usage amount is the third-largest after azo dyes, anthraquinone dye,
A large amount of waste water are generated in production, use process.Such waste water color is deep, it is difficult to which environment is seriously polluted in biodegrade.Wherein most allusion quotation
The malachite green of type is used for ceramics, textile industry, leather industry and cytochemical staining as industrial dye；Because it is with antibacterial
The effect of desinsection, also frequently as fungicide.However, there is malachite green high toxicity, high residue and carcinogenic, teratogenesis, mutagenesis to make
With, and since its is soluble easily in water and is widely used, easily enter water body and cause water environment pollution problem, influences the strong of the mankind
Health.It can be seen that the malachite green in removal sewage is most important.
So far, the malachite green method for being mainly used for removing in aqueous solution includes light degradation, biodegrade and absorption
Effect.But due to malachite green not only light and heat effect under it is relatively stable, but also to oxidation and biodegrade have it is certain
Resistance, thus malachite green is removed as a kind of most effective method using suction-operated.Absorption method is as a kind of
Traditional wastewater treatment method, have many advantages, such as it is simple, efficient, economical, be acknowledged as effective ways in sewage treatment it
One.In absorption method, the selection of adsorbent is particularly important.Common adsorbents, such as active carbon, diatomite, resin, absorption effect
Rate is usually limited by specific surface area, difficult separation and recycling, the shortage conditions such as selectivity and dynamics.However, cyclodextrin modified
Magnetic Nano material not only possess biggish specific surface area, higher adsorption capacity, but also there is superparamagnetism, table outstanding
Now be exactly under conditions of externally-applied magnetic field, adsorbent can quick separating and recycling, effectively reduce secondary pollution, reduce economy
Cost.
In addition, carrying out functionalization to magnetic Nano material with macrocyclic host molecule is also current research hotspot.
Cyclodextrin has unique internal drainage, the structure of external hydrophilicity, can pass through molecule with pollutant as second generation supermolecule main block
Recognition reaction forms Host-guest inclusion complex, to reach the function of removal pollutant.Magnetic Nano material is mutually tied with cyclodextrin
It closes, forms the magnetic nanocomposites of cyclodextrin functionalization, it is made to have both the excellent magnetic property of magnetic nano-particle and oversubscription
The molecular recognition function of son, shows huge application potential in environmental area.
Summary of the invention
The purpose of the present invention is synthesize a kind of cyclodextrin supermolecule polymer/Fe3O4Magnetic nano-particle complex and its
Application in wastewater treatment.Complex be used for wastewater treatment when, under the action of externally-applied magnetic field, complex can quick separating and return
It receives, secondary pollution can be effectively reduced, reduce cost.
A kind of cyclodextrin supermolecule polymer/Fe provided by the invention3O4Magnetic nano-particle complex, by including such as
The method of lower step is prepared:
(1) preparation of β-CDSP: β-CD (1 equivalent) being added and dissolves and stirs in appropriate dimethyl sulfoxide (DMSO), after
A certain amount of triethylamine (the 1/4 of DMSO volume) is added, after five minutes, crosslinking agent pyromellitic acid anhydride (PMA) (2-4 is added
Equivalent), it reacts at room temperature, reaction solution gradually gelation；Fully reacting after 16-24h becomes blocky, with mortar grinder, after
It with secondary distilled water and acetone washing and filters respectively, then with after secondary water washing 3 times filterings, freeze-drying obtains white powder
β-CDSP；
(2) Fe of β-CDSP modification3O4The preparation of-MNPs: the FeCl for being 5 ︰ 1-2 of 10-8.5 ︰ by the mass ratio of the material3·
6H2O、 FeCl2·4H2O and β-CDSP is placed in reactor, the secondary water of addition reactor capacity 1/3-2/3, under nitrogen protection
To dissolving, 80 DEG C of temperature are kept for 5 minutes, and concentrated ammonia liquor is added dropwise and is adjusted to the pH of reaction solution 9-11 (preferably 10), mechanical for heating, stirring
It stirs (preferably 800r/min) and reacts 1.5-3 (preferably 2) hour, be cooled to room temperature, magnetic hysteresis separation, dark brown precipitating uses secondary water
Washing, then with ethanol washing to neutrality, 40-70 DEG C (preferably 60 DEG C) is dried in vacuo 12 hours, obtains β-CDSP-MNPs；
The method for removing water removal middle-jiao yang, function of the spleen and stomach ion triphenylmenthane pollutant with above-mentioned prepared β-CDSP-MNPs complex,
Step includes:
It will be in the waste water (preferably malachite green) for the cationic triphenylmethane dye pollutant that concentration is 3-40mg/L
Above-mentioned obtained β-CDSP-MNPs complex is added, the concentration of β-CDSP-MNPs is 0.125mg/mL, is vibrated at normal temperature
After 7h, magnetic hysteresis separation；Complex anhydrous ethanol elution, after sonic oscillation 10min, magnetic hysteresis separation, then with secondary water with
Dehydrated alcohol washs three times respectively, and vacuum drying obtains the magnetic nano complex of desorption, carries out cycling and reutilization.
Beneficial effects of the present invention compared with prior art:
The present invention is in Fe3O4The cyclodextrin of Cross-linked has been grafted on magnetic nano-particle, preparation method is simple, and it is low in cost,
Stability and favorable dispersibility.It combines the high-specific surface area of magnetic nano-particle, magnetic response feature and beta-cyclodextrin polymerization
The characteristics of object is to the packet of cationic triphenylmenthane pollutant and effect and electrostatic interaction, thus it is dirty to triphenylmethane in solution
Dye object has excellent adsorption capacity, can separate with solution rapidly in external magnetic field, Yi Huishou, reusable after desorption,
Save economic cost, easy to operate, Yi Shixian scale application.
Detailed description of the invention
Adsorption effect of Fig. 1 β-CDSP-MNPs in malachite green aqueous dye solutions.In figure: the left side is 2 × 10-5mol/L
Malachite green aqueous dye solutions；The effect picture that centre disperses for addition β-CDSP-MNPs；The right is magnetic hysteresis point after adsorption equilibrium
From effect picture.
The infrared spectrogram of Fig. 2 MNPs, β-CDSP and β-CDSP-MNPs.
The transmission electron microscope photo of Fig. 3 MNPs and β-CDSP-MNPs.
The x-ray diffraction pattern of Fig. 4 β-CDSP-MNPs.
The hysteresis loop figure of Fig. 5 MNPs and β-CDSP-MNPs.
The thermogravimetric analysis figure of Fig. 6 MNPs and β-CDSP-MNPs.
Influence of Fig. 7 pH to β-CDSP-MNPs and malachite green Dye Adsorption, supernatant after A: β-CDSP-MNPs absorption
The absorbance of liquid Malachite Green, A0: the absorbance of malachite green.
Influence of Fig. 8 ionic strength to β-CDSP-MNPs and malachite green Dye Adsorption, A: β-CDSP-MNPs absorption
The absorbance of supernatant Malachite Green afterwards, A0: the absorbance of malachite green.
Fig. 9 β-CDSP-MNPs is to malachite green curve of adsorption kinetics.
Figure 10 β-CDSP-MNPs is linear to the pseudo-first-order dynamics (a) of malachite green and pseudo-second order kinetic (b) model
Fitting
Figure 11 β-CDSP-MNPs is to malachite green adsorption isotherm curve.
Linear pass of Figure 12 β-CDSP-MNPs to Langmuir (a) and Freundlich (b) adsorption equilibrium of malachite green
System.
Figure 13 β-CDSP-MNPs's recycles figure.
Specific embodiment
The preparation of 1: β-CDSP-MNPs of embodiment
(1) preparation of β-CDSP: 2g β-CD is added and dissolves and stirs in 8mL dimethyl sulfoxide (DMSO), is added
2mL triethylamine is added 1.345g crosslinking agent pyromellitic acid anhydride (PMA), reacts at room temperature, reaction solution is gradually after five minutes
Gelation.Fully reacting after 16h becomes blocky, with mortar grinder, after with secondary distilled water and acetone washing and take out respectively
Filter, then with secondary water washing 3 times, freeze-drying obtains white powder β-CDSP.
(2) preparation of the MNPs of β-CDSP modification: by 1g FeCl3·6H2O、0.45g FeCl2·4H2O and 0.9g β-
CDSP is placed in reactor, and the secondary water of 200mL is added, and to dissolving, 80 DEG C of temperature are kept for 5 points for heating, stirring under nitrogen protection
Clock is added dropwise concentrated ammonia liquor for the pH of reaction solution and is adjusted to 10, mechanic whirl-nett reaction 2 hours, is cooled to room temperature, magnetic hysteresis separation, dark brown
Precipitate secondary water washing, then with ethanol washing to neutrality, 60 DEG C vacuum drying 12 hours, obtain β-CDSP-MNPs.
Unmodified MNPs is prepared under conditions of being added without β-CDSP with method identical with β-CDSP-MNPs,
With as a comparison.
It is shown from Fig. 2 infrared spectrogram, in the infrared spectroscopy of β-CDSP, 3500-3200cm-1Locating very strong broad peak is O-H
Form the association peak of hydrogen bond, 2930cm-1It is the stretching vibration peak of C-H on saccharide ring skeleton, 900-1200cm-1It is the spy of cyclodextrin
Peak is levied, the presence of cyclodextrin structure is shown.1730cm-1Place is the stretching vibration peak of C=O in carboxyl, 1345cm-1It is carboxyl
The stretching vibration peak of middle C-O, 1243cm-1It is the in-plane bending vibration peak of O-H in carboxyl, 931cm-1It is O- in carboxyl on phenyl ring
The out-of-plane bending vibration peak of H, 1478cm-1And 1591cm-1It is the framework deformation vibration peak of the C=C on phenyl ring, 839-706cm-1
It is the out-of-plane bending vibration peak of C-H on phenyl ring, sufficiently demonstrates Pyromellitic Acid and cyclodextrin is crosslinked, and maintain
Cellular construction it is complete.Compared with β-CDSP, the infrared spectroscopy of β-CDSP-MNPs has also appeared 587,1626,1400cm-13
Characteristic absorption peak, 587cm-1It is Fe for Fe-O key stretching vibration3O4The characteristic absorption peak of magnetic nano-particle；1626,
1400cm-12 characteristic absorption peaks are due to polymer surfaces-COOH and Fe3O4- the OH on magnetic nano-particle surface reacts life
Caused by the carboxylic acid type body for producing iron.Illustrate that β-CDSP is successfully grafted on MNPs.
The transmission electron microscope photo of Fig. 3 is shown: a and b is respectively the TEM photo of MNPs and β-CDSP-MNPs in figure.From figure
MNPs and β-CDSP-MNPs shape almost spherical or elliposoidal can be seen, favorable dispersibility has slight agglomeration.It is average
Partial size is not much different, and the average grain diameter of β-CDSP-MNPs is about 15nm, slightly larger than the average grain diameter of MNPs (approximate 12nm), this
It may be since the cyclodextrin molecular of crosslinking is grafted on caused by the surface of MNPs.
Fig. 4 is the X-ray diffracting spectrum (XRD) of β-CDSP-MNPs.2 θ are located at 30.90,35.58,43.01 in figure,
53.73,57.39,62.95 corresponding diffraction maximums correspond respectively to Fe3O4Face-centred cubic (220), (311), (400),
(422), (511) and (440) diffraction surfaces.The map one of bloodstone in the above results and JCPDS (No.85-1436) standard card
It causes, shows that the β-CDSP-MNPs of synthesis has cubic spinel structure.The most strong diffraction maximum (311) for choosing β-CDSP-MNPs is used
It is estimated in partial size, the average grain diameter that β-CDSP-MNPs is calculated by Scherrer formula (1) is 15.2nm, is measured with TEM
Particle size data is close.
D=0.89 λ/Bcos θ (1)
Wherein, D is average diameter/nm of particle, and 0.89 is Scherrer constant, and λ 0.154nm is X-ray wavelength,
B is the half-peak breadth of diffraction maximum, and θ is the angle of diffraction/rad.
Fig. 5 is the hysteresis loop figure of MNPs and β-CDSP-MNPs.Abscissa is applied field strengths, and ordinate is unit
Induced magnetism size of quality magnetic substance in the presence of externally-applied magnetic field.From the following figure, it can be seen that, two curves all pass through origin.
When externally-applied magnetic field is 0, the magnetic induction intensity of both the above substance is all 0, meets the concept of superparamagnetic, illustrates both the above object
Matter is superparamagnetism.It is tested to obtain result according to magnetic torque are as follows: the saturation magnetisation value of MNPs can reach 62emu/g, by it
Magnetic nanocomposites magnetization value is down to 59emu/g after grafting β-CDSP is wrapped up.Reason is analyzed it is considered that grafting β-CDSP
Afterwards, magnetic without significantly reduction MNPs.
It further confirms that β-CDSP is grafted the surface MNPs using thermogravimetric analysis (TGA), and determines containing for coating material
Amount.The thermogravimetric curve of MNPs and β-CDSP-MNPs is as shown in Figure 6.MNPs occurs weightlessness for the first time at 120 DEG C or so, this is
Caused by solvent (the water or ethyl alcohol) volatilization of MNPs adsorption.β-CDSP-MNPs within the scope of 50-150 DEG C remove first by weightlessness
After removing adsorption solvent, then due to the thermal decomposition of β-CDSP is weightless, weight-loss ratio 13.82%.Compared with MNPs, β-CDSP
Total weight-loss ratio is 18.54%, hence it is evident that than MNPs high, illustrates that β-CDSP is successfully modified to the surface MNPs.
Absorption of 2: the β-CDSP-MNPs of embodiment to malachite green dyestuff
(1) influence of the pH to β-CDSP-MNPs absorption property
Measure pure water and different pH (3-10) (NaCl of 0.001mol/L being added, adjust pH with HCl and NaOH afterwards) condition
Lower β-CDSP-MNPs adsorbs malachite green (2 × 10-5M the absorbance before and after) probes into pH to β-CDSP-MNPs absorption property
It influences.
(2) influence of the ionic strength to β-CDSP-MNPs absorption property
It measures under various concentration in the NaCl solution of (0,0.01,0.1,0.5,1,1.5,2mol/L), β-CDSP-MNPs
Adsorb malachite green (2 × 10-5M the absorbance before and after) probes into influence of the ionic strength to β-CDSP-MNPs absorption property.
(3) standard curve and its range of linearity of malachite green
Malachite green stock solution (2 × 10 is measured respectively-3M) 2 μ L, 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L, 60 μ L, 70 μ
L, 80 μ L, 90 μ L, 100 μ L, with secondary water constant volume to 4mL, sample solution surveys its absorbance at 617nm.With malachite green
Substance withdrawl syndrome (mol/L) is abscissa, and absorbance is ordinate, draws standard curve.
(4) research of the β-CDSP-MNPs to malachite green absorption property
Adsorption dynamics adsorption kinetics: it weighs 1.0mg β-CDSP-MNPs and is added to 4mL 4 × 10-5In M malachite green solution, in shaking table
Oscillation, different time points (0.5,1,2,3,4,5,6h) measure rapidly the absorbance value of supernatant, draw its adsorption dynamics adsorption kinetics song
Line.
Adsorption isotherm: it weighs 1mg β-CDSP-MNPs and is added to the malachite green aqueous solution that 4mL concentration is 3-40mg/L
In, after vibrating 7h at normal temperature, in the absorbance for measuring supernatant on ultraviolet-visible spectrophotometer after magnetic hysteresis separation
(at 617nm), and ask β-CDSP-MNPs to the adsorbance q of malachite green by formula 1e(mg/g):
In formula, ρ0It is initial concentration (mg/L), ρeIt is residual mass concentration (mg/L), V is adsorbent solution volume (L),
M is adsorbent mass (g), draws its adsorption isotherm.
From Fig. 7, it can be seen that under strong acid and basic conditions, the absorption property of β-CDSP-MNPs is bad, this is because being permitted
Polycation dyestuff mutability, aggregation, precipitating, unstable chemcial property under the conditions of strong acid and strong base；It is respectively 6,7,8,9 in pH
And when under the conditions of secondary water, absorption property is preferable, illustrates that this adsorbent application range is wider, and the subsequent selection of this experiment is secondary
It is carried out in water.
As shown in Figure 8, in the NaCl solution under secondary water and various concentration, the adsorption capacity of β-CDSP-MNPs changes
Less, illustrate that influence of the ion concentration to this adsorbent is little.As it can be seen that the application range of the adsorbent is wider, has and preferably answer
Use prospect.
β-CDSP-MNPs is to the adsorption dynamics adsorption kinetics of malachite green as shown in figure 9, due to a large amount of malachite green point at the beginning
Son diffuses to the surface β-CDSP-MNPs from solution, and mass transfer force is larger, and the rate of adsorption is higher, so adsorbance is in 60min
Inside increase rapidly.With the progress of adsorption process, the concentration difference of adsorbent surface and solution Malachite Green is strongly reduced, peacock
Malachite green molecule increases to the resistance of β-CDSP-MNPs diffusion into the surface, so that the rate of adsorption reduces, therefore the 1-6h rate of adsorption is more next
Slower, absorption basically reaches balance after 7h.
The kinetics equation that β-CDSP-MNPs is adsorbed after malachite green fitting is linearly as shown in Figure 10, pseudo-second order kinetic
Linear fit related coefficient (the R of equation2=0.99554) higher, show that the adsorption process of β-CDSP-MNPs more meets quasi- second level
Kinetics equation, adsorption process are chemisorption.
β-CDSP-MNPs is as shown in figure 11 to the adsorption isotherm of malachite green, as the increase of malachite green concentration is inhaled
Attached amount is gradually increased, and when equilibrium concentration increases to 20mg/L, absorption reaches balance.In order to further probe into its adsorption capacity, use
The analysis of Langmuir and Freundlich Isothermal Model, as shown in figure 12, the linearly dependent coefficient (R of Langmuir2=
0.99656) higher, maximal absorptive capacity 83mg/g shows that β-CDSP-MNPs more meets the adsorption process of malachite green
Langmuir Adsorption Model, the uniform adsorption of Ming Unit molecular layer of Shuoing play a leading role in adsorption process.
Embodiment 3: desorption and recycling situation are investigated
Complex does eluent with dehydrated alcohol, after sonic oscillation 10min, magnetic hysteresis separation, then with secondary water and anhydrous second
Alcohol washs three times respectively, and 60 DEG C of vacuum drying obtain the magnetic nano complex of desorption, carry out cycling and reutilization.The circulation weight
It carries out 3 times again, adsorbance of the β-CDSP-MNPs to malachite green in each circulation of calculating.
As shown in Figure 13, after β-CDSP-MNPs recycles 3 times, still there is higher adsorbance, illustrate β-CDSP-
MNPs is a kind of reusable Dye Adsorption material.Show that the complex has in dyestuff contaminant adsorbing domain preferably to answer
Use prospect.
Claims (6)
1. cyclodextrin supermolecule polymer/Fe3 O4 Magnetic nano-particle complex is in Liquidity limit type triphenylmethane dye
Application in pollutant；
Cyclodextrin supermolecule polymer/the Fe3 O4 Magnetic nano-particle complex, is prepared by a method comprising the following steps
It obtains:
(1) preparation of β-CDSP: β-CD is added and dissolves and stirs in appropriate dimethyl sulfoxide (DMSO), is then added a certain amount of
Triethylamine, after five minutes, be added crosslinking agent pyromellitic acid anhydride (PMA), react at room temperature, reaction solution gradually gelation；
Become bulk after 16-24h, after being grinded with a mortar, with secondary distilled water and acetone washing and filters respectively, obtained solid is washed again
3 times, filtering, freeze-drying obtains white powder β-CDSP；Wherein: the molar ratio of β-CD and pyromellitic acid anhydride is 1 ︰ 2-4；
(2) preparation of the MNPs of β-CDSP modification: being 5 ︰ 1-2 of 10-8.5 ︰ by FeCl by the mass ratio of the material3 ·6H2 O、
FeCl2 ·4H2 O and β-CDSP is placed in reactor, and the secondary water of reactor capacity 1/3-2/3 is added, adds under nitrogen protection
To dissolving, 80 DEG C of temperature are kept for 5 minutes, and concentrated ammonia liquor is added dropwise by the pH of reaction solution and is adjusted to 9-11, mechanic whirl-nett reaction for heat, stirring
It 1.5-3 hours, is cooled to room temperature, magnetic hysteresis separation, dark brown precipitates secondary water washing, then with ethanol washing to neutrality, 40-70
DEG C vacuum drying 12 hours, obtain β-CDSP-MNPs.
2. cyclodextrin supermolecule polymer/Fe as described in claim 13 O4 Magnetic nano-particle complex is in Liquidity limit
Application in type triphenylmethane dye pollutant, which is characterized in that the additional amount of triethylamine is DMSO body in the step (1)
Long-pending 1/4.
3. cyclodextrin supermolecule polymer/Fe as described in claim 13 O4 Magnetic nano-particle complex is in Liquidity limit
Application in type triphenylmethane dye pollutant, which is characterized in that the pH of reaction solution is adjusted to 10 in the step (2), machinery
Speed of agitator 800r/min reacts 2 hours.
4. cyclodextrin supermolecule polymer/Fe as described in claim 13 O4 Magnetic nano-particle complex is in Liquidity limit
Application in type triphenylmethane dye pollutant, which is characterized in that vacuum drying temperature is 60 DEG C in the step (2).
5. a kind of method for handling cationic triphenylmethane dye pollutant, which is characterized in that step includes: to be by concentration
β-CDSP- described in claim 1 is added in the waste water of the cationic triphenylmethane dye pollutant of 3-40mg/L
MNPs complex, the concentration of β-CDSP-MNPs is 0.125mg/mL, after vibrating 7h at normal temperature, magnetic hysteresis separation.
6. a kind of method for handling cationic triphenylmethane dye pollutant as claimed in claim 5, which is characterized in that
The cationic triphenylmethane dye pollutant is malachite green.
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| CN114279792B (en) * | 2021-12-30 | 2023-07-18 | 湖北大学 | Cyclodextrin/gold nanoparticle functionalized cotton fabric and preparation method and application thereof |
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| CN103977772B (en) * | 2014-05-16 | 2016-01-13 | 大连理工大学 | The preparation method of cyclodextrin modified magnetic nanometer adsorbent and the application in haemodialysis adsorption system thereof |
| CN104353434A (en) * | 2014-10-27 | 2015-02-18 | 山西大学 | Method for preparing magnetic nano-composites and removing phenols pollutants in water |
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