CN114887592A - Preparation and application of thiosemicarbazone silicon dioxide microsphere material - Google Patents
Preparation and application of thiosemicarbazone silicon dioxide microsphere material Download PDFInfo
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Abstract
The invention relates to a preparation method of thiosemicarbazide functionalized silica microspheres and a heavy metal ion Hg thereof 2+ The adsorption application research of (1); firstly introducing 3-glycidol ether oxypropyl on the surface of a silicon dioxide microsphere, then carrying out ring opening on ethylene oxide in the 3-glycidol ether oxypropyl through amino in thiosemicarbazide to prepare the thiosemicarbazide functionalized silicon dioxide microsphere, wherein the preparation process of the material is simple, the reaction condition is mild, and the material is successfully applied to heavy metal ions Hg 2+ Adsorption of (3).
Description
Technical Field
The invention belongs to the field of material synthesis and application, and particularly relates to heavy metal ion Hg 2+ An adsorbing material, in particular toPreparation of thiosemicarbazide functionalized silicon dioxide microsphere material and application of thiosemicarbazide functionalized silicon dioxide microsphere material in heavy metal ion Hg 2+ Application in adsorption.
Background
Mercury is one of the well-recognized highly toxic substances, is not biodegradable, and is prone to build up along the food chain, and has long been of interest. Mercury exists in aquatic systems in forms of mainly Hg (0), Hg (I) and Hg (II), wherein Hg (II) is most stable and widely spread in the environment (1. Kim et. Al "EXAFS study of mercury (II) solution to Fe-and Al- (hydr) oxides: I. Effects of pH"; Journal of Colloid and Interface Science, 2004, 271(1), 1-15.). Mercury contamination in water bodies can cause serious damage to the brain, kidneys, lungs and other organs through the drinking water and food chain (Nolan et. al "Tools and tactics for the optical detection of clinical" Chemical Reviews ", 2008, 108, 3443-" 3480 "). Therefore, the removal of mercury (II) pollution in water bodies is of great significance for maintaining human health and ecological environment. The existing methods for removing mercury (II) comprise conventional coagulation methods, chemical precipitation methods, membrane separation methods, ion exchange methods, adsorption methods and the like. Among these techniques, the adsorption method is most widely used because it is easy to handle, low in cost, and easy to regenerate the adsorbent (reference 3. Matlock, et. al "Irreproducible prediction of Mercury and lead", "Journal of Hazardous Materials", 2001, 84, 73-82. reference 4. Chiarle, et. al "Mercury removal from Water by exchange adsorption" Water Research 2000, 34(11), 2971-. Currently, adsorbent materials such as activated carbon, polymers, silicate minerals, zeolites, clay minerals and metal oxides can be used for adsorbing mercury (II) ions in water, but some of the adsorbents have poor selectivity, poor adsorption performance, slow material regeneration rate and are easy to generate secondary pollution. (document 5. Fu, et. al "Post-functionalization of UiO-66-NH) 2 by 2,5-dimer capto-1,3,4-thiadiazole for the high efficiency removal of Hg (II) in water "[ Journal of Hazardous Materials ], 2019, 368, 42-51 ]. Materials that are surface-derivatized with sulfur, nitrogen, and oxygen atoms generally have a high mercury affinityAffinity, and thus much research has focused on the derivation of sulfur, nitrogen, and oxygen atoms from the surface of materials. Researchers connect triamino monomers and 2, 5-divinyl-1, 4-benzene dicarbaldehyde through Schiff base reaction, and then prepare a covalent organic framework material (COF-S-SH) containing sulfhydryl through a sulfhydryl-alkene click chemical reaction, wherein the material is used for treating Hg in sewage 2+ The removal effect of the catalyst can reach 94.1 percent. (document 6. Li, et. al, "Novel thio-functionalized synergistic organic frame as adsorbent for simultaneousremoval of BTEX and marcury (II)" Chemical Engineering Journal, 2020, 398, 125566.). In UiO-66-NH 2 After the metal organic framework material UiO-66-DMTD obtained by modifying 2,5-dimercapto-1,3,4-thiadiazole (DMTD) is continuously used for ten times, Hg is treated 2+ The removal effect of (2) is reduced by only 13.5%, and Zn is added 2+ 、 Co 4+ 、 Ni 2+ 、Cd 2+ 、Mg 2+ 、Fe 3+ 、Ca 2+ And Cu 2+ In the case of simultaneous presence of the material in Hg 2+ Has excellent selectivity. (document 5. Fu, et. al "Post-functionalization of UiO-66-NH) 2 by 2,5-dimer capto-1,3,4-thiadiazole for the high efficiency removal of Hg (II) in water "[ Journal of Hazardous Materials ], 2019, 368, 42-51 ]. COF and MOF materials can achieve the aim of increasing Hg in a material pair solution by introducing nitrogen atoms and sulfur atoms through a post-modification mode 2+ But the synthesis routes of these monomers are long, which is not suitable for large-scale preparation and is costly. The sulfur-containing investigator substituted 2-hydroxyacetophenone- 4 The material obtained by fixing the N-pyrroline thiosemicarbazone to the mesoporous material ZSM-5 in a physical adsorption mode can selectively remove Hg in the solution 2+ Although the specific surface area of the mesoporous silicon is large, the problems of long synthesis route, high cost and the like of functional monomers containing nitrogen and sulfur atoms exist in the preparation process of the material, and the material is not suitable for large-scale preparation; physical adsorption also has the problem of weak interaction, and the organic fragments are easy to be lost during the application process (document 7. Abbas, et. al "A ligand and adsorbed conjugated adsorbed for effective reactive (II) detection and removal from amino groups media 'Chemical Engineering Journal, 2018, 334, 432-443'). The silica microspheres have the characteristics of low price, strong acid and alkali resistance, easy modification of surface rich silicon-containing hydroxyl groups, large specific surface area, high thermal stability and mechanical strength and the like (document 8, Zhu, et. al "Removal of Cd (II) and Fe (III) from DMSO by silica gel supported PAMAM dendrimers: Equisibrium, thermdamics, kinetics and mechanism" [ Ecotoxicology and Environmental Safety ], 2018, 162 and 253-260.). Thiosemicarbazide is an important organic compound, is commonly used as a pesticide intermediate, a rubber assistant, a synthetic resin additive, an analytical reagent and the like, has low cost, and can be coordinated with Hg by sulfur and nitrogen atoms in molecules 2+ Chelate formation (Wang, et. al "Removal of aqueous Hg (II) by polyanilines: absorption characteristics and mechanisms" [ Environmental Science and Technology ], 2009, 43(14), 5223-. Therefore, the method has great potential and application prospect. Based on the advantages of thiosemicarbazide, the amino in the thiosemicarbazide is utilized to carry out epoxy ring-opening reaction on the silicon dioxide microsphere containing the ethylene oxide to prepare the silicon dioxide microsphere (SiO) with the thiosemicarbazide on the surface 2 @ Glycidoxy @ Thiosemicarbazide) and its application to heavy metal ions Hg 2+ Adsorption of (3). The results show that it is applicable to a wide pH range and that it is compatible with Hg over a wide pH range 2+ The adsorption effect of (A) is close to 100%; the saturated adsorption capacity can reach 80 mg/g; for Hg 2+ The adsorption specificity is high; after 5 times of recycling, the material is aligned to Hg 2+ The adsorption performance of the adsorbent can still reach 100 percent.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method and application of a condensed thiosemicarbazide silicon dioxide microsphere material, which can be used for removing heavy metal ions Hg in water 2+ 。
In order to achieve the purpose, the technical scheme of the invention is as follows:
one object of the present invention is to provide an aminosulfuryl silica microsphere, the structure of which is shown in formula 1:
the particle size of the thiosemicarbazone-based silica microsphere is 5-500 mu m, the pore diameter is 10-50nm, and the specific surface area is 100-400m 2 /g。
The invention also aims to provide a preparation method of the thiosemicarbazone silica microsphere material, which comprises the following steps: modifying 3-glycidyl ether oxypropyl on the surface of a silicon dioxide microsphere, adding thiosemicarbazone, and grafting thiosemicarbazone on the surface of the silicon dioxide microsphere through the ring-opening reaction of amino in the thiosemicarbazone and ethylene oxide on the surface of the silicon dioxide microsphere to obtain the thiosemicarbazone silicon dioxide microsphere material.
The process route is as follows:
further, the method specifically comprises the following steps:
(1) silica microsphere surface modified 3-glycidyl ether oxygen propyl (SiO) 2 @ Glycidoxy): dispersing silicon dioxide microspheres in anhydrous toluene under the action of ultrasound, dropwise adding 3-glycidyl ether oxypropyl trimethoxy silane at room temperature, refluxing in an oil bath, taking out, washing with anhydrous ethanol, and drying in a vacuum drying oven at 40-80 ℃ for 2-24h to obtain dried silicon dioxide microspheres with surface modified 3-glycidyl ether oxypropyl;
(2) preparation of thiosemicarbazone silica microspheres (SiO) 2 @ Glycidoxy @ Thiosemicarbazide): taking the dried silicon dioxide microsphere surface modified 3-glycidyl ether oxypropyl to disperse in ethanol, weighing thiosemicarbazone to dissolve in the ethanol, dropwise adding the thiosemicarbazone into the solution, washing the final mixture with absolute ethanol after reaction, and then drying the mixture in a vacuum drying oven at the temperature of 40-80 ℃ for 2-24 hours to obtain the thiosemicarbazone silicon dioxide microsphere.
Further, in the step (1), the mass-to-volume ratio of the silica microspheres to the anhydrous toluene is 0.01-0.30 g/mL; the mass-volume ratio of the silicon dioxide microspheres to the 3-glycidyl ether oxypropyl trimethoxy silane is 0.3-2.5 g/mL.
Further, in the step (1), the reflux temperature in the oil bath is 80-120 ℃; the time of reflux in the oil bath was 10-40 ℃.
Further, in the step (2), the mass ratio of the 3-glycidoxypropyl group modified on the surface of the silica microsphere to the thiosemicarbazide is 0.03-3: 1. Preferably, the mass ratio of the surface modified 3-glycidyl ether oxygen propyl to the thiosemicarbazide of the silica microspheres is 0.375-2.67.
Further, in the step (2), the mass-to-volume ratio of the 3-glycidyl ether oxypropyl group modified on the surface of the silica microspheres to ethanol is 0.004-0.04 g/mL; the mass-volume ratio of the thiosemicarbazide to the ethanol is 0.15-0.40 g/mL.
Further, in the step (2), the temperature of the reaction is 25-80 ℃; the reaction time is 10-40 h.
The invention also aims to provide an application of the thiosemicarbazone silica microsphere material, and the thiosemicarbazone silica microsphere is used as an adsorbing material for applying heavy metal ions Hg 2+ And (4) removing.
The invention has the beneficial effects that:
1. the synthetic route has few steps, mild reaction conditions and high reaction efficiency, and is favorable for the rapid and efficient synthesis of the thiosemicarbazone silicon dioxide microspheres.
2. The thiosemicarbazone silicon dioxide microspheres have the characteristics of acid and alkali resistance, large specific surface area, high mechanical strength and the like.
3. The invention utilizes amino in thiosemicarbazide to carry out epoxy ring-opening reaction on silicon dioxide microspheres containing ethylene oxide to prepare silicon dioxide microspheres (SiO) with thiosemicarbazide on the surface 2 @ Glycidoxy @ Thiosemicarbazide) and its application to heavy metal ions Hg 2+ Adsorption of (3). The results show that it is applicable to a wide pH range and that it is compatible with Hg over a wide pH range 2+ The adsorption effect of (A) is close to 100%; the saturated adsorption capacity can reach 80 mg/g; for Hg 2+ The adsorption specificity is high; after 5 times of recycling, the material is paired with Hg 2+ The adsorption performance of the adsorbent can still reach 100 percent.
Drawings
FIG. 1 is a schematic diagram of the preparation of a condensed thiosemicarbazide silica microsphere.
FIG. 2 is an infrared spectrum of the material of example 1: (a) SiO2 2 ，(b)SiO 2 @Glycidoxy，(c)SiO 2 @Glycidoxy@Thiosemicarbazide。
FIG. 3 shows the pH vs. Hg adsorption for the three materials of example 1 2+ The influence of (c).
FIG. 4 shows three materials vs. Hg in example 1 2+ The saturated adsorption amount of (3).
FIG. 5 shows three materials vs. Hg in example 1 2+ And competitive adsorption properties with other metal ions.
FIG. 6 is SiO of example 1 2 The ability to regenerate @ Glycidoxy @ Thiosemicarbazine materials.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
(1) Silica microsphere surface modified 3-glycidyl ether oxypropyl functional group (SiO) 2 @Glycidoxy)；
The method specifically comprises the following steps: dispersing 1.0-2.0g of silicon dioxide microspheres (with the particle size of 5-500 mu m) in 30-90mL of anhydrous toluene under the action of ultrasound, dropwise adding 1-3mL of 3-glycidyl ether oxypropyl trimethoxysilane at room temperature, refluxing in an oil bath at 80-120 ℃ for 10-40h, taking out the silicon dioxide microspheres, washing with anhydrous ethanol, and then placing in a vacuum drying oven at 40-80 ℃ for drying for 2-24 h;
(2) silicon dioxide microsphere (SiO) modified by thiosemicarbazide 2 @ Glycidoxy @ Thiosemicarbazide);
the method comprises the following specific steps: taking 0.3-0.8g of dried 3-glycidoxypropyl functionalized silica microspheres to disperse in 20-70mL of ethanol, weighing 0.3-0.8g of thiosemicarbazide to dissolve in 2mL of ethanol, dropwise adding the thiosemicarbazide into the solution, stirring the final mixture at the temperature of 25-80 ℃ for 10-40h, washing the mixture with absolute ethanol, and then drying the mixture in a vacuum drying oven at the temperature of 40-80 ℃ for 2-24 h;
(3) pH adsorption of Hg on three materials 2+ The influence of (c);
the method specifically comprises the following steps: respectively taking 3-10mg of dry SiO 2 ，SiO 2 @ Glycidoxy and SiO 2 Putting the three materials of @ Glycidoxy @ Thiosemicarbazine into a centrifugal tube, and respectively adding 0.1-250mg/L Hg into the centrifugal tube 2+ Placing 2-10mL standard solution (pH1-8) on a shaker for reaction for 1-1440min, centrifuging after the reaction is finished, filtering supernate through a filter head with the diameter of 0.45 mu m, and testing by using atomic emission spectroscopy.
(4) Three materials to Hg 2+ Saturated adsorption amount of (4);
the method specifically comprises the following steps: respectively taking 3-10mg of dry SiO 2 ，SiO 2 @ Glycidoxy and SiO 2 The three materials of @ Glycidoxy @ Thiosemicarbazine are placed in a centrifuge tube, and Hg with the concentration of 0.1-250mg/L is respectively added into the centrifuge tube under the optimized pH value 2+ After the standard solution is 2-10mL, the solution is placed on a shaking table oscillator to react for 1-1440min, and other treatments are the same as in (3) after the reaction is finished.
(5) Adsorption of three materials to Hg 2+ Testing competitive adsorption performance with other metal ions;
the method specifically comprises the following steps: respectively taking 3-10mg of dry SiO 2 ，SiO 2 @ Glycidoxy and SiO 2 @ Glycidoxy @ Thiosemicarbazine three materials are placed in a centrifuge tube, and 0.1-250mg/L Mn-containing material is added into the centrifuge tube under the optimized pH value 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Ni 2+ 、Co 2+ 、Hg 2+ After the standard solution is 2-10mL, placing the standard solution on a shaking table oscillator for reaction for 1-1440min, and after the reaction is finished, the rest is the same as (3).
(6) SiO 2 The regeneration experiment of @ Glycidoxy @ Thiosemicarbazine materials:
the method specifically comprises the following steps: taking 3-30mg of dry SiO 2 @ Glycidoxy @ Thiosemicarbazine material is placed in a centrifuge tube, and 0.1-250mg/L Hg is added thereto at the above optimized pH 2+ And placing the standard solution on a shaker oscillator after 20-100mL for reaction for 1-1440min, and taking a supernatant for testing after the reaction is finished. Adsorbed Hg 2+ The material is treated with 0.05-1mol/L HCl 5Ultrasonic washing with 0-100mL for 1-10 times for regeneration, washing the regenerated material with 5-30mL deionized water to neutrality, and placing in 0.1-250mg/L Hg 2+ And placing the standard solution 20-100mL later on a shaking table oscillator for reaction for 1-1440min, and taking the supernatant for testing after the reaction is finished. The cycle is repeated 3-10 times.
Example 1
Preparing thiosemicarbazone silicon dioxide microspheres:
1) dispersing 1.0g of silicon dioxide microspheres (5 mu m) into 40mL of dry toluene, then adding 1mL of 3-glycidoxy propyl trimethoxy silane, refluxing the final reaction in an oil bath at 110 ℃ for 12h, washing the product with 30mL of ethanol for 5 times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain the 3-glycidoxy propyl functionalized silicon dioxide microspheres (SiO) 2 @Glycidoxy)。
2) Take 0.5g SiO 2 Dispersing @ Glycidoxy in 30mL of ethanol, weighing 0.5g of thiosemicarbazide, dissolving in 2mL of ethanol, dropwise adding the solution, stirring the final mixture at 50 ℃ for 12h, washing with absolute ethanol, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain the thiosemicarbazone silica microspheres (SiO) 2 @ Glycidoxy @ Thiosemicarbazide); the obtained thiosemicarbazide-based silica microspheres have the particle size of 5 mu m, the pore diameter of 20nm and the specific surface area of 300m 2 /g。
3) Respectively weighing dry three materials of SiO 2， SiO 2 @ Glycidoxy and SiO 2 @ Glycidoxy @ Thiosemicarbazine each 5mg in a centrifuge tube, where SiO is present 2 And SiO 2 @ Glycidoxy was used as a control material for SiO2@ Glycidoxy @ Thiosemicarbazide to which Hg at pH1, 2, 3,4, 5, 6, 7 and 8 was added, respectively 2+ 5mL of the standard solution (1 mg/L) was placed on a shaker and reacted for 720 min. After the reaction is finished, centrifuging the supernatant, filtering the supernatant by a filter head of 0.45 mu m, testing the supernatant by using an atomic emission spectrum, and calculating the removal rate; the test results are shown in fig. 3.
4) Respectively weighing dry three materials of SiO 2 ，SiO 2 @ Glycidoxy and SiO 2 @ Glycidoxy @ Thiosemicarbazide 5mg each was placed in a centrifuge tube, preferably as described aboveAt a pH of the solution, Hg with a concentration of 0.2-250mg/L is added thereto 2+ Placing 5mL of standard solution on a shaking table oscillator to react for 720min, and the rest is 3) after the reaction is finished; the test results are shown in fig. 4.
5) Respectively weighing dry three materials of SiO 2 ，SiO 2 @ Glycidoxy and SiO 2 @ Glycidoxy @ Thiosemicarbazides each 5mg are placed in a centrifuge tube, and 1mg/L Mn-containing material is added to the centrifuge tube under the optimized pH 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Ni 2+ 、Co 2+ 、Hg 2+ Placing 5mL of standard solution on a shaking table oscillator for reacting for 720min, and after the reaction is finished, the rest is 3); the test results are shown in fig. 5. Taking dry SiO 2 @ Glycidoxy @ Thiosemicarbazine material 20mg was placed in a centrifuge tube to which 1mg/L Hg was added at the above-described optimized pH 2+ After 20mL of the standard solution is placed on a shaking table oscillator for reaction for 720min, and after the reaction is finished, a supernatant is taken for testing. Adsorbed Hg 2+ The material is regenerated by ultrasonic washing 5 times with 0.1mol/L HCl 50mL, and the regenerated material is washed 3 times with 10mL deionized water and then placed in 1mg/L Hg again 2+ After 20mL of the standard solution is placed on a shaker for reaction for 720min, and after the reaction is finished, a supernatant is taken for testing. The circulation is carried out for 5 times; the test results are shown in fig. 6.
Example 2
Preparing thiosemicarbazone silicon dioxide microspheres:
1) dispersing 2.0g of silicon dioxide microspheres (100 mu m) into 30mL of dry toluene, then adding 1mL of 3-glycidoxy propyl trimethoxy silane, refluxing the final reaction in an oil bath at 80 ℃ for 10h, washing the product with 30mL of ethanol for 5 times, and drying in a vacuum drying oven at 40 ℃ for 2h to obtain the 3-glycidoxy propyl functionalized silicon dioxide microspheres (SiO) 2 @Glycidoxy)；
2) Take 0.8g SiO 2 @ Glycidoxy is dispersed in 20mL of ethanol, 0.8g of thiosemicarbazone is weighed and dissolved in 2mL of ethanol, the solution is dropwise added, the final mixture is stirred at 40 ℃ for 2h, then is washed by absolute ethanol, and then is placed in a vacuum drying oven at 40 ℃ for drying for 2h to obtain thiosemicarbazone dioxideSilicon microspheres (SiO) 2 @Glycidoxy@Thiosemicarbazide)。
The method for detecting the mercury ion removal performance of the thiosemicarbazone silicon dioxide microsphere material is the same as the steps 3), 4) and 5) in the example 1, and the detection result is similar to that in the example 1.
Example 3
Preparing thiosemicarbazone silicon dioxide microspheres:
1) dispersing 1.0g of silicon dioxide microspheres (500 mu m) into 90mL of dry toluene, adding 3mL of 3-glycidyl ether oxypropyl trimethoxy silane, refluxing the final reaction in an oil bath at 80 ℃ for 40h, washing the product with 30mL of ethanol for 5 times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain the 3-glycidyl ether oxypropyl functionalized silicon dioxide microspheres (SiO) 2 @Glycidoxy)；
2) Take 0.3g SiO 2 @ Glycidoxy is dispersed in 70mL ethanol, 0.3g of thiosemicarbazone is weighed and dissolved in 2mL ethanol, the solution is dripped into the solution, the final mixture is stirred at 80 ℃ for 24h and then washed by absolute ethanol, and then the mixture is placed in a vacuum drying oven at 80 ℃ for drying for 24h to obtain thiosemicarbazone silicon dioxide microspheres (SiO 2) 2 @Glycidoxy@Thiosemicarbazide)。
The method for detecting the mercury ion removal performance of the thiosemicarbazone silicon dioxide microsphere material is the same as the steps 3), 4) and 5) in the example 1, and the detection result is similar to that in the example 1.
Product characterization
The infrared spectrum of the product of example 1 was checked and the results are shown in FIG. 2, in the FT-IR spectrum (FIG. 2), 471, 807 and 1100cm −1 Respectively belonging to Si-O-Si stretching vibration, [ SiO4]Ring vibration and bending vibration of Si-O. In SiO 2 @ Glycidoxy (FIG. 2 (b)) in the FT-IR spectrum, newly appeared 2950cm −1 Left and right belong to CH 2 The peak of vibration absorption indicates that 3-glycidoxypropyl has been successfully grafted on the surface of silica microspheres. SiO2 2 FT-IR spectra of @ Glycidoxy @ Thiourea (FIG. 2(c)) at 3370, 3273 and 3196cm −1 Absorb the N-H stretching vibration corresponding to the peak, 1650 cm and 1622cm −1 The absorption peak of (A) is a bending vibration of the amino group of 1280cm −1 Is suckedThe peak was taken to correspond to the stretching vibration of the C = S double bond, indicating that the thiosemicarbazide was successfully grafted onto the silica microsphere surface.
And (3) analysis results: the condensed thiosemicarbazide silica microspheres can realize heavy metal ions Hg at the pH value of 1-8 2+ High efficiency adsorption and excellent selectivity.
The material has simple preparation process and mild reaction condition, and is successfully applied to heavy metal ions Hg 2+ Separation of (4).
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (9)
1. The thiosemicarbazone silica microsphere material is characterized in that the structural formula of the thiosemicarbazone silica microsphere material is shown as the formula (1):
2. the preparation method of the thiosemicarbazone silica microsphere material disclosed by claim 1, which is characterized by comprising the following steps of: modifying 3-glycidyl ether oxypropyl on the surface of a silicon dioxide microsphere, adding thiosemicarbazone, and grafting thiosemicarbazone on the surface of the silicon dioxide microsphere through the ring-opening reaction of amino in the thiosemicarbazone and ethylene oxide on the surface of the silicon dioxide microsphere to obtain the thiosemicarbazone silicon dioxide microsphere material.
3. The preparation method of the thiosemicarbazone silica microsphere material according to claim 2, which is characterized by comprising the following steps:
(1) modifying the surface of the silicon dioxide microsphere with 3-glycidyl ether oxygen propyl: dispersing silicon dioxide microspheres in anhydrous toluene under the action of ultrasound, dropwise adding 3-glycidyl ether oxypropyl trimethoxy silane at room temperature, refluxing in an oil bath, taking out, washing with anhydrous ethanol, and drying in a vacuum drying oven at 40-80 ℃ for 2-24h to obtain dried silicon dioxide microspheres with surface modified 3-glycidyl ether oxypropyl;
(2) preparing thiosemicarbazone silicon dioxide microspheres: taking the dried silicon dioxide microsphere surface modified 3-glycidyl ether oxypropyl to disperse in ethanol, weighing thiosemicarbazone to dissolve in the ethanol, dropwise adding the thiosemicarbazone into the solution, washing the final mixture with absolute ethanol after reaction, and then drying the mixture in a vacuum drying oven at the temperature of 40-80 ℃ for 2-24 hours to obtain the thiosemicarbazone silicon dioxide microsphere.
4. The method for preparing thiosemicarbazone silica microsphere material according to claim 3, wherein in the step (1), the mass-to-volume ratio of the silica microspheres to the anhydrous toluene is 0.01-0.30 g/mL; the mass-volume ratio of the silicon dioxide microspheres to the 3-glycidyl ether oxypropyl trimethoxy silane is 0.3-2.5 g/mL.
5. The method for preparing thiosemicarbazone silica microsphere material according to claim 3, wherein in the step (1), the temperature of the reflux in the oil bath is 80-120 ℃; the time of reflux in the oil bath was 10-40 ℃.
6. The method for preparing thiosemicarbazone silica microsphere material according to claim 3, wherein in the step (2), the mass ratio of the 3-glycidyl ether oxypropyl group to the thiosemicarbazone on the surface of the silica microsphere is 0.03-3: 1.
7. The preparation method of thiosemicarbazone silica microsphere material according to claim 3, characterized in that in the step (2), the mass-to-volume ratio of the surface modification 3-glycidoxypropyl group of the silica microspheres to the ethanol is 0.004 to 0.04 g/mL; the mass-volume ratio of the thiosemicarbazide to the ethanol is 0.15-0.40 g/mL.
8. The method for preparing thiosemicarbazone silica microsphere material according to claim 3, wherein in the step (2), the reaction temperature is 25-80 ℃; the reaction time is 10-40 h.
9. Use of the thiosemicarbazone silica microsphere material according to any one of claims 1 to 8, wherein the thiosemicarbazone silica microspheres are used as an adsorbing material for heavy metal ions Hg 2+ And (4) removing.
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