CN113209950A - Hollow reduced graphene oxide/magnesium silicate composite microsphere and application thereof - Google Patents
Hollow reduced graphene oxide/magnesium silicate composite microsphere and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000391 magnesium silicate Substances 0.000 title claims abstract description 63
- 229910052919 magnesium silicate Inorganic materials 0.000 title claims abstract description 63
- 235000019792 magnesium silicate Nutrition 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000004793 Polystyrene Substances 0.000 claims abstract description 65
- 229920002223 polystyrene Polymers 0.000 claims abstract description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 32
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 8
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 58
- 239000003463 adsorbent Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 239000002351 wastewater Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- 238000005485 electric heating Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
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- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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Abstract
The invention discloses a hollow graphene oxide/magnesium silicate composite microsphere and application thereof, belonging to the technical field of inorganic adsorption materials. Firstly preparing polystyrene microspheres, then wrapping a layer of graphene oxide on the polystyrene microspheres, then growing a layer of magnesium silicate on the surface of GO in situ, reducing GO into RGO in the magnesium silicate growth process to obtain PS @ RGO @ MS, and finally removing the polystyrene microspheres by using toluene to obtain the hollow reduced graphene oxide/magnesium silicate composite microspheres. In the obtained composite microsphere, the surfaces of the RGO and the magnesium silicate can adsorb methylene blue, so that the adsorption capacity can be further improved under the synergistic effect of the RGO and the magnesium silicate, and meanwhile, the hollow structure of the composite microsphere not only has a large specific surface, but also reduces the overall quality and density of the microsphere, thereby improving the adsorption effect. The invention can provide new thought and exploration for developing novel adsorbents in future, and has great social and economic benefits in practical application.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic adsorption materials, and particularly relates to hollow reduced graphene oxide/magnesium silicate composite microspheres and application thereof in adsorption of organic dye methylene blue.
Background
Polystyrene microsphere (PS)) has uniform physicochemical properties such as size, shape and the like, and as a novel high polymer material, PS has the characteristics of large specific surface area, controllable particle size, easy functionalization, stable structure, strong adsorption performance and the like, and has great potential in the adsorption field.
Reduced Graphene Oxide (RGO) may be used as a soft buffer to stabilize inorganic structures and may be used as a spacer to prevent inorganic nanomaterials from aggregating, thereby reducing BET surface area and reducing adsorption capacity. RGO can also enhance the adsorption of ions and molecules by electrostatic attraction or conjugation.
Magnesium silicate has a unique layered structure of silicate in terms of structure, and its crystal structure is formed by alternately combining a layered structure composed of metal oxide and hydroxide and a layered structure of silicon-oxygen tetrahedron, and its bonding force between metal ions and oxygen of silicon-oxygen tetrahedron is weak, so that it can freely move between layers. In terms of performance, magnesium silicate is widely researched in the adsorption field due to the advantages of good thermal stability, high specific surface area, high wear resistance, environmental friendliness and the like.
Disclosure of Invention
The invention aims to provide a hollow reduced graphene oxide/magnesium silicate composite microsphere and application thereof. The method is scientific and reasonable, the process flow is simple and practical, and aiming at the problems of poor adsorption capacity, poor material and water dispersibility, poor environmental weather resistance and the like of the traditional adsorbent, the composite microsphere obtained by forming the hollow structure and combining the large specific surface area of the reduced graphene oxide and the hydroxyl on the surface of the magnesium silicate has excellent adsorption performance and good biocompatibility, and has great application prospect and great social and economic benefits.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hollow reduced graphene oxide/magnesium silicate composite microsphere is prepared by preparing a polystyrene microsphere, loading graphene oxide on the polystyrene microsphere, and grafting silicon dioxide on the surface of the graphene oxide-loaded microsphere to obtain PS @ GO @ SiO2And then transferring the product to a high-pressure reaction kettle with a polytetrafluoroethylene liner, converting silicon dioxide into magnesium silicate through a hydrothermal reaction, reducing graphene oxide to obtain PS @ RGO @ MS, and finally removing polystyrene microspheres by using toluene to obtain the hollow reduced graphene oxide/magnesium silicate composite microspheres HG @ MS. The preparation method comprises the following specific steps:
step 1: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of Benzoyl Peroxide (BPO) and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃ to obtain emulsion containing polystyrene microspheres, and standing for 24h for later use; the obtained polystyrene microspheres are monodisperse and have the size of 1 micron;
step 2: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding in a mortar to obtain microspheres loaded with the graphene oxide;
and step 3: adding 50mg of microspheres loaded with graphene oxide into a beaker filled with 50ml of deionized water, adjusting the pH to be =9 by using ammonia water, dropwise adding 1.5-12 ml of Tetraethoxysilane (TEOS), reacting at room temperature for 48 hours, and then performing suction filtration, washing and freeze-drying to obtain PS @ GO @ SiO2(ii) a The obtained PS @ GO @ SiO2Adding the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 50-400 mg of magnesium chloride hexahydrate and 500-4000 mg of ammonium chloride, adjusting the pH to be =10 by using ammonia water, and then putting the mixture into an oven to react for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; adding the obtained PS @ RGO @ MS into 50ml of toluene, reacting for 24 hours at room temperature, filtering, and freeze-drying to obtain a hollow reduction productGraphene oxide/magnesium silicate composite microspheres HG @ MS.
The obtained hollow reduced graphene oxide/magnesium silicate composite microspheres can be used for adsorbing organic dye methylene blue.
The invention adopts the polystyrene microsphere as a precursor, which has a monodisperse structure, the size of about 1 micron and good dispersibility. And then, graphene oxide is prepared by a hummers method and is wrapped on the surface of the polystyrene microsphere, so that sites are provided for subsequent silicon dioxide grafting and magnesium silicate modification, and the adsorption to methylene blue is improved. The magnesium silicate surface has a large number of lamellar structures, so that a large specific surface area is provided for the magnesium silicate surface, active sites can be provided for the adsorption of methylene blue, and hydroxyl groups on the magnesium silicate surface are biocompatible.
The invention has the beneficial effects that:
1. according to the method, polystyrene is used as a hard template to obtain the magnesium silicate composite material growing on the surface of reduced graphene oxide in situ, and finally the template is removed through methylbenzene to obtain the reduced graphene oxide magnesium silicate composite material with a hollow structure. The method is environment-friendly, scientific and reasonable, has simple process flow and has practical production possibility.
2. According to the invention, magnesium silicate grows on graphene oxide by utilizing reaction sites on the graphene oxide, so that an integral body is formed, and the adsorption capacities of the two are combined.
3. The hollow reduced graphene oxide/magnesium silicate composite microspheres obtained by the method have the advantages of large specific surface area, light weight, small density, good adsorption effect and the like.
4. Compared with the traditional adsorbent, the hollow reduced graphene oxide magnesium silicate composite microsphere has the advantages of large specific surface area, small dosage, environmental friendliness, good biocompatibility, obvious adsorption effect and the like.
5. The adsorbing material also provides new ideas and explorations for developing novel adsorbents in future, and has huge social and economic benefits in practical application.
Drawings
Fig. 1 is an XRD pattern of the hollow reduced graphene oxide/magnesium silicate composite microsphere prepared in example 4.
Fig. 2 is an SEM image of the polystyrene/graphene oxide microspheres prepared in example 4.
Fig. 3 is an SEM image of the hollow reduced graphene oxide/magnesium silicate composite microsphere prepared in example 4.
Fig. 4 is a TEM image of the hollow reduced graphene oxide/magnesium silicate composite microsphere prepared in example 4.
Fig. 5 is a BET diagram of the hollow reduced graphene oxide/magnesium silicate composite microspheres prepared in example 4.
Fig. 6 is a graph showing how the hollow reduced graphene oxide/magnesium silicate composite microspheres prepared in example 4 adsorb methylene blue for different times (the adsorption time from left to right is 0min, 10min, 20min, 40min, and 60 min).
Fig. 7 is a cyclic adsorption test chart of the hollow reduced graphene oxide/magnesium silicate composite microspheres prepared in example 4.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
1. Preparation of hollow reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparing a hollow reduced graphene oxide/magnesium silicate microsphere HG @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH =9 with ammonia water, then dropwise adding 1.5ml of TEOS, reacting at room temperature for 48h, then performing suction filtration, washing and freeze-drying, adding the freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 50mg of magnesium chloride hexahydrate and 500mg of ammonium chloride, adjusting the pH =10 with ammonia water, then placing into an oven, and reacting at 140 ℃ for 24h to obtain @ PS RGO @ MS; the PS @ RGO @ MS is added into 50ml of toluene, reacted for 24 hours at room temperature, filtered and freeze-dried to obtain HG @ MS.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 381.6 mg/g.
Example 2
1. Preparation of hollow reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparing a hollow reduced graphene oxide/magnesium silicate microsphere HG @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH =9 with ammonia water, then dropwise adding 3ml of TEOS, reacting for 48 hours at room temperature, then performing suction filtration, washing and freeze-drying, adding the freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 100mg of magnesium chloride hexahydrate and 1000mg of ammonium chloride, adjusting the pH =10 with ammonia water, then placing into an oven, and reacting for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; the PS @ RGO @ MS is added into 50ml of toluene, reacted for 24 hours at room temperature, filtered and freeze-dried to obtain HG @ MS.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 439.5 mg/g.
Example 3
1. Preparation of hollow reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparing a hollow reduced graphene oxide/magnesium silicate microsphere HG @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH =9 with ammonia water, then dropwise adding 6ml of TEOS, reacting for 48 hours at room temperature, then performing suction filtration, washing and freeze-drying, adding the freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 200mg of magnesium chloride hexahydrate and 2000mg of ammonium chloride, adjusting the pH =10 with ammonia water, then placing into an oven, and reacting for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; the PS @ RGO @ MS is added into 50ml of toluene, reacted for 24 hours at room temperature, filtered and freeze-dried to obtain HG @ MS.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 500.7 mg/g.
Example 4
1. Preparation of hollow reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparing a hollow reduced graphene oxide/magnesium silicate microsphere HG @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH =9 by using ammonia water, then dropwise adding 9ml of TEOS, reacting for 48 hours at room temperature, then performing suction filtration, washing and freeze-drying, adding the freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 300mg of magnesium chloride hexahydrate and 3000mg of ammonium chloride, adjusting the pH =10 by using ammonia water, then placing into an oven, and reacting for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; the PS @ RGO @ MS is added into 50ml of toluene, reacted for 24 hours at room temperature, filtered and freeze-dried to obtain HG @ MS.
Fig. 1 is an XRD chart of the prepared hollow reduced graphene oxide/magnesium silicate composite microsphere. In the figure, the existence of the reduced graphene oxide and the magnesium silicate is proved by characteristic peaks at the positions of 20 degrees, 40 degrees and 60 degrees of 2 theta.
Fig. 2 is an SEM image of the prepared polystyrene/graphene oxide microspheres. The graph shows that graphene oxide is coated on the surface of the polystyrene microsphere.
Fig. 3 is an SEM image of the prepared hollow reduced graphene oxide/magnesium silicate composite microsphere. As can be seen from the figure, the hollow reduced graphene oxide/magnesium silicate composite material still maintains the microsphere structure after PS is removed.
Fig. 4 is a TEM image of the prepared hollow reduced graphene oxide/magnesium silicate composite microsphere. As can be seen from the figure, the hollow reduced graphene oxide/magnesium silicate composite material shows a hollow structure after PS is removed.
FIG. 5 is a BET diagram of the prepared hollow reduced graphene oxide/magnesium silicate composite microsphere. As can be seen from the figure, BET of the hollow reduced graphene oxide/magnesium silicate composite microspheres is 570 m2In terms of a/g, the mean pore diameter is 3.9 nm.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 595.2 mg/g.
Fig. 6 is a graph of how the prepared hollow reduced graphene oxide/magnesium silicate composite microspheres adsorb methylene blue for different times (the adsorption time from left to right is 0min, 10min, 20min, 40min, 60 min). As can be seen from the figure, as the adsorption time increases, the adsorption of the hollow reduced graphene oxide/magnesium silicate composite microspheres to MB increases, and the color of the solution becomes lighter.
Example 5
1. Preparation of hollow reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparing a hollow reduced graphene oxide/magnesium silicate microsphere HG @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH to be =9 by using ammonia water, then dropwise adding 12ml of TEOS, reacting for 48 hours at room temperature, then performing suction filtration, washing and freeze-drying, adding a freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 400mg of magnesium chloride hexahydrate and 4000mg of ammonium chloride, adjusting the pH to be =10 by using ammonia water, then placing the product into an oven, and reacting for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; the PS @ RGO @ MS is added into 50ml of toluene, reacted for 24 hours at room temperature, filtered and freeze-dried to obtain HG @ MS.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 564.8 mg/g.
Comparative example 1
1. Preparation of polystyrene graphene oxide/silicon dioxide composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) polystyrene/reduced graphene oxide/silicon dioxide PS @ GO @ SiO2The preparation of (1): adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH to be =9 by using ammonia water, dropwise adding 9ml of TEOS, reacting at room temperature for 48 hours, and then performing suction filtration, washing and freeze-drying to obtain PS @ GO @ SiO2。
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorption at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 315.8 mg/g.
Comparative example 2
1. Preparation of polystyrene/reduced graphene oxide/magnesium silicate composite microspheres
1) Preparation of polystyrene microsphere PS: adding 50ml of styrene into 50ml of absolute ethyl alcohol, stirring for 0.5h at room temperature under the condition of high-speed magnetic stirring, then transferring to a three-neck flask, introducing nitrogen for protection, dropwise adding 0.7 g of BPO and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, then carrying out polymerization reaction for 8h in a constant-temperature electric heating jacket at 80 ℃, and standing the emulsion containing the polystyrene microspheres obtained after the reaction for 24h for later use;
2) preparation of polystyrene/graphene oxide PS @ GO: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding the emulsion into a beaker filled with 50ml of deionized water, then adding 0.3g of graphene oxide, carrying out ultrasonic reaction for 1 hour, stirring at room temperature for 2 hours, then centrifuging and freeze-drying a product, and grinding the product in a mortar to obtain microspheres loaded with the graphene oxide;
3) preparation of polystyrene/graphene oxide/magnesium silicate PS @ RGO @ MS: adding 50mg of graphene oxide microspheres into a beaker filled with 50ml of deionized water, adjusting the pH =9 by using ammonia water, then dropwise adding 9ml of TEOS, reacting for 48h at room temperature, then performing suction filtration, washing and freeze-drying, adding the freeze-dried product into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 300mg of magnesium chloride hexahydrate and 3000mg of ammonium chloride, adjusting the pH =10 by using ammonia water, then placing into an oven, and reacting for 24h at 140 ℃ to obtain PS @ RGO @ MS.
2. Measurement of adsorption Property (adsorption test of simulated wastewater containing methylene blue)
120ml of simulated wastewater (pH 7) containing methylene blue at a concentration of 100mg/L was taken. Adding the composite microsphere adsorbent prepared in the embodiment into simulated wastewater, stirring at constant temperature for 24 hours, standing, measuring the concentration of residual methylene blue of filtrate by using a spectrophotometer method, and calculating the maximum adsorption capacity.
And (3) testing results: the dosage of the adsorbent is 20mg, and after stirring and adsorbing at room temperature (25 ℃) for 24 hours, the maximum adsorption quantity is 47.3 mg/g.
TABLE 1 comparison of specific surface area Properties of different materials
Performance testing
After the adsorption experiment, the hollow reduced graphene oxide/magnesium silicate composite microspheres obtained in the example 4 are recovered and placed in 0.1 mol/L HCl solution, and are desorbed for 180min in an ultrasonic environment with room temperature and 60 kHz working power, and then are washed and dried by deionized water to perform a cycle performance test.
As can be seen from fig. 7, the maximum adsorption amount of the adsorbent still reached 86% after 5 cycles of the adsorption-desorption process.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A hollow reduced graphene oxide/magnesium silicate composite microsphere is characterized in that: firstly preparing polystyrene microspheres, then loading graphene oxide by using the polystyrene microspheres, and grafting silicon dioxide on the surfaces of the microspheres loaded with graphene oxide to obtain PS @ GO @ SiO2And then transferring the product to a high-pressure reaction kettle with a polytetrafluoroethylene liner, converting silicon dioxide into magnesium silicate through hydrothermal reaction, reducing graphene oxide to obtain PS @ RGO @ MS, and finally removing polystyrene microspheres by using toluene to obtain the hollow reduced graphene oxide/magnesium silicate composite microspheres.
2. The hollow reduced graphene oxide/magnesium silicate composite microspheres according to claim 1, wherein: the preparation method comprises the following specific steps:
step 1: adding 50ml of styrene into 50ml of absolute ethyl alcohol, magnetically stirring for 0.5h at room temperature, introducing nitrogen for protection, dropwise adding 0.7 g of benzoyl peroxide and 30ml of ethanol solution containing 5g of polyvinylpyrrolidone, carrying out constant-temperature polymerization reaction for 8h at 80 ℃ to obtain emulsion containing polystyrene microspheres, and standing for 24h for later use;
step 2: taking 0.6g of the emulsion containing the polystyrene microspheres prepared in the step 1, adding 50ml of deionized water and 0.3g of graphene oxide, carrying out ultrasonic reaction for 1h, stirring at room temperature for 2h, centrifuging and freeze-drying a product, and grinding in a mortar to obtain microspheres loaded with graphene oxide;
and step 3: adding 50mg of microspheres loaded with graphene oxide into 50ml of deionized water, adjusting the pH to be =9 by using ammonia water, dropwise adding 1.5-12 ml of ethyl orthosilicate, reacting at room temperature for 48 hours, and then performing suction filtration, washing and freeze-drying to obtain PS @ GO @ SiO2(ii) a The obtained PS @ GO @ SiO2Adding the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, performing ultrasonic dispersion, adding 50-400 mg of magnesium chloride hexahydrate and 500-4000 mg of ammonium chloride, adjusting the pH to be =10 by using ammonia water, and then putting the mixture into an oven to react for 24 hours at 140 ℃ to obtain PS @ RGO @ MS; and adding the PS @ RGO @ MS into 50ml of toluene, reacting at room temperature for 24 hours, filtering, and freeze-drying to obtain the hollow reduced graphene oxide/magnesium silicate composite microspheres.
3. The hollow reduced graphene oxide/magnesium silicate composite microspheres according to claim 2, wherein: the polystyrene microsphere obtained in the step 1) is monodisperse and has the size of 1 micron.
4. The use of the hollow reduced graphene oxide/magnesium silicate composite microspheres according to claim 1 for adsorbing an organic dye, methylene blue.
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