CN102240537A - Method for preparing organic dye absorbent - Google Patents
Method for preparing organic dye absorbent Download PDFInfo
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- CN102240537A CN102240537A CN2011101774472A CN201110177447A CN102240537A CN 102240537 A CN102240537 A CN 102240537A CN 2011101774472 A CN2011101774472 A CN 2011101774472A CN 201110177447 A CN201110177447 A CN 201110177447A CN 102240537 A CN102240537 A CN 102240537A
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Abstract
The invention provides a method for preparing an organic dye absorbent, which comprises the following steps: mixing graphite oxide and OH<-> in a solvent, reacting, regulating the pH value to 6 to 8, and thus obtaining solution A; adding Fe<3+> and Fe<2+> into the solution A, stirring and thus obtaining solution B; and adding OH<-> into the solution B, reacting, heating and thus obtaining the organic dye absorbent. Compared with the prior art, the method prepares the organic dye absorbent by using a coprecipitation process, avoids using toxic raw materials and helps to protect the environment. In addition, the invention also provides a method for removing organic micropollutants from water, which comprises the following steps: providing an aqueous solution which contains organic dye micropollutants having benzene rings; and adding the organic dye absorbent into the aqueous solution, so that the organic dye micropollutants are absorbed onto the organic dye absorbent. Experiment results indicate the method provided by the invention can remove organic dye micropollutants from water effectively.
Description
Technical field
The present invention relates to water and pollute processing technology field, more particularly, relate to a kind of preparation method of organic dye adsorbent namely.
Background technology
Along with the continuous development of industry, the water pollution problems that becomes increasingly conspicuous is also having a strong impact on expanding economy in the normal life that is threatening people.The pollutant that water pollutes mainly comprises inorganic micropollutants and organic micro-pollutants, and the pollutant that utilizes absorbent filtering to remove in the water is that present water pollutes the common method of handling.The existing more report of the adsorbent that water pollutes, as active carbon, activated alumina, silicon gel, polymeric material etc.But, problem such as the adsorbent of above-mentioned report exists can not recycling use, adsorption capacity is not strong.
(Science 2006 for " science " magazine, 314, the report nano ferriferrous oxide granule has very strong suction-operated to arsenic ion 964-967), (the Chem Commun of Britain imperial family chemistry meeting " chemical communication " simultaneously, 2007,4230-4232) the report nano ferriferrous oxide granule also has very strong suction-operated to the silver in the water, mercury and lead ion.In addition, nano ferriferrous oxide granule is the paramagnetism nano particle, can effectively separate it under the effect of outside magnetic field.Therefore, the correlative study personnel constantly study the adsorbent based on nano ferriferrous oxide granule.
(Small 2010 openly to have reported a kind of method based on growing nano ferriferrous oxide particles on the graphite oxide in the prior art; 6; No.2; 169-173); this method is dispersed in the graphite oxide of preparation in the kayexalate earlier; utilize the hydrazine hydrate reduction Graphene; Graphene after the reduction that will obtain after with washed with de-ionized water and ferric acetyl acetonade ultrasonic dispersion 30 minutes in three ethylidine glycol then; the rate of heat addition with 3 ℃/min is heated to 278 ℃ under magneton stirring and protection of nitrogen gas at last, obtains nano ferriferrous oxide granule.But, need be reactant with highly toxic hydrazine hydrate in the above-mentioned reported method, the hydrazine hydrate long term exposure in air or the short time can explosive decomposition when being subjected to high temperature action, and if the enrichment excessive concentration of hydrazine compound in the air, can cause atmosphere pollution, have potential carcinogenicity.
Therefore, the inventor considers, a kind of preparation method of organic dye adsorbent namely is provided, and it is raw material that this method need not with the noxious material, prepares a kind of organic dye adsorbent namely.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of organic dye adsorbent namely, and it is raw material that this method need not with the noxious material, prepares a kind of organic dye adsorbent namely.
The invention provides a kind of preparation method of organic dye adsorbent namely, may further comprise the steps:
With graphite oxide and OH
-Mix in solvent, pH value to 6～8 are regulated in the reaction back, obtain first solution;
In described first solution, add Fe
3+And Fe
2+, obtain second solution after the stirring;
In described second solution, add OH
-, the heating of reaction back obtains organic dye adsorbent namely.
Preferably, the pH value of described first solution is 6.8～7.2.
Preferably, describedly in first solution, add Fe
3+And Fe
2+Be specially:
In first solution, add FeCl
36H
2O and FeCl
24H
2The aqueous solution of O.
Preferably, described Fe
3+With Fe
2+Mol ratio be 1.5～2.5: 2.5～3.5.
Preferably, described Fe
3+With Fe
2+Mol ratio be 2: 3.
Preferably, the described mixing time that obtains second solution is 5～15h.
Preferably, the described mixing time that obtains second solution is 7h.
Preferably, describedly in second solution, add OH
-Be specially:
The ammoniacal liquor that in second solution, adds 1.5mol/L.
Accordingly, the present invention also provides a kind of method of removing the organic dyestuff micropollutants from water, comprising:
The aqueous solution is provided, and the described aqueous solution comprises the organic dyestuff micropollutants that contain phenyl ring;
The organic dye adsorbent namely of technique scheme preparation is placed the described aqueous solution, described organic dyestuff micropollutants are adsorbed on the described organic dye adsorbent namely.
Preferably, described organic micro-pollutants is rhodamine B, rose-red, orange, sour indigo plant, malachite green and/or famille rose.
The invention provides a kind of preparation method of organic dye adsorbent namely, may further comprise the steps: with graphite oxide and OH
-Mix in solvent, pH value to 6～8 are regulated in the reaction back, obtain first solution; In described first solution, add Fe
3+And Fe
2+, obtain second solution after the stirring; In described second solution, add OH
-, the heating of reaction back obtains organic dye adsorbent namely.Compared with prior art, the present invention is at first with graphite oxide and OH
-Reaction, thus the carboxyl on graphite oxide surface is converted into carboxylic acid ion, in described first solution, add Fe then
3+And Fe
2+, make Fe
3+And Fe
2+Be adsorbed in the graphite oxide surface, in second solution, add OH at last
-Thereby, Fe
3+, Fe
2+With OH
-Reaction, obtaining Graphene-ferriferrous oxide nano compound is organic dye adsorbent namely.Therefore, adopt coprecipitation to prepare organic dye adsorbent namely, need not with the noxious material is raw material, has protected environment.Experimental result shows that the organic dye adsorbent namely of the present invention's preparation has the performance of cycling and reutilization.
In addition, the present invention also provides a kind of method of removing the organic dyestuff micropollutants from water, and comprising: the aqueous solution is provided, and the described aqueous solution comprises the organic dyestuff micropollutants that contain phenyl ring; The organic dye adsorbent namely of technique scheme preparation is placed the described aqueous solution, described organic dyestuff micropollutants are adsorbed on the described organic dye adsorbent namely.Experimental result shows that method provided by the invention can be removed the organic dyestuff micropollutants in the water effectively.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the transmission electron microscope picture of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 2 is the transmission electron microscope picture of Graphene nano surface particle in the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 3 is the X ray diffracting spectrum of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 4 is the narrow journey scanning spectrum of Fe2p photoelectron spectroscopy of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 5 is the narrow journey scanning spectrum of Fe2p photoelectron spectroscopy of the organic dye adsorbent namely of a recycling in the embodiment of the invention 2;
Fig. 6 is the scanning tunneling microscope photo of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 7 is the scanning tunneling microscope photo of the organic dye adsorbent namely of a recycling in the embodiment of the invention 2;
Fig. 8 is the narrow journey scanning spectrum of photoelectron spectroscopy of O1s of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Fig. 9 is the narrow journey scanning spectrum of the photoelectron spectroscopy of the O1s of the organic dye adsorbent namely of a recycling in the embodiment of the invention 2;
Figure 10 is the magnetization curve of the organic dye adsorbent namely of the embodiment of the invention 1 preparation;
Figure 11 is the magnetization curve of the organic dye adsorbent namely of a recycling in the embodiment of the invention 2;
Figure 12 is organic dye adsorbent namely, the organic dye adsorbent namely before and after the recycling and the Raman spectrum of rhodamine B of the embodiment of the invention 1 preparation;
Figure 13 is the absorption property block diagram of organic dye adsorbent namely in the embodiment of the invention 3;
Figure 14 is the absorption property block diagram behind the organic dye adsorbent namely cycling and reutilization in the embodiment of the invention 4;
Figure 15 is the scanning tunneling microscope photo of the nano ferriferrous oxide granule of comparative example 1 preparation of the present invention;
Figure 16 is comparative example 1 a disclosed rhodamine B solution absorbency collection of illustrative plates of the present invention.
The specific embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
The invention discloses a kind of preparation method of organic dye adsorbent namely, may further comprise the steps:
With graphite oxide and OH
-Mix in solvent, pH value to 6～8 are regulated in the reaction back, obtain first solution;
In described first solution, add Fe
3+And Fe
2+, obtain second solution after the stirring;
In described second solution, add OH
-, the heating of reaction back obtains organic dye adsorbent namely.
The graphite oxide that the present invention adopts is preferably the graphite oxide that adopts the preparation of Hummers method.Described with graphite oxide and OH
-The step of mixing in solvent is specially: graphite oxide is added deionized water for ultrasonic disperse, add NaOH solution then.Described adjusting pH value to 6～8 are specially: the solution that will obtain after will reacting is dialysed to the pH value and is 6～8, and preferred, described pH value is 6.8～7.2, most preferably is 7.
Because the present invention is at first with graphite oxide and OH
-Reaction is converted into carboxylic acid ion with the carboxyl on graphite oxide surface, adds Fe then in described first solution
3+And Fe
2+Thereby, make Fe
3+And Fe
2+Be adsorbed in the graphite oxide surface.
After obtaining first solution, in described first solution, add Fe
3+And Fe
2+, be specially: in first solution, add FeCl
36H
2O and FeCl
24H
2The aqueous solution of O.Described Fe
3+With Fe
2+Mol ratio be preferably 1.5～2.5: 2.5～3.5, more preferably 2: 3.The described mixing time that obtains second solution is preferably 5～15h, and more preferably 6～10h most preferably is 7h.After obtaining second solution, in described second solution, add OH
-Be specially: the ammoniacal liquor that in second solution, adds 1.5mol/L.By in described second solution, adding OH
-, following reaction has taken place:
Fe
2++2Fe
3++8OH
-→Fe
3O
4+4H
2O
Described heating-up temperature is preferably 60～70 ℃, more preferably 65 ℃; Be preferably 2～5h, more preferably 2～3h described heat time heating time; Described mode of heating preferably adopts the water-bath heating.
This experimental technique is to adopt the coprecipitation ferroferric oxide nano granules of growing on graphite oxide, because Fe in this method
3+Be far longer than Fe with the affinity of carboxylic acid ion
2+, simultaneously in course of reaction, the Fe of part
2+Also easily be oxidized to Fe
3+, therefore, Fe described in the present invention
3+And Fe
2+Mol ratio most preferably be 2: 3.
RGO-Fe in the present invention's preparation
3O
4In the nano-complex, because Graphene has very strong absorption property to various organic dyestuff, has bigger adsorption capacity, tri-iron tetroxide also can adsorb inorganic heavy metal ion simultaneously, in addition, tri-iron tetroxide is as a kind of paramagnetic material, under the effect of outside magnetic field easily with its adsorbent and moisture from, thereby reach the purpose of recovery.
Compared with prior art, the present invention is at first with graphite oxide and OH
-Reaction, thus the carboxyl on graphite oxide surface is converted into carboxylic acid ion, in described first solution, add Fe then
3+And Fe
2+, make Fe
3+And Fe
2+Be adsorbed in the graphite oxide surface, in second solution, add OH at last
-, Fe
3+, Fe
2+With OH
-Reaction, obtaining Graphene-ferriferrous oxide nano compound is organic dye adsorbent namely.Therefore, adopt coprecipitation to prepare organic dye adsorbent namely, need not with the noxious material is raw material, has protected environment, can not produce harm to human body.In addition, preparation method provided by the invention need not the high temperature heating, and is simple to operate.
In addition, the present invention also provides a kind of method of removing the organic dyestuff micropollutants from water, comprising:
The aqueous solution is provided, and the described aqueous solution comprises the organic dyestuff micropollutants that contain phenyl ring;
The organic dye adsorbent namely of technique scheme preparation is placed the described aqueous solution, described organic dyestuff micropollutants are adsorbed on the described organic dye adsorbent namely.
The organic dye adsorbent namely that is adsorbed with the organic dye micropollutants is calcined under 400 ℃, the environment of argon gas, the organic dyestuff micropollutants are fully degraded, the organic dye adsorbent namely of the preparation of the present invention simultaneously can reuse.
For Graphene and graphite oxide, because himself particular structure makes it generally form π-πGong Ezuoyong with the organic matter that has phenyl ring.Because the interaction force of this conjugation makes Graphene or graphite oxide to the organic matter that has phenyl ring very strong absorption property be arranged all.Therefore, the organic dyestuff micropollutants that contain phenyl ring are easy to form π-πGong Ezuoyong with the organic dye adsorbent namely of the present invention's preparation, experimental result shows that the organic dye adsorbent namely of the present invention's preparation has very strong absorption property to the organic dyestuff micropollutants that contain phenyl ring.
Organic micro-pollutants described in the present invention is preferably rhodamine B (Rhodamine B), rose-red (Rhodamine 6G), orange (Orange pure), acid blue (Acid blue), malachite green (Manachint green) and/or famille rose (New coccine pure).The organic dye adsorbent namely of the present invention's preparation all has absorption for the organic dye molecule of above-mentioned organic dyestuff in the visible region, all have it to absorb characteristic peak.Therefore, the present invention preferably by utilizing the uv-visible absorption spectra instrument to measure the variation of the absorbance behind the adsorbents adsorb organic dyestuff, calculates the adsorbance of adsorbent to organic dyestuff.
Because adsorbent, can reclaim and prerequisite that repeatedly cycling and reutilization is its maximum that enters society.The organic dye adsorbent namely of the present invention's preparation has the nano-complex of tri-iron tetroxide for the Graphene superficial growth, because tri-iron tetroxide is a paramagnet, easily separate under the effect of outside magnetic field, thereby provide advantageous conditions for the recovery of the adsorbent of the present invention preparation.
In order to further specify technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment 1
The preparation organic dye adsorbent namely:
The graphite oxide that takes by weighing the preparation of 20mg Hummers method adds in the deionized water of 40mL, and ultrasonic dispersion under lower powered ultrasonic machine, the scattered fully NaOH solution with employing 0.1mol/L is regulated its pH to 12, leave standstill after 2 hours in its bag filter of packing into, dialyse with deionized water, take out bag filter when the PH of extracellular fluid dialysis is 7 left and right sides, demarcating with deionized water is 60ml, obtains first solution;
Getting 15mL, to contain quality be three mouthfuls of round-bottomed flasks that described first solution of the graphite oxide of 5mg is put into 50mL, stirs at the mechanical agitation speed lower magnetic force of 1500rpm, and letting nitrogen in and deoxidizing 1h adds 1mL then and contains 6mg FeCl
36H
2The first source of iron solution and the 1.5mL of O contain 95mg FeCl
24H
2The second source of iron solution of O continues to stir and letting nitrogen in and deoxidizing 7h, obtains second solution;
In described second solution, dropwise add the NH that concentration is 1.5M
4OH solution 1.5mL, vigorous stirring, and in 65 ℃ water-bath, heat 2.5h, the black precipitate RGO-Fe that obtains
3O
4, promptly organic dye adsorbent namely (is called for short RGO-Fe
3O
4).
After the organic dye adsorbent namely of above-mentioned preparation spent deionised water sample three times, the aaerosol solution of this adsorbent is dripped on 2～3 plating carbon film copper mesh of using to testing electronic microscope, after treating that solvent volatilizees fully, it is that 200,000 volts JOEL2100 type high resolution transmission electron microscopy is observed down that the plating carbon film copper mesh that is loaded with adsorbent is positioned over accelerating potential.Fig. 1 is the transmission electron microscope picture of the organic dye adsorbent namely of present embodiment preparation, and as can be seen from the figure, ferroferric oxide nano granules is dispersed on the Graphene surface, and average diameter is 30 ± 10nm.Fig. 2 is (220) face of the tri-iron tetroxide of cubic system by the spacing of lattice analysis, thereby has proved that nano particle is a tri-iron tetroxide for the transmission electron microscope picture of Graphene nano surface particle in the organic dye adsorbent namely of the present invention's preparation.
Fig. 3 is the X ray diffracting spectrum of the organic dye adsorbent namely of present embodiment preparation, and the incident wavelength of X ray is 1.541841A °, and diffraction maximum is corresponding with the diffraction data of tri-iron tetroxide among the JCPDS No.86-1361 in this collection of illustrative plates.
Embodiment 2
The nano-complex that detects embodiment 1 preparation is to the attached effect of the absorption-desorption of rhodamine B:
The organic dye adsorbent namely of embodiment 1 preparation is mixed with rhodamine B, after 12 hours, separate organic dye adsorbent namely and rhodamine B by magnet, and spend deionised water repeatedly, do not present up to supernatant till the redness of rhodamine B, with the sample freeze drying, get sample segment afterwards, and to put it in the tube furnace in argon stream be 100sccm, annealed 1 hour down, obtain the organic dye adsorbent namely after the annealing in process one time for 400 ℃.
Fig. 4 is the narrow journey scanning spectrum of Fe2p photoelectron spectroscopy of the organic dye adsorbent namely of the embodiment of the invention 1 preparation, and curve a is RGO-Fe
3O
4The narrow journey scanning spectrum of photoelectron spectroscopy of Fe2p; B is for passing through Thermo Scientific Avantage with RGO-Fe
3O
4The Fe2p of narrow journey scanning spectrum swarming of photoelectron spectroscopy of Fe2p
1/2C is for passing through Thermo Scientific Avantage with RGO-Fe
3O
4The Fe2p of narrow journey scanning spectrum swarming of photoelectron spectroscopy of Fe2p
3/2Fig. 5 is the narrow journey scanning spectrum of Fe2p photoelectron spectroscopy of the organic dye adsorbent namely of a recycling in the present embodiment, and d is through the RGO-Fe of a recycling in the present embodiment
3O
4The narrow journey scanning spectrum of photoelectron spectroscopy of Fe2p; E is will be through the RGO-Fe of a recycling by Thermo Scientific Avantage
3O
4The Fe2p of narrow journey scanning spectrum swarming of photoelectron spectroscopy of Fe2p
1/2F is will be through the RGO-Fe of a recycling by Thermo Scientific Avantage
3O
4The Fe2p of narrow journey scanning spectrum swarming of photoelectron spectroscopy of Fe2p
3/2Can draw by comparison diagram 4 and Fig. 5, two peaks that are positioned at 710.66eV and 723.72eV correspond respectively to Fe
3O
4Middle Fe2p
1/2And Fe2p
3/2Electron binding energy, and near 719eV, do not have tangible shock excitation satellite peak to occur, hence one can see that, the organic dye adsorbent namely of embodiment 1 preparation and through all there not being γ-Fe in the organic dye adsorbent namely of a recycling
2O
3Thereby, proved that annealing is to Fe under this condition
3O
4Nano particle is influence not.
Fig. 6 is the scanning tunneling microscope photo of the organic dye adsorbent namely of embodiment 1 preparation; Fig. 7 is the scanning tunneling microscope photo of the organic dye adsorbent namely of a recycling in the present embodiment, as can be seen from Figures 6 and 7, significant change does not take place in the ferroferric oxide nano granules pattern in the organic dye adsorbent namely of a recycling.
Fig. 8 is the narrow journey scanning spectrum of photoelectron spectroscopy of O1s of the organic dye adsorbent namely of embodiment 1 preparation; Curve a is RGO-Fe
3O
4The narrow journey scanning spectrum of photoelectron spectroscopy of O1s; B is for passing through Thermo Scientific Avantage with RGO-Fe
3O
4The Fe-O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s; C is for passing through Thermo Scientific Avantage with RGO-Fe
3O
4The C=O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s; D is for passing through Thermo Scientific Avantage with RGO-Fe
3O
4The C-O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s.Fig. 9 is the narrow journey scanning spectrum of the photoelectron spectroscopy of the O1s of the organic dye adsorbent namely of a recycling in the present embodiment 2, and e is the RGO-Fe through a recycling
3O
4The narrow journey scanning spectrum of photoelectron spectroscopy of O1s; F is will be through the RGO-Fe of a recycling by Thermo Scientific Avantage
3O
4The Fe-O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s; G is will be through the RGO-Fe of a recycling by Thermo Scientific Avantage
3O
4The C=O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s; H is will be through the RGO-Fe of a recycling by Thermo Scientific Avantage
3O
4The C-O peak of narrow journey scanning spectrum swarming of photoelectron spectroscopy of O1s.By Fig. 8 and Fig. 9 as can be seen, the reducing degree of the graphite oxide after the annealing improves.
Figure 10 is the magnetization curve (M-H curve) of the organic dye adsorbent namely of embodiment 1 preparation; Figure 11 is the M-H curve of the organic dye adsorbent namely of a recycling in the present embodiment 2.From Figure 10 and Figure 11 as can be seen, RGO-Fe
3O
4The regenerative process of compound is to the almost not influence of magnetic property of ferroferric oxide nano granules.
The organic dye adsorbent namely and the concentration of a recycling in the organic dye adsorbent namely of embodiment 1 preparation, the present embodiment for carrying out Raman, the 0.05mol/L rhodamine B are characterized, as shown in figure 12, Figure 12 is organic dye adsorbent namely, the organic dye adsorbent namely before and after the recycling and the Raman spectrum of rhodamine B of the embodiment of the invention 1 preparation; Curve a is the Raman spectrum of Rhb; B is that Rhb is by RGO-Fe
3O
4Raman spectrum after the adsorbents adsorb; C is RGO-Fe
3O
4Raman spectrum; D is that Rhb is by RGO-Fe
3O
4Be 100sccm in argon stream after the adsorbents adsorb, at 400 ℃ of annealing Raman spectrums after 1 hour down.As can be seen from Figure 10, the organic dye adsorbent namely of preparation has only the D peak and the G peak characteristic peak of two Graphenes, and two apparent in view 1200cm occurred for the adsorbent that adsorbed rhodamine B
-1And 1512cm
-1The characteristic peak of rhodamine B, having proved that rhodamine B is adsorbed rather than is decomposed waits other reason, and also only find two characteristic peaks of Graphene for adsorbing the sample of annealing later, illustrate that rhodamine B has been thermal decomposited or, also proved the cycling and reutilization that to realize adsorbent with this processing method by desorption.
Embodiment 3
At first get 12 cleaned vials, configuration concentration is 5 * 10 respectively
-3The mol/L rhodamine B, rose-red, orange, acid is blue, malachite green, carmine six kinds of organic dyestuff, in 6 bottles wherein, add the deionized water of 20mL and 6 kinds of organic dyestuff of 20 μ L, add the deionized water of 19.8mL and 6 kinds of organic dyestuff of 20 μ L in other 6 bottles, in the bottle of adding 19.8mL deionized water, add the organic dye adsorbent namely that 0.2mL contains the embodiment of the invention 1 preparation of 10mg then respectively, observation obtains: the initial concentration of 6 kinds of dyestuffs is the same, the organic dye adsorbent namely absorption that is implemented example 1 preparation is after 1 minute, and under the external magnet effect, organic dye adsorbent namely is split into the bottom of bottle, discovery that can be clearly adds the color of the various dyestuffs in the bottle of adsorbent takes off fully, becomes as clear as crystal free of contamination water.
The test concrete steps of maximum adsorption value are as follows:
At first dispose the organic dyestuff solution of series of standards concentration, survey its absorbance by ultraviolet-visible spectrometer and obtain the normal concentration curve, next configuration concentration scope organic dyestuff solution in the normal concentration curve, get the centrifuge tube of 11 10mL, to the organic dyestuff solution that wherein adds 10mL, last configuration concentration is the adsorbent suspension of 25mg adsorbent/1mL deionized water respectively, adds 10 μ L in the 10 organic dyestuff solution centrifugal pipes in 11 respectively after shaking up, 20 μ L, 30 μ L, 40 μ L, 50 μ L, 10 μ L, 20 μ L, 30 μ L, 40 μ L, the suspension of the adsorbent of 50 μ L, one of them does not add, and after 12 hours, tests the variation of its absorbance excessively, the reference standard concentration curve draws the maximum adsorption value of sample, averages at last.In like manner, the peaked assay method of the absorption of other various organic dyestuff all adopts this method, thereby has obtained the maximum adsorption value of adsorbent to various organic dyestuff.Figure 13 is the absorption property block diagram of organic dye adsorbent namely in the present embodiment.
Embodiment 4
Adsorbent is to the performance of the attached cycling and reutilization of the absorption-desorption of rhodamine B:
RGO-Fe with embodiment 1 preparation
3O
4The rhodamine B that adsorbents adsorb is excessive, after 12 hours, separate by magnet, spend deionised water repeatedly, do not present up to supernatant till the color of rhodamine B solution, with the sample freeze drying, and to put it in the tube furnace in argon stream be 100sccm, annealed 1 hour down at 400 ℃, repeat to test among the embodiment 2 various organic dyestuff with its sample again and adsorb peaked experimental technique, measurement was moved back once fire back sample to the suction-operated of rhodamine B sample, the fire experiment of retiring from active military service of laying equal stress on is carried out cycling and reutilization to sample and is tested its absorption maximum.Figure 14 is the absorption property block diagram behind the organic dye adsorbent namely cycling and reutilization in the present embodiment, as can be seen from the figure, adopt the absorption property of the method adsorbent of annealing not have too much influence, after four annealing, the variation of its maximum adsorption value is very little, therefore, the RGO-Fe of the present invention's preparation
3O
4Adsorbent has the performance of cycling and reutilization.
Comparative example 1
Measure the absorption property of ferroferric oxide nano granules to rhodamine B:
With the deionized water letting nitrogen in and deoxidizing of 15mL, and under 65 ℃, heat 15min, add the FeCl that 5mL contains 6mg
36H
2The FeCl of O and 95mg
24H
2The deionized water solution of O dropwise adds the NH that 2mL concentration is 1.5M behind the water-bath 5min
4OH, vigorous stirring adds NH
4Behind the OH solution is heated about 15min in air atmosphere, utilize the magnet partition method to spend the deionised water sample three times, the gained black precipitate is ferroferric oxide nano granules.
Get above-mentioned sample aaerosol solution dropping 2～3 and drip to SiO
2On the substrate, treat that solvent volatilizees fully after, will be loaded with the SiO of product
2Substrate is put to being to take pictures under 10000 volts the Sirion 200 type scanning tunneling microscopes at accelerating potential.As shown in figure 15, be the scanning tunneling microscope photo of the nano ferriferrous oxide granule of this comparative example preparation.As can be seen from the figure, the average diameter of the nano ferriferrous oxide granule size of this comparative example preparation is at 30 ± 10nm, with the sizableness of the ferroferric oxide nano granules of product among the embodiment 1.
With the preparation ferroferric oxide nano granules carry out vacuum freeze drying after, the nano ferriferrous oxide granule that takes by weighing the above-mentioned preparation of 10mg afterwards joins in the rhodamine B solution, test ferroferric oxide nano granules respectively and add variation preceding and the rhodamine B solution absorbency of ferroferric oxide nano granules adding after 9 hours, as shown in Figure 5, be rhodamine B solution absorbency collection of illustrative plates in this comparative example, a curve is the absorption spectra of the rhodamine B solution of normal concentration; The b curve is the Fe that adds 10mg in the Rhb of normal concentration
3O
4The absorption spectra of nano particle absorption after 9 hours.As can be seen from the figure, almost do not change with the rhodamine B solution absorbency of ferroferric oxide nano granules adding after 9 hours before ferroferric oxide nano granules adds, proved that ferroferric oxide nano granules does not have suction-operated to rhodamine B.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of an organic dye adsorbent namely may further comprise the steps:
With graphite oxide and OH
-Mix in solvent, pH value to 6～8 are regulated in the reaction back, obtain first solution;
In described first solution, add Fe
3+And Fe
2+, obtain second solution after the stirring;
In described second solution, add OH
-, the heating of reaction back obtains organic dye adsorbent namely.
2. preparation method according to claim 1 is characterized in that, the pH value of described first solution is 6.8～7.2.
3. preparation method according to claim 1 is characterized in that, describedly adds Fe in first solution
3+And Fe
2+Be specially:
In first solution, add FeCl
36H
2O and FeCl
24H
2The aqueous solution of O.
4. preparation method according to claim 1 is characterized in that, described Fe
3+With Fe
2+Mol ratio be 1.5～2.5: 2.5～3.5.
5. preparation method according to claim 1 is characterized in that, described Fe
3+With Fe
2+Mol ratio be 2: 3.
6. preparation method according to claim 1 is characterized in that, the described mixing time that obtains second solution is 5～15h.
7. preparation method according to claim 6 is characterized in that, the described mixing time that obtains second solution is 7h.
8. preparation method according to claim 1 is characterized in that, describedly adds OH in second solution
-Be specially:
The ammoniacal liquor that in second solution, adds 1.5mol/L.
9. method of removing the organic dyestuff micropollutants from water comprises:
The aqueous solution is provided, and the described aqueous solution comprises the organic dyestuff micropollutants that contain phenyl ring;
The organic dye adsorbent namely of any preparation of claim 1～8 is placed the described aqueous solution, described organic dyestuff micropollutants are adsorbed on the described organic dye adsorbent namely.
10. method according to claim 9 is characterized in that, described organic micro-pollutants is rhodamine B, rose-red, orange, sour indigo plant, malachite green and/or famille rose.
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| CN106268637A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | A kind of viscose rayon adsorbing material modified based on graphene oxide and preparation thereof and application |
| CN106390915A (en) * | 2016-12-05 | 2017-02-15 | 郑州丽福爱生物技术有限公司 | Dye pollution adsorbent, and preparation method and application thereof |
| CN108479703A (en) * | 2018-04-18 | 2018-09-04 | 安徽农业大学 | A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal |
| CN110586024A (en) * | 2019-10-18 | 2019-12-20 | 北京工业大学 | Arsenic removal magnetic nano adsorbent gamma-Fe prepared based on biological filter backwashing iron mud2O3Method (2) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102583336A (en) * | 2012-01-20 | 2012-07-18 | 厦门大学 | Preparation method of magnetic-functionalized graphene composite material |
| CN102583336B (en) * | 2012-01-20 | 2014-09-03 | 厦门大学 | Preparation method of magnetic-functionalized graphene composite material |
| CN106268637A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | A kind of viscose rayon adsorbing material modified based on graphene oxide and preparation thereof and application |
| CN106390915A (en) * | 2016-12-05 | 2017-02-15 | 郑州丽福爱生物技术有限公司 | Dye pollution adsorbent, and preparation method and application thereof |
| CN108479703A (en) * | 2018-04-18 | 2018-09-04 | 安徽农业大学 | A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal |
| CN110586024A (en) * | 2019-10-18 | 2019-12-20 | 北京工业大学 | Arsenic removal magnetic nano adsorbent gamma-Fe prepared based on biological filter backwashing iron mud2O3Method (2) |
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