CN107970878B - Preparation method of phosphate group functionalized hollow mesoporous silica microspheres - Google Patents
Preparation method of phosphate group functionalized hollow mesoporous silica microspheres Download PDFInfo
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a synthesis method of a phosphate group functionalized hollow mesoporous silica microsphere composite material, which comprises the following three steps of firstly preparing large-particle-size monodisperse carbon spheres by a glucose hydrothermal method, then synthesizing hollow mesoporous silica microspheres by using the synthesized carbon spheres as a hard template and Cetyl Trimethyl Ammonium Bromide (CTAB) as a soft template, and finally grafting phosphate groups by a post-grafting method on the basis to synthesize the phosphate group functionalized hollow mesoporous silica microspheres. The synthesized functionalized hollow mesoporous material has a regular mesoporous structure, monodisperse particle size distribution and a stable shell-core structure, has high-efficiency adsorption performance on trace antimony, and has good application prospects in the aspects of trace antimony water body pollution treatment and drinking water standard treatment.
Description
Technical Field
The invention belongs to synthesis of organic and inorganic composite functional materials, and particularly relates to a preparation method of a phosphate group functionalized hollow mesoporous silica microsphere material.
Background
The pollution and control of water resources are always important global problems, along with the influence of industrial development and human activities, the concentration of antimony in a water environment is increased year by year, and antimony ore is not only a collection place of antimony resources, but also a large pollution source due to waste discharge. The concentration of antimony in the natural fresh water is less than 1 mug/L, but the content of antimony in the water body of the mining area can reach hundreds or even thousands of mug/L. Antimony has carcinogenicity, and when a human body drinks polluted water, sulfydryl in protein in the human body can be combined with antimony to inhibit the activity of the hydrophobe enzyme, so that great harm is brought to health. The existing mature antimony removal technology comprises reverse osmosis, solvent extraction, ion exchange, adsorption and the like, wherein the adsorption method is widely applied due to the characteristics of simplicity, rapidness, economy, high efficiency, reproducibility and the like, and the adsorption effect of the currently adopted adsorbent on trace antimony is generally poor. Therefore, an inexpensive and efficient method for treating the trace antimony-containing waste water is urgently needed.
Mesoporous SiO2The microsphere has the excellent properties of high specific surface area, large pore volume, large amount of modifiable silicon hydroxyl on the surface, good chemical inertness, biocompatibility and the like, and almost meets all the requirements of people on an ideal carrier. Compared with the traditional mesoporous SiO2Compared with the microsphere, the mesoporous SiO with hollow interior and permeability2Hollow mesoporous SiO of shell structure2The microspheres (HMSs) also have the characteristics of low density, huge cavities for storing more guest molecules and the like. However, the material is mainly used in the fields of drug carriers and sustained release at present, such as Zhu et al (Zhu Y, Shi J, Chen H, et al A surface method to synthesis pore volume porous silica spheres and advanced storage property [ J]Microporous and Mesoporous Materials, 2005, 84(1): 218-2Loading of microspheres onto ibuprofen drug molecules, Guo et al (Guo H, Qian H, Sun S, et al. Hollow mesoporous silica nanoparticles for intracellular delivery of ibuprofen fluorescent dye[J]Chemistry Central Journal, 2011, 5(1): 1.) Synthesis of a sol-gel/emulsion with an average pore size of 2 nm and a surface area of 880 m2Per g mesoporous hollow SiO2Particles and their adsorption to fluorescent isothiocyanates was studied to mimic drug transport behavior. The hollow mesoporous silica microsphere material has few researches and applications in the aspect of adsorption treatment of heavy metals in water. Therefore, a novel functionalized hollow silica adsorption material is developed, so that the material has the good performance of a hollow mesoporous silica microsphere material and the high-efficiency adsorption performance of a modified group to antimony, and has important theoretical significance and practical application value.
Researchers, Marcinko et al (Marcinko, Stephen, and Y.F. Alexander. Hydrolytic stability of organic monolayers supported on TiO2 and ZrO2 Langmuir, 2004, 20(06): 2270-2273.) found that phosphoric acid functional groups had robustness and stability to metal and-OSi chemical bonds, superior to other organic functional groups. The phosphate group is grafted to the silicon-based adsorbent material, so that the number of adsorption sites can be increased, the adsorption mechanism is changed, the range of pH value is widened, and the selectivity of target metal is improved, thereby greatly improving the reactivity of the microsphere. The grafting method of the mesoporous material is mainly divided into two methods: post-grafting and copolymerization. The influence of the post-grafting method on the mesoporous structure of the hollow silicon spheres is weak, so that the content of organic functional groups grafted on the outer surface and the inner part of the shell is generally higher than that of a copolymerization method, Wang and the like (Xinghui Wang, Guiru Zhu, Feng Guo, Removal of uranium (VI) from aqueous solution by SBA-15. Annals of Nuclear Energy, 2013, 56: 151) which respectively adopt two methods to prepare the silicon spheres (SBA-15), and the silicon sphere adopting the post-grafting method has a larger adsorption rate constant and a higher saturated adsorption capacity. The phosphoric acid functional group has high compatibility with other organic functional groups, enabling it to be surface-modified efficiently, and can be carried out in various solvents including water.
Disclosure of Invention
The invention aims to provide a synthesis method of a phosphoric acid functionalized hollow mesoporous silica material, which aims to solve the problem of low efficiency of an adsorbent in treating low-concentration antimony-containing wastewater and widen the application of hollow mesoporous silica in the field of heavy metal adsorption treatment.
The invention is realized by firstly synthesizing monodisperse carbon spheres, and the specific process is as follows:
preparing a certain amount of glucose solution 70mL, adding a certain amount of 25% NH3·H2O, then transferring the mixture into a 100mL hydrothermal reaction kettle, introducing protective gas at the speed of 200 mL/min for a certain time, sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying oven, adjusting the temperature to 200 ℃ to carry out hydrothermal reaction for 12 hours, and then naturally cooling the hydrothermal reaction kettle along with the oven; and pouring out a product obtained in the hydrothermal reaction kettle, centrifuging for 5min at the speed of 5000r/min by using a high-speed centrifuge, cleaning precipitates by using ethanol and deionized water with certain gradient concentration for three times in a circulating ultrasonic manner until the solution is neutral, and drying the obtained sample in a vacuum drying oven at 70 ℃ for 8h to obtain black powder, namely the monodisperse carbon sphere material (CSs).
Further, the concentration of the glucose solution prepared as described above was 0.1g/mL, and the amount of the 25% concentrated ammonia solution was 0.05 mol/L.
Further, the gas introduced as described above was nitrogen, and the introduction time was 15 min.
Further, the cleaning step of the precipitate is to use gradient concentration ethanol (25%, 50%, 75%) and deionized water to circularly and ultrasonically clean.
Then, Carbon Spheres (CSs) are used as hard templates to synthesize the hollow mesoporous silica material, and the specific process is as follows:
ultrasonically dispersing a certain amount of monodisperse Carbon Spheres (CSs) obtained in the first step into 10mL of 1mol/L NaOH solution, placing the solution in a constant temperature oscillator, adjusting the rotating speed to 150r/min at the temperature of 60 ℃, carrying out surface treatment for 3 hours, carrying out centrifugal separation and vacuum drying; taking a certain amount of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) solid and 25% of NH3·H2O and Anhydrous ethanol (C)2H6O) and deionized water to prepare a mixed solution, dispersing the carbon spheres treated by the NaOH solution in the mixed solution, and adjusting the pH value to 9 by using 1mol/L NaOH solution. Dispersing the solution in an ultrasonic cell disruptor 1And (3) quickly adding a certain amount of silicon source Tetraethoxysilane (TEOS) into the mixed solution, continuously reacting the reaction system in ultrasonic for 10min, and then placing the reaction system in an electric heating constant-temperature air-blast drying oven to react for 3h at the temperature of 80 ℃. The cleaning step of the prepared precipitate is the same as the first step, and the precipitate is dried for 8 hours at the temperature of 70 ℃ to obtain the hollow mesoporous silica microsphere material of which the white powder is the template agent CSs and CTAB. And then transferring the white powder into a muffle furnace, and calcining for 6 hours at 700 ℃ to remove the template agent to obtain the white powder, namely the hollow mesoporous silica microspheres (HMSs).
Further, the mass ratio of the substances is CSs: CTAB: NH (NH)3·H2O：C2H6O：H2O: TEOS = 0.3: 0.2: 1.8: 60: 10: x, wherein x (x = molar mass) is 0.1, 0.2, 0.3, 0.4.
Further, a silicon source of tetraethyl orthosilicate (TEOS) was rapidly added to the mixed solution as described above, and the reaction system was carried out in ultrasound.
Finally, synthesizing the phosphate group functionalized hollow mesoporous silica microsphere material on the basis of the hollow mesoporous silica microsphere material, which comprises the following specific processes:
taking a certain amount of Diethylphosphorylethyltriethoxysilane (DPTS) and glacial acetic acid (C)2H4O2) Carrying out hydrothermal reaction for 6h in a constant-temperature water bath kettle at 80 ℃ under the protection of nitrogen, and cooling to room temperature; adding a certain amount of the hollow mesoporous silica microspheres (HMSs) prepared in the second step into the mixed solution under the protection of nitrogen, adding 50mL of toluene, and transferring the mixture into a three-neck flask to reflux at 110 ℃ for 2 h. And centrifuging the obtained precipitate, performing circulating ultrasonic washing by using methanol and ethanol, and drying in vacuum at 70 ℃ for 12h to obtain the phosphate group functionalized hollow mesoporous silica microspheres (PHMSs).
Further, the volume ratio of the substances is CSs: DPTS: glacial acetic acid = y: 0.8: 23.5, wherein y (y = mass) is 0.1, 0.5, 1.0, 1.5.
Further, the cleaning step of the precipitate is to adopt methanol and ethanol for circulating ultrasonic cleaning.
Further, the phosphate group functionalized hollow mesoporous silica microsphere material synthesized in the above way is used for adsorbing trace antimony, the initial concentration of antimony during adsorption is controlled to be 100 mug/L, the concentration of an adsorbent is controlled to be 1-2mL, the adsorption time is within 24 hours, the adsorption temperature is normal temperature, and the pH is controlled to be 1.0-7.0.
The synthesis method of the phosphate group functionalized hollow mesoporous silica microsphere composite material comprises the following three steps of firstly preparing large-particle-size monodisperse carbon spheres by adopting a glucose hydrothermal method, then synthesizing hollow mesoporous silica microspheres by using the synthesized carbon spheres as hard templates and CTAB as soft templates, and finally grafting phosphate groups by adopting a post-grafting method on the basis to synthesize the phosphate group functionalized hollow mesoporous silica microspheres. The synthesized functionalized hollow mesoporous material has a regular mesoporous structure, monodisperse particle size distribution and a stable shell-core structure, has high-efficiency adsorption performance on trace antimony, and has good application prospects in the aspects of trace antimony water body pollution treatment and drinking water standard treatment.
Drawings
Fig. 1 is a flow chart of a synthesis method of a phosphate-functionalized hollow mesoporous silica microsphere material according to an embodiment of the present invention.
Fig. 2 is a particle size distribution diagram of monodisperse carbon spheres provided in an embodiment of the present invention.
FIG. 3 is an electron micrograph of a hard template, an intermediate product and a target product provided by an embodiment of the present invention: wherein a is a scanning electron micrograph of the monodisperse carbon spheres; b is a transmission electron microscope of the hollow mesoporous silicon dioxide microsphere material; c is a transmission electron microscope of the phosphoric acid functionalized hollow mesoporous silicon dioxide microsphere material.
FIG. 4 is an infrared spectrum of a hard template, an intermediate product and a target product provided by an embodiment of the present invention: wherein, a is an infrared spectrogram of a monodisperse carbon sphere; b is an infrared spectrogram of the hollow mesoporous silica microsphere material; c is an infrared spectrogram of the phosphoric acid functionalized hollow mesoporous silica microsphere material.
Fig. 5 is a nitrogen adsorption-desorption isotherm and a pore size distribution curve of monodisperse carbon spheres provided in an example of the present invention.
Fig. 6 is a nitrogen adsorption-desorption isotherm and a pore size distribution curve of the hollow mesoporous silica microsphere material provided in the embodiment of the present invention.
Fig. 7 is a nitrogen adsorption-desorption isotherm and a pore size distribution curve of the phosphoric acid functionalized hollow mesoporous silica microsphere material provided by the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application of the principles of the present invention will be further described with reference to the accompanying drawings and specific embodiments.
The invention relates to a synthesis method of a phosphate group functionalized hollow mesoporous silica microsphere material suitable for efficiently treating low-concentration antimony-containing wastewater, which specifically comprises the following steps (please refer to figure 1):
the first step is that the phosphate group functionalized hollow mesoporous silica microsphere material is prepared by the following method: preparing 70mL of 0.1g/mL glucose solution, adding 25% NH3·H2O, enabling the concentration of ammonia water to be 0.05mol/L, then transferring the ammonia water into a 100mL hydrothermal reaction kettle, introducing nitrogen for 15min at the speed of 200 mL/min, sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying oven, adjusting the temperature to 200 ℃ to enable the hydrothermal reaction to be carried out for 12h, and then naturally cooling the hydrothermal reaction kettle along with the oven; and pouring out a product obtained in the hydrothermal reaction kettle, centrifuging for 5min at the speed of 5000r/min by using a high-speed centrifuge, cleaning precipitates by using ethanol (25%, 50% and 75%) with gradient concentration and deionized water for three times in a circulating ultrasonic manner until the solution is neutral, and drying the obtained sample in a vacuum drying oven at 70 ℃ for 8h to obtain black powder, namely the monodisperse carbon sphere material (CSs).
The second step is that the hollow mesoporous silica microsphere material with the functional phosphate group is prepared by the following method: 0.3g of monodisperse Carbon Spheres (CSs) obtained in the first step are ultrasonically dispersed in 10mL1mol/L NaOH solution is put into a constant temperature oscillator to adjust the rotating speed to 150r/min at the temperature of 60 ℃, and after surface treatment is carried out for 3 hours, centrifugal separation and vacuum drying are carried out; 0.2g of the surfactant cetyltrimethylammonium bromide (CTAB) as a solid and 1.8mL of 25% NH were taken3·H2O and 60mL of absolute ethanol (C)2H6O) and 10mL of deionized water to prepare a mixed solution, dispersing the carbon spheres treated by the NaOH solution in the mixed solution, and adjusting the pH value to 9 by using 1mol/L NaOH solution. Dispersing the solution in an ultrasonic cell disruption instrument for 10min, rapidly adding 1mmol of silicon source Tetraethoxysilane (TEOS) into the mixed solution, continuously reacting the reaction system in ultrasonic for 10min, and then placing the reaction system in an electric heating constant temperature air-blast drying oven for reaction for 3h at 80 ℃. And the cleaning step of the prepared precipitate is the same as the first step, and the precipitate is dried at 70 ℃ for 8 hours to obtain the white powder which is the hollow mesoporous silica microsphere material (CSs-CTAB-HMSs) containing the template agents CSs and CTAB. And then transferring the white powder into a muffle furnace, and calcining for 6 hours at 700 ℃ to remove the template agent to obtain the white powder, namely the hollow mesoporous silica microspheres (HMSs).
Thirdly, the phosphate group functionalized hollow mesoporous silica microsphere material is prepared by the following method: 0.8mL of Diethylphosphorylethyltriethoxysilane (DPTS) and 23.5mL of glacial acetic acid (C)2H4O2) Carrying out hydrothermal reaction for 6h in a constant-temperature water bath kettle at 80 ℃ under the protection of nitrogen, and cooling to room temperature; 1.0g of the hollow mesoporous silica microspheres (HMSs) prepared in the second step is added into the mixed solution under the protection of nitrogen, 50mL of toluene is added, and the mixture is transferred into a three-neck flask to be refluxed for 2 hours at 110 ℃. And centrifuging the obtained precipitate, performing circulating ultrasonic washing by using methanol and ethanol, and drying in vacuum at 70 ℃ for 12h to obtain the phosphate group functionalized hollow mesoporous silica microspheres (PHMSs).
The phosphate group functionalized hollow mesoporous silica microsphere material synthesized by the invention has high-efficiency adsorption performance and selectivity on antimony in low-concentration antimony-containing wastewater, and when the phosphate group functionalized hollow mesoporous silica microsphere material is specifically applied, the initial concentration of antimony is controlled at 100 mug/L, the concentration of an adsorbent is controlled at 1-2mL, the phosphate group functionalized hollow mesoporous silica microsphere material is subjected to constant-temperature oscillation at 25 ℃ and 150r/min for 24 hours, and the pH value is controlled at 1.0-7.0; when trace antimony exists alone in water, the removal rate of the phosphate group functionalized hollow mesoporous silica microsphere material on antimony can reach 96.01%, so the invention also provides the method for adsorbing heavy metals;
the invention has the following advantages: according to the invention, on the basis of the current situation that trace antimony adsorption efficiency is low, phosphoric acid functional groups with high-efficiency adsorption to heavy metals are selected as organic groups of materials, hollow mesoporous silica microspheres with strong mechanical strength, stable shell-core structure and large specific surface area are selected as inorganic carriers, and phosphoric acid groups are introduced into mesopores and the inner and outer surfaces by adopting a post-grafting method to synthesize the phosphoric acid group functionalized hollow mesoporous silica microsphere materials. The material is applied to the first attempt of selective adsorption of the waste water containing trace antimony, and a new method and a new way are provided for the efficient treatment of the waste water containing trace antimony. The method has the advantages of simple synthetic route, mild reaction conditions, high yield and small dosage, and the phosphate group functionalized hollow mesoporous silica microsphere material prepared by the method has extremely high adsorption performance and selectivity on trace antimony, has the characteristics of high adsorption rate, large adsorption capacity and the like, and is suitable for treating waste water containing trace antimony.
The invention is further illustrated, but not limited, by the following examples:
the first embodiment is as follows: preparation of phosphate group functionalized hollow mesoporous silica microspheres
1. Preparation of monodisperse carbon spheres
Firstly, preparing 70mL of 0.1g/mL glucose solution, adding 0.05mol/L of 25% concentrated ammonia solution, then transferring the solution into a 100mL hydrothermal reaction kettle, introducing nitrogen for 15min at the speed of 200 mL/min, sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant temperature air blowing drying oven, adjusting the temperature to 200 ℃ to carry out hydrothermal reaction for 12h, and then naturally cooling the hydrothermal reaction kettle along with the oven; pouring out the product obtained in the hydrothermal reaction kettle, centrifuging for 5min at the speed of 5000r/min by using a high-speed centrifuge, cleaning the precipitate by using ethanol (25%, 50% and 75%) with gradient concentration and deionized water for three times in a circulating ultrasonic manner until the solution is neutral, and drying the obtained sample in a vacuum drying oven at 70 ℃ for 8h to obtain black powder which is the single componentCarbon sphere dispersed materials (CSs). The particle size distribution diagram of the material is shown in figure 2, the scanning electron microscope is shown in figure 3a, the infrared spectrogram is shown in figure 4a, and the nitrogen adsorption-desorption isotherm and the pore size distribution curve are shown in figure 5. The specific surface area of the material is 33.59m2·g-1The average particle size is 14.68 mu m, and 3450 cm can be obtained from an infrared spectrogram 4a-1The absorption peak is attributed to O-H stretching vibration, 1637cm-1And 1381cm-1The absorption peak is attributed to C = O stretching vibration, which indicates that a large amount of hydroxyl groups exist on the surface of the monodisperse carbon sphere material, or C = O which can be converted into hydroxyl groups through alkali treatment, thereby proving that the carbon sphere can be used as a hard template for synthesizing hollow silicon spheres.
2. Preparation of hollow mesoporous silica microspheres
Secondly, ultrasonically dispersing 0.3g of monodisperse Carbon Spheres (CSs) obtained in the first step into 10mL of 1mol/L NaOH solution, placing the solution in a constant temperature oscillator, adjusting the rotating speed to 150r/min at the temperature of 60 ℃, carrying out surface treatment for 3 hours, carrying out centrifugal separation and vacuum drying; 0.2g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) solid, 1.57mL of 25% concentrated ammonia solution, 71.4mL of absolute ethyl alcohol and 10mL of deionized water are taken to prepare a mixed solution, carbon spheres treated by the NaOH solution are dispersed in the mixed solution, and the PH value is adjusted to 9 by using 1mol/L NaOH solution. Dispersing the solution in an ultrasonic cell disruption instrument for 10min, quickly adding 1mmol (0.208 g) of silicon source Tetraethoxysilane (TEOS) into the mixed solution, continuously reacting the reaction system in ultrasonic for 10min, and then placing the reaction system in an electric heating constant temperature air-blast drying oven for reacting for 3h at 80 ℃. The cleaning step of the prepared precipitate is the same as the first step, and the precipitate is dried for 8 hours at the temperature of 70 ℃ to obtain the hollow mesoporous silica microsphere material of which the white powder is the template agent CSs and CTAB. And then transferring the white powder into a muffle furnace, and calcining for 6 hours at 700 ℃ to remove the template agent to obtain the white powder, namely the hollow mesoporous silica microspheres (HMSs). The scanning electron microscope of the material is shown in figure 3b, the infrared spectrogram is shown in figure 4b, and the nitrogen adsorption-desorption isotherm and the pore size distribution curve are shown in figure 6. The specific surface area of the material is 209.06m2·g-1The pore diameter is 2.5nm and the pore volume is 0.34cm3·g-13444 cm from FIG. 4b-1And 1640cm-1The absorption peak is attributed to the stretching vibration of Si-OH, which shows that the hollow mesoporous silica microsphere material can provide more binding sites for the grafting of the phosphoric acid functional group.
3. Preparation of phosphate group functionalized hollow mesoporous silica microspheres
Taking 2.5mmol (0.8 mL) of Diethylphosphorylethyltriethoxysilane (DPTS) and 23.5mL of glacial acetic acid, carrying out hydrothermal reaction in a constant-temperature water bath kettle at 80 ℃ for 6h under the protection of nitrogen, and cooling to room temperature; 1.0g of the hollow mesoporous silica microspheres (HMSs) prepared in the second step is added into the mixed solution under the protection of nitrogen, 50mL of toluene is added, and the mixture is transferred into a three-neck flask to be refluxed for 2 hours at 110 ℃. And centrifuging the obtained precipitate, performing circulating ultrasonic washing by using methanol and ethanol, and drying in vacuum at 70 ℃ for 12h to obtain the phosphate group functionalized hollow mesoporous silica microspheres (PHMSs). The scanning electron microscope of the material is shown in figure 3c, the infrared spectrogram is shown in figure 4c, and the nitrogen adsorption-desorption isotherm and the pore size distribution curve are shown in figure 7. The specific surface area of the material is 425.64m2·g-1The pore diameter is 2.3nm and the pore volume is 0.31cm3·g-1. After the hollow mesoporous silica microsphere material is functionalized by phosphoric acid, 1220 cm is arranged on an infrared spectrogram 4c of the hollow mesoporous silica microsphere material-1The absorption peak at (A) is due to the stretching vibration of P = O, 1405-1456 cm-1The absorption peak is attributed to Si-CH2The stretching vibration of the DPTS proves that the phosphate group of the DPTS is successfully grafted on the hollow mesoporous silica microsphere material.
Example two:
and (2) putting 500mL of 100 microgram/L antimony-containing solution into a 2L conical flask, controlling the temperature to be 25 ℃, adjusting the pH value to be 1.0-7.0, weighing 1mg of the phosphate group functionalized hollow mesoporous silica microsphere material prepared in the first example into the conical flask, oscillating at the constant temperature of 150r/min for 60min, filtering, taking 10mL of filtrate, and measuring the residual concentration of antimony by using an atomic fluorescence spectrophotometry, wherein the result shows that the adsorption effect is best when the pH is =6.0, and the removal rate of antimony reaches 95.17%.
Example three:
taking 500mL of 100 microgram/L antimony-containing solution into a 2L conical flask, controlling the temperature to be 25 ℃, adjusting the pH value to be 6.0, weighing 1mg of the phosphate group functionalized hollow mesoporous silica microsphere material prepared in the first embodiment into the conical flask, oscillating at a constant temperature of 150r/min, taking out part of the solution every 10min, filtering, and measuring the residual concentration of antimony, wherein the first 40min is a rapid adsorption process, and the removal rate of antimony reaches 94.66%; 40-80 min, the adsorption is relatively slow, and mainly antimony ions enter the pore channel for adsorption through diffusion; after 80min, the adsorption changes slowly, which shows that the adsorption equilibrium is reached after 80min of adsorption, and the antimony removal rate reaches 96.02%.
Example four:
preparing 1% Na by referring to the content of alkali metal and alkaline earth metal in seawater+、1‰K+、1‰Mg2+、1‰Ca2+And 100 mug/L of Sb (III) coexisting aqueous solution, performing an adsorption experiment according to the method in example 4, and determining the concentration of the remaining antimony by adopting an atomic fluorescence spectrophotometry, wherein the result shows that the removal rate of the phosphate group functionalized hollow mesoporous silica microsphere material on antimony can still reach more than 95%, and the result shows that coexisting ions Na+、 K+ 、Mg2+ 、Ca2+The influence on the material to adsorb antimony is small, and phosphate groups introduced into the mesoporous silica material have good selectivity on antimony ions and are more likely to form complexes with the antimony ions.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of a phosphate group functionalized hollow mesoporous silica microsphere is characterized by comprising the following steps:
firstly, preparing large-particle-size monodisperse carbon spheres by a glucose hydrothermal method; specifically, 25% NH is added into glucose solution3·H2O, transferring the mixture into a hydrothermal reaction kettle, introducing protective gas, and cooling the obtained product after the hydrothermal reaction is finished; centrifuging the resulting product, subjecting the precipitate to a gradient of ethanol andperforming ultrasonic cleaning to neutrality by ion water circulation, and performing vacuum drying on the obtained sample to obtain a monodisperse carbon sphere material;
secondly, synthesizing hollow mesoporous silica microspheres by using the synthesized carbon spheres as hard templates and cetyl trimethyl ammonium bromide as soft templates;
thirdly, grafting phosphate groups on the hollow mesoporous silica microspheres by adopting a post-grafting method, and synthesizing to obtain phosphate group functionalized hollow mesoporous silica microspheres; the third step comprises the following specific steps: taking diethyl phosphoryl ethyl triethoxysilane and glacial acetic acid, carrying out hydrothermal reaction under protective gas, and cooling to room temperature; and adding the hollow mesoporous silica microspheres prepared in the second step into the mixed solution under the protection of protective gas, adding toluene, refluxing to obtain a precipitate, centrifuging, circularly and ultrasonically washing by using methanol and ethanol, and drying in a vacuum drying oven to obtain the phosphate group functionalized hollow mesoporous silica microspheres.
2. The method for preparing the phosphate-functionalized hollow mesoporous silica microspheres according to claim 1, wherein the second step comprises: ultrasonically dispersing the monodisperse carbon spheres obtained in the first step into a NaOH solution, placing the solution into a constant-temperature oscillator for surface treatment, and then centrifugally separating and vacuum drying the solution; dispersing the carbon spheres treated by the NaOH solution in cetyl trimethyl ammonium bromide solid and 25 percent of NH3·H2Adjusting the pH value of a mixed solution prepared from O, absolute ethyl alcohol and deionized water; dispersing the solution in an ultrasonic cell disruption instrument, quickly adding silicon source ethyl orthosilicate into the mixed solution, continuously reacting the reaction system in ultrasonic for 10min, and placing the reaction system in an electric heating constant-temperature air-blast drying oven to react for 3h at 80 ℃; and the cleaning step of the prepared precipitate is the same as the cleaning step in the first step, then white powder is obtained by drying, and the white powder is transferred to a muffle furnace to be calcined so as to remove the template agent, so that the white powder, namely the hollow mesoporous silica microspheres, is obtained.
3. The method for preparing hollow mesoporous silica microspheres with functionalized phosphate groups according to claim 1, wherein the concentration of the glucose solution in the first step is 0.1g/mL, and the concentration of ammonia water in the solution is 0.05 mol/L; in the first step, the introduced protective gas is nitrogen, and the introduction time is 15 min.
4. The method for preparing the phosphate-functionalized hollow mesoporous silica microspheres according to claim 1, wherein the first step of cleaning the precipitate is a circulating ultrasonic cleaning with 25%, 50%, 75% ethanol and deionized water in gradient concentration.
5. The method for preparing the phosphate-functionalized hollow mesoporous silica microspheres according to claim 2, wherein the second step comprises the following steps: the monodisperse carbon spheres CSs obtained in the first step: CTAB: 25% NH3·H2O：C2H6O：H2O：TEOS=0.3g：0.2g：1.8 mL：60mL：10mL：1mmol。
6. The method for preparing the phosphate-functionalized hollow mesoporous silica microspheres according to claim 1, wherein the third step comprises the following steps: the hollow mesoporous silica microspheres HMSs prepared in the second step: DPTS: glacial acetic acid = yg: 0.8 mL: 23.5mL, wherein y is 0.1, 0.5, 1.0 or 1.5, and the third step of cleaning the precipitate is ultrasonic cleaning by circulating methanol and ethanol.
7. The use of the hollow mesoporous silica microspheres functionalized by phosphate groups prepared by the preparation method according to any one of claims 1 to 6 in the adsorption of trace antimony.
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| CN111889135B (en) * | 2020-08-13 | 2023-04-25 | 重庆邮电大学 | Preparation method of chiral phosphonic acid loaded hollow mesoporous nano microsphere, product and application thereof |
| CN111889144B (en) * | 2020-08-13 | 2023-04-25 | 重庆邮电大学 | Preparation method of chiral heteropolyacid loaded hollow mesoporous nano microsphere, product and application thereof |
| CN113173631B (en) * | 2021-04-30 | 2022-09-23 | 中国科学院地球化学研究所 | Method for promoting ferrous sulfide to remove Sb (III) in polluted water |
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