CN107970878A - A kind of preparation method of phosphate group functionalization hollow mesoporous silica microsphere - Google Patents
A kind of preparation method of phosphate group functionalization hollow mesoporous silica microsphere Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of phosphate group functionalization hollow mesoporous silica microsphere composite material, synthetic route is divided into three steps, the monodispersed carbon ball of big particle diameter is prepared using glucose hydro-thermal method first, the use of the carbon ball of synthesis is then hard template, cetyl trimethylammonium bromide（CTAB）Hollow mesoporous silica microsphere is synthesized for soft template, phosphate group functionalization hollow mesoporous silica microsphere is finally synthesized using rear grafting grafting phosphate group on this basis.The hollow mesoporous material of functionalization of synthesis has the core-shell structure of well-regulated meso-hole structure, monodispersed particle diameter distribution and stabilization, there is efficient absorption property to Determination of Trace Amounts of Antimony, have a good application prospect in terms of Determination of Trace Amounts of Antimony water pollution processing and drinking water processing up to standard.
Description
Technical field
The invention belongs to organo-mineral complexing functionalization materials synthesis, and in particular to a kind of hollow Jie of phosphate group functionalization
The preparation method of hole silicon dioxide microsphere material.
Background technology
The pollution and prevention of water resource is all the time global important topic, with industrial development and mankind's activity
Influence, the concentration of antimony increases year by year in water environment, antimony ore be both antimony resource locality, since waste discharge is big dirt again
Dye source.The concentration of antimony is less than 1 μ g/L in natural fresh water, but the content of antimony is up to hundreds of or even thousands of μ in the water body in minery
g/L.Antimony has carcinogenicity, and when human body is by drinking contaminant water, the sulfydryl in people's vivo protein can be combined with antimony, suppress to dredge
The activity of base enzyme, carrys out very big harm to health care belt.The antimony removal technology of comparative maturity includes reverse osmosis, solvent extraction at present, from
Son exchanges and absorption etc., wherein absorption method with its simple and quick, economical and efficient, it is renewable the features such as and be widely used, and mesh
Adsorbent is generally bad to the adsorption effect of Determination of Trace Amounts of Antimony used by preceding.Therefore, there is an urgent need to a kind of cheap efficient method pair
Increasing trace stibium-containing wastewater is administered.
Mesoporous SiO2There is microballoon high-specific surface area, big pore volume, surface to have a large amount of modifiable silicone hydroxyls, good
The advantageous property such as chemical inertness and biocompatibility, almost meets people's being required to ideal carrier.It is mesoporous with tradition
SiO2Microballoon is compared, and has hollow inside and the mesoporous SiO of permeability2The hollow mesoporous SiO of shell structure2Microballoon（HMSs）Also have
There is the cavity that density is low, huge to store the characteristics such as more guest molecules.But the material is currently used primarily in pharmaceutical carrier with delaying
Release field, such as Zhu（Zhu Y, Shi J, Chen H, et al. A facile method to synthesize
novel hollow mesoporous silica spheres and advanced storage property[J].
Microporous and Mesoporous Materials, 2005, 84(1): 218-222.）It has studied mesoporous hollow
SiO2Microballoon is to the useful load of ibuprofen pharmaceutical molecule, Guo etc.（Guo H, Qian H, Sun S, et al. Hollow
mesoporous silica nanoparticles for intracellular delivery of fluorescent dye
[J]. Chemistry Central Journal, 2011, 5(1): 1.）Synthesized using the method for sol-gel/lotion
Average pore size is 2 nm, surface area is 880 m2The mesoporous hollow SiO of/g2Particle, and study its suction to fluorescein isothiocyanate
It is attached come aids drug transportation behavior.In terms of adsorption treatment of the hollow mesoporous silica microsphere material as heavy metal in water
Research is few with application.Therefore, a kind of new function hollow silica sorbing material is developed, it had both been possessed hollow Jie
High efficiency of additive capability of the superperformance of hole silicon dioxide microsphere material but also with modified group for antimony, has important theory
Meaning and actual application value.
Researcher Marcinko etc.（Marcinko, Stephen, and Y. F. Alexander. Hydrolytic
stability of organic monolayers supported on TiO2 and ZrO2. Langmuir, 2004,
20(06): 2270-2273.）It was found that robustness and stability that phosphonic functional groups have metal and-OSi chemical bonds, are better than
Other organo-functional groups.Phosphate group is grafted on silica-based adsorbent material, the quantity of adsorption site can be increased, changes absorption
Mechanism, widens the scope of pH value, improves the selectivity of target metal, so as to greatly improve the reactivity of microballoon.Mesoporous material
Engrafting method is broadly divided into two kinds：Grafting and copolymerization method afterwards.Grafting is micro- due to being influenced on the meso-hole structure of hollow silicon ball afterwards
It is weak, it is grafted on the organic functional mass contg inside outer surface and shell and is generally higher than copolymerization method, Wang etc.（Xinghui Wang,
Guiru Zhu, Feng Guo. Removal of uranium(Ⅵ) ion from aqueous solution by SBA-
15. Annals of Nuclear Energy, 2013, 56:151-157.）Two methods are respectively adopted and prepare silicon ball（SBA-
15）, find the silicon ball adsorbing filament technique bigger using rear grafting, saturated extent of adsorption higher.Phosphonic functional groups have with other
Machine functional group has the compatibility of height, and surface modification can be effectively performed, and can be a variety of molten including water
Carried out in agent.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of the hollow Metaporous silicon dioxide material of phosphoric acid functionalized, it is intended to
Solve the problems, such as that adsorbent is low in the efficiency of processing low concentration stibium-containing wastewater, and widen hollow mesoporous silicon oxide in heavy metal
The application in adsorption treatment field.
The present invention is achieved in that synthesis single dispersing carbon ball, detailed process are as follows first：
A certain amount of glucose solution 70mL is prepared, adds a certain amount of 25% NH3·H2O, is then transferred to the hydrothermal reaction kettle of 100mL
In, protective gas certain time is passed through with the speed of 200 mL/min, hydrothermal reaction kettle sealing is placed in electric heating constant temperature air blast does
After 200 DEG C are adjusted the temperature in dry case making its hydro-thermal reaction 12h, with case natural cooling；Products therefrom in hydrothermal reaction kettle is fallen
Go out, 5min is centrifuged with the speed of 5000r/min using supercentrifuge, the cleaning of sediment uses the ethanol of certain gradient concentration
It is three times neutrality to solution with the cleaning of deionized water circulating ultrasonic, the sample of acquisition is dry at 70 DEG C in vacuum drying chamber
8h, it is single dispersing carbon ball material to obtain black powder（CSs）.
Further, the concentration for the glucose solution prepared as described above is 0.1g/mL, and 25% liquor ammoniae fortis dosage is
0.05mol/L。
Further, it is nitrogen to be passed through gas as described above, and it is 15min to be passed through the time.
Further, the cleaning step of sediment as described above is the ethanol using gradient concentration（25%, 50%, 75%）With go
Ionized water circulating ultrasonic cleans.
Then with carbon ball（CSs）For hard template, hollow Metaporous silicon dioxide material is synthesized, detailed process is as follows：
Take a certain amount of single dispersing carbon ball obtained by the first step（CSs）Ultrasonic disperse is placed in perseverance in the 1mol/L NaOH solutions of 10mL
Rotating speed is adjusted in warm oscillator to 150r/min, temperature 60 C, when surface treatment 3 is small after, centrifuge and be dried in vacuo；Take one
Quantitative surfactant cetyl trimethylammonium bromide（CTAB）Solid and 25% NH3·H2O and absolute ethyl alcohol（C2H6O）With
Deionized water is configured to mixed solution, and the carbon ball that above-mentioned NaOH solution is handled well is dispersed in the mixed solution, uses 1mol/L
NaOH solution adjust PH to 9.Above-mentioned solution is disperseed into 10min in ultrasonic cell disintegration instrument, rapidly by a certain amount of silicon source just
Silester（TEOS）Mixed solution is added, reaction system after successive reaction 10min, is placed in electric heating constant temperature air blast and does in ultrasound
80 DEG C of reaction 3h in dry case.The same first step of cleaning step of sediment, and the dry 8h at 70 DEG C is made, obtaining white powder is
Hollow mesoporous silica microsphere material containing template CSs and CTAB.Then white powder is transferred to Muffle furnace, 700
To remove template agent removing when calcining 6 is small at DEG C, it is hollow mesoporous silica microsphere to obtain white powder（HMSs）.
Further, the quality proportioning of each material is CSs as described above：CTAB：NH3·H2O：C2H6O：H2O：TEOS=0.3：
0.2：1.8：60：10：X, wherein x（X=molal weight）0.1,0.2,0.3,0.4.
Further, as described above by silicon source ethyl orthosilicate（TEOS）Mixed solution is rapidly added, and reaction system is super
Carried out in sound.
The hollow mesoporous dioxy of phosphate group functionalization is finally synthesized on the basis of hollow mesoporous silica microsphere material
SiClx micro-sphere material, detailed process are as follows：
Take a certain amount of diethylphosphoryl ethyl triethoxysilane（DPTS）And glacial acetic acid（C2H4O2）, under nitrogen protection in 80
After DEG C thermostat water bath hydro-thermal reaction 6h, it is cooled to room temperature；A certain amount of second step system is added in mixed solution under nitrogen protection
Standby hollow mesoporous silica microsphere（HMSs）, 50mL toluene is added, is transferred in three-necked flask the 2h that flows back in 110 DEG C.
After the sediment centrifugation arrived, washed using methanol and ethanol circulating ultrasonic, be placed in 70 DEG C of dry 12h in vacuum drying, obtain phosphorus
Acid groups functionalization hollow mesoporous silica microsphere（PHMSs）.
Further, the volume proportion of material as described above is CSs：DPTS：Glacial acetic acid=y：0.8：23.5, wherein y（Y=matter
Amount）0.1,0.5,1.0,1.5.
Further, the cleaning step of sediment as described above is to be cleaned using methanol and ethanol circulating ultrasonic.
Further, synthesized phosphate group functionalization hollow mesoporous silica microsphere material as described above is used for trace
The absorption of antimony, the initial concentration control of antimony is in 100 μ g/L during absorption, and absorbent concentration control is in 1-2mL, when adsorption time 24 is small
Within, adsorption temp is room temperature, and pH is controlled in 1.0-7.0.
The synthetic method of the phosphate group functionalization hollow mesoporous silica microsphere composite material of the present invention, it synthesizes road
Line is divided into three steps, i.e., prepares the monodispersed carbon ball of big particle diameter using glucose hydro-thermal method first, then using the carbon of synthesis
Ball is hard template, CTAB is soft template synthesis hollow mesoporous silica microsphere, is finally connect on this basis using rear grafting
Branch phosphate group, synthesizes phosphate group functionalization hollow mesoporous silica microsphere.The hollow mesoporous material tool of functionalization of synthesis
The core-shell structure of well-regulated meso-hole structure, monodispersed particle diameter distribution and stabilization, has efficient adsorptivity to Determination of Trace Amounts of Antimony
Can, have a good application prospect in terms of Determination of Trace Amounts of Antimony water pollution processing and drinking water processing up to standard.
Brief description of the drawings
Fig. 1 is the synthesis side of phosphate group functionalization hollow mesoporous silica microsphere material provided in an embodiment of the present invention
Method flow chart.
Fig. 2 is the grain size distribution of single dispersing carbon ball provided in an embodiment of the present invention.
Fig. 3 is the electron microscope of hard template provided in an embodiment of the present invention, intermediate product and target product：Wherein, a is single point
Dissipate the stereoscan photograph of carbon ball；B is the transmission electron microscope of hollow mesoporous silica microsphere material；C is that phosphoric acid functionalized is hollow
The transmission electron microscope of mesoporous silicon dioxide micro-sphere material.
Fig. 4 is the infrared spectrogram of hard template provided in an embodiment of the present invention, intermediate product and target product：Wherein, a is mono-
The infrared spectrogram of scattered carbon ball；B is the infrared spectrogram of hollow mesoporous silica microsphere material；C is in phosphoric acid functionalized
The infrared spectrogram of empty mesoporous silicon dioxide micro-sphere material.
Fig. 5 is the nitrogen adsorption-desorption isotherm and pore size distribution curve of single dispersing carbon ball provided in an embodiment of the present invention.
Fig. 6 is nitrogen adsorption-desorption isotherm of hollow mesoporous silica microsphere material provided in an embodiment of the present invention
And pore size distribution curve.
Fig. 7 be phosphoric acid functionalized hollow mesoporous silica microsphere material provided in an embodiment of the present invention nitrogen adsorption-
Desorption isotherm and pore size distribution curve.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Below in conjunction with the accompanying drawings and specific embodiment is further described the application principle of the present invention.
The hollow mesoporous silicon oxide of phosphate group functionalization that the present invention is suitable for low concentration stibium-containing wastewater efficient process is micro-
The synthetic method of ball material, specifically comprises the following steps（Refer to Fig. 1）：
The first step, a kind of phosphate group functionalization hollow mesoporous silica microsphere material, the single dispersing carbon ball material are
Prepare with the following method：The glucose solution 70mL of 0.1g/mL is prepared, adds 25% NH3·H2O makes the ammonia concn be
0.05mol/L, is then transferred in the hydrothermal reaction kettle of 100mL, nitrogen 15min is passed through with the speed of 200 mL/min, by hydro-thermal
Reaction kettle sealing be placed in electric heating constant-temperature blowing drying box adjust the temperature to 200 DEG C make its hydro-thermal reaction 12h after, it is naturally cold with case
But；Products therefrom in hydrothermal reaction kettle is poured out, 5min, sediment are centrifuged with the speed of 5000r/min using supercentrifuge
Cleaning using gradient concentration ethanol（25%, 50%, 75%）It is three times neutrality to solution with the cleaning of deionized water circulating ultrasonic,
The sample of acquisition is dried to 8h in vacuum drying chamber, it is single dispersing carbon ball material to obtain black powder at 70 DEG C（CSs）.
Second step, a kind of phosphate group functionalization hollow mesoporous silica microsphere material, the hollow mesoporous dioxy
SiClx micro-sphere material is prepared with the following method：Take single dispersing carbon ball obtained by the first step（CSs）0.3g ultrasonic disperses are in 10mL
1mol/L NaOH solutions in, be placed in constant temperature oscillator and adjust rotating speed to 150r/min, temperature 60 C, when surface treatment 3 is small
Afterwards, centrifuge and be dried in vacuo；Take 0.2g surfactant cetyl trimethylammonium bromides（CTAB）Solid and
1.8mL25% NH3·H2O and 60mL absolute ethyl alcohols（C2H6O）Mixed solution is configured to 10mL deionized waters, by above-mentioned NaOH
The good carbon ball of solution treatment is dispersed in the mixed solution, and PH to 9 is adjusted with the NaOH solution of 1mol/L.By above-mentioned solution super
Disperse 10min in sound cell crushing instrument, rapidly by 1mmol silicon source ethyl orthosilicates（TEOS）Add mixed solution, reaction system
In ultrasound after successive reaction 10min, 80 DEG C of reaction 3h in electric heating constant-temperature blowing drying box are placed in.The cleaning step of sediment is made
The rapid same first step, and the dry 8h at 70 DEG C, it is the hollow meso-porous titanium dioxide containing template CSs and CTAB to obtain white powder
Silicon micro-sphere material（CSs-CTAB-HMSs）.Then white powder is transferred to Muffle furnace, calcined at 700 DEG C 6 it is small when to remove mould
Plate agent, it is hollow mesoporous silica microsphere to obtain white powder（HMSs）.
A kind of 3rd step, phosphate group functionalization hollow mesoporous silica microsphere material, prepares with the following method：
Take 0.8mL diethylphosphoryl ethyl triethoxysilanes（DPTS）With 23.5mL glacial acetic acid（C2H4O2）, under nitrogen protection in 80
After DEG C thermostat water bath hydro-thermal reaction 6h, it is cooled to room temperature；1.0g second steps are added under nitrogen protection in mixed solution to prepare
Hollow mesoporous silica microsphere（HMSs）, 50mL toluene is added, is transferred in three-necked flask the 2h that flows back in 110 DEG C.Obtain
Sediment centrifugation after, washed using methanol and ethanol circulating ultrasonic, be placed in 70 DEG C of dry 12h in vacuum drying, obtain phosphoric acid
Group functionalization's hollow mesoporous silica microsphere（PHMSs）.
The phosphate group functionalization hollow mesoporous silica microsphere material that the present invention synthesizes is in low concentration stibium-containing wastewater
Antimony there is efficient absorption property and selectivity, during concrete application, the initial concentration control of antimony is dense in 100 μ g/L, adsorbent
Degree is controlled in 1-2mL, and at 25 DEG C, when constant temperature oscillation 24 is small under 150r/min, pH is controlled 1.0 ~ 7.0；Determination of Trace Amounts of Antimony is single in water
In the presence of solely, phosphate group functionalization hollow mesoporous silica microsphere material to the removal rate of antimony up to 96.01%, thus, this
The method that invention also provides above-mentioned absorption heavy metal；
The present invention has following advantage：The present invention selects have height to heavy metal from the low present situation of Determination of Trace Amounts of Antimony adsorption efficiency
Organic group of the phosphonic functional groups of adsorptivity as material is imitated, selection has strong mechanical strength, stablizes core-shell structure, compares table greatly
The hollow mesoporous silica microsphere of area introduces phosphate using rear grafting as inorganic carrier in mesoporous and surfaces externally and internally
Group, synthesizes phosphate group functionalization hollow mesoporous silica microsphere material.The materials application is selected in waste water containing Determination of Trace Amounts of Antimony
Property absorption trial first, for waste water high-efficiency containing Determination of Trace Amounts of Antimony processing provide a kind of new method and approach.Advantages of the present invention
It is simple to also reside in synthetic route, reaction condition is gentle, and yield is high, adding less, the phosphorus prepared using method provided by the invention
Acid groups functionalization hollow mesoporous silica microsphere material has high absorption property and selectivity to Determination of Trace Amounts of Antimony, has at the same time
There is the features such as rate of adsorption is fast, and adsorption capacity is big, suitable for the processing of the waste water containing Determination of Trace Amounts of Antimony.
With reference to example, the invention will be further described, but is not limitation of the present invention：
Embodiment one：Prepare phosphate group functionalization hollow mesoporous silica microsphere
1. the preparation of single dispersing carbon ball
The first step, prepares the glucose solution 70mL of 0.1g/mL, adds 25% liquor ammoniae fortis 0.05mol/L, is then transferred to
In the hydrothermal reaction kettle of 100mL, nitrogen 15min is passed through with the speed of 200 mL/min, hydrothermal reaction kettle sealing is placed in electric heating
After 200 DEG C are adjusted the temperature in constant temperature blast drying oven making its hydro-thermal reaction 12h, with case natural cooling；By in hydrothermal reaction kettle
Products therefrom is poured out, and centrifuges 5min using supercentrifuge with the speed of 5000r/min, the cleaning of sediment uses gradient concentration
Ethanol（25%, 50%, 75%）It is three times neutrality to solution with the cleaning of deionized water circulating ultrasonic, by the sample of acquisition in vacuum
Dry 8h at 70 DEG C in drying box, it is single dispersing carbon ball material to obtain black powder（CSs）.The grain size distribution of the material is such as
Fig. 2, scanning electron microscope such as Fig. 3 a, infrared spectrogram such as Fig. 4 a, nitrogen adsorption-desorption isotherm and pore size distribution curve such as Fig. 5.Should
The specific surface area of material is 33.59m2·g-1, particle mean size is 14.68 μm, and 3450 cm can be obtained by infrared spectrogram 4a-1Place
Absworption peak is attributed to O-H stretching vibrations, 1637cm-1And 1381cm-1The absworption peak at place is attributed to C=O stretching vibrations, instruction sheet point
C=O of hydroxyl can be changed into there are great amount of hydroxy group, or by alkali process by dissipating carbon ball material surface, so as to confirm that carbon ball can conduct
Synthesize the hard template of hollow silicon ball.
2. the preparation of hollow mesoporous silica microsphere
Second step, takes 0.3g single dispersing carbon balls obtained by the first step（CSs）Ultrasonic disperse in the 1mol/L NaOH solutions of 10mL,
Be placed in constant temperature oscillator and adjust rotating speed to 150r/min, temperature 60 C, when surface treatment 3 is small after, centrifuge and vacuum done
It is dry；Take surfactant cetyl trimethylammonium bromide（CTAB）Solid 0.2g, 25% liquor ammoniae fortis 1.57mL, absolute ethyl alcohol
71.4mL, deionized water 10mL are configured to mixed solution, and the carbon ball that above-mentioned NaOH solution is handled well is dispersed in the mixed solution
In, adjust PH to 9 with the NaOH solution of 1mol/L.Above-mentioned solution is disperseed into 10min in ultrasonic cell disintegration instrument, rapidly will
1mmol（0.208g）Silicon source ethyl orthosilicate（TEOS）Add mixed solution, reaction system successive reaction 10min in ultrasound
Afterwards, 80 DEG C of reaction 3h in electric heating constant-temperature blowing drying box are placed in.The same first step of cleaning step of sediment is made, and at 70 DEG C
Dry 8h, it is the hollow mesoporous silica microsphere material containing template CSs and CTAB to obtain white powder.Then by white
Powder is transferred to Muffle furnace, and to remove template agent removing when calcining 6 is small at 700 DEG C, it is hollow meso-porous titanium dioxide to obtain white powder
Silicon microballoon（HMSs）.The scanning electron microscope of the material such as Fig. 3 b, infrared spectrogram such as Fig. 4 b, nitrogen adsorption-desorption isotherm and hole
Footpath distribution curve such as Fig. 6.The specific surface area of the material is 209.06m2·g-1, aperture 2.5nm, pore volume 0.34cm3·g-1,
3444 cm can be obtained by infrared spectrogram 4b-1And 1640cm-1The absworption peak at place is attributed to the stretching vibration of Si-OH, the stretching vibration
Show that more multiple binding sites can be provided for the grafting of phosphonic functional groups from hollow mesoporous silica microsphere material.
3. the preparation of phosphate group functionalization hollow mesoporous silica microsphere
Take diethylphosphoryl ethyl triethoxysilane（DPTS）2.5mmol（0.8mL）, glacial acetic acid 23.5mL, nitrogen protect
Under after 80 DEG C of thermostat water bath hydro-thermal reaction 6h, be cooled to room temperature；1.0g second is added in mixed solution under nitrogen protection
Walk the hollow mesoporous silica microsphere prepared（HMSs）, 50mL toluene is added, is transferred in three-necked flask in 110 DEG C of reflux
2h.After obtained sediment centrifugation, washed using methanol and ethanol circulating ultrasonic, be placed in 70 DEG C of dry 12h in vacuum drying, obtain
To phosphate group functionalization hollow mesoporous silica microsphere（PHMSs）.The scanning electron microscope of the material such as Fig. 3 c, infrared spectrogram
Such as Fig. 4 c, nitrogen adsorption-desorption isotherm and pore size distribution curve such as Fig. 7.The specific surface area of the material is 425.64m2·g-1,
Aperture is 2.3nm, pore volume 0.31cm3·g-1.For hollow mesoporous silica microsphere material after phosphoric acid functionalized, its is infrared
Upper 1220 cm of spectrogram 4c-1The absworption peak at place is attributed to the stretching vibration of P=O, 1405-1456 cm-1The absworption peak at place is attributed to
Si-CH2Stretching vibration, illustrate that the phosphate group of DPTS is grafted successfully on hollow mesoporous silica microsphere material.
Embodiment two：
The antimony-containing solution of 100 μ g/L of 500mL is taken in 2L conical flasks, controlled at 25 DEG C, adjust pH value for 1.0-7.0 it
Between, the phosphate group functionalization hollow mesoporous silica microsphere material 1mg prepared by example one is weighed in above-mentioned conical flask,
Filtered after 150r/min constant temperature oscillations 60min, take the filtrate of 10mL, utilize the residue of atomic fluorescence spectrum measure antimony
Concentration, the results showed that adsorption effect is best in pH=6.0, reaches 95.17% to the removal rate of antimony.
Embodiment three：
The antimony-containing solution of 100 μ g/L of 500mL is taken in 2L conical flasks, controlled at 25 DEG C, it is 6.0 to adjust pH value, is weighed
Phosphate group functionalization hollow mesoporous silica microsphere material 1mg prepared by embodiment one in above-mentioned conical flask,
150r/min constant temperature oscillations, take out part solution filtering every 10min, survey the residual concentration of antimony, the results showed that, in preceding 40min
For quick adsorption process, to antimony removal rate up to 94.66%；40min ~ 80min, absorption is more relatively slow, and mainly antimony ion leads to
Diffusion is crossed into the absorption in duct；It is very slow that change is adsorbed after 80min, shows that absorption has reached suction in 80min
Attached balance, to antimony removal rate up to 96.02%.
Example IV：
With reference to the content of alkali metal, alkaline-earth metal in the seawater, 1%Na is prepared+、1‰K+、1‰Mg2+、1‰Ca2+With 100 μ g/L
The aqueous solutions that coexist of Sb (III), carry out adsorption experiment by the method in embodiment 4, surveyed using atomic fluorescence spectrum
The concentration of fixed residue antimony, the results showed that phosphate group functionalization hollow mesoporous silica microsphere material still may be used the removal rate of antimony
Reach more than 95%, show coexisting ion Na+、 K+ 、Mg2+ 、Ca2+Influence to material absorption antimony is smaller, mesoporous silicon oxide
The phosphate group introduced in material has antimony ion preferable selectivity, is more easy to form complex with antimony ion.
The foregoing is merely the preferred embodiments of the present invention, it is not intended to limit the invention, all spirit in the present invention
With all any modification, equivalent and improvement made within principle etc., it should all be included in the protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of phosphate group functionalization hollow mesoporous silica microsphere, it is characterised in that the preparation of the material Method includes the following steps：The first step prepares the monodispersed carbon ball of big particle diameter using glucose hydro-thermal method；Carbon ball synthesized by second step use is hard template, cetyl trimethylammonium bromide is soft template synthesis hollow mesoporous two Silicon oxide microsphere；3rd step is grafted phosphate group using rear grafting on the hollow mesoporous silica microsphere, and synthesis obtains phosphate The functionalized hollow mesoporous silica microsphere of group.
- 2. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 1, its feature exist It is in first step specific practice：Add NH in glucose solution3·H2O, is transferred in hydrothermal reaction kettle, is passed through protective gas, hydro-thermal After the completion of reaction, products therefrom is cooled down；Products therefrom is centrifuged, sediment is circulated using the ethanol and deionized water of gradient concentration It is cleaned by ultrasonic to neutrality, is single dispersing carbon ball material by the sample vacuum drying of acquisition.
- 3. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 1, its feature exist It is in second step specific practice：The single dispersing carbon ball ultrasonic disperse obtained by the first step is taken to be placed in constant temperature oscillation in NaOH solution After surface treatment, centrifuge and be dried in vacuo；The carbon ball that above-mentioned NaOH solution is handled well is dispersed in cetyl trimethyl Ammonium bromide solid and NH3·H2In the mixed solution that O and absolute ethyl alcohol and deionized water are configured to, pH value is adjusted；By the solution After disperseing in ultrasonic cell disintegration instrument, silicon source ethyl orthosilicate is added into mixed solution rapidly, reaction system is anti-in ultrasound Should, it is placed in air-dried；The cleaning step of sediment is made with cleaning step in the first step, is then dried to obtain white powder, and incite somebody to action White powder is transferred to Muffle furnace calcining to remove template agent removing, and it is hollow mesoporous silica microsphere to obtain white powder.
- 4. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 1, its feature exist It is in the 3rd step specific practice：Diethylphosphoryl ethyl triethoxysilane and glacial acetic acid are taken, under a shielding gas hydro-thermal reaction, It is cooled to room temperature；Hollow mesoporous silica microsphere prepared by second step is added in mixed solution under protective gas protection, Toluene is added, after the sediment centrifugation to flow back, is washed, is placed in vacuum drying using methanol and ethanol circulating ultrasonic, Obtain phosphate group functionalization hollow mesoporous silica microsphere.
- 5. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 2, its feature exist In the concentration for the glucose solution prepared described in the first step be 0.1g/mL, 25%NH3·H2O dosages are 0.05mol/L；The first step The protective gas that is passed through is nitrogen, and it is 15min to be passed through the time.
- 6. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 2, its feature exist In first step sediment cleaning step be using the 25% of gradient concentration, 50%, 75% ethanol and deionized water circulating ultrasonic it is clear Wash.
- 7. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 1, its feature exist In the quality proportioning of each material described in second step be CSs：CTAB：NH3·H2O：C2H6O：H2O：TEOS=0.3：0.2：1.8：60： 10：X, wherein x（X=molal weight）0.1,0.2,0.3,0.4.
- 8. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 3, its feature exist In described in second step by silicon source ethyl orthosilicate（TEOS）Mixed solution is rapidly added, and reaction system carries out in ultrasound.
- 9. the preparation method of phosphate group functionalization hollow mesoporous silica microsphere as claimed in claim 4, its feature exist In the volume proportion of material described in the 3rd step be CSs：DPTS：Glacial acetic acid=y：0.8：23.5, wherein y（Y=quality）0.1,0.5, 1.0,1.5, the cleaning step of three-step precipitation thing is to be cleaned using methanol and ethanol circulating ultrasonic.
- 10. the hollow meso-porous titanium dioxide of phosphate group functionalization that the preparation method as described in claim 1 to 9 is any is prepared Silicon microballoon is used for the application in the absorption of Determination of Trace Amounts of Antimony.
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