CN110496609B - Graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and preparation method thereof - Google Patents
Graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel which can realize high-efficiency adsorption of various oils/organic solvents and fluorine ions in water. The preparation method comprises the following steps: (1) mixing GO water dispersion, HAP nanowire water dispersion and a chemical reducing agent, stirring and ultrasonically dispersing the mixture uniformly; (2) carrying out mild chemical reduction-freeze thawing-deep reduction process self-assembly on the blended dispersion liquid to obtain rGO/HAP hydrogel; (3) freezing and drying the hydrogel to obtain rGO/HAP aerogel; (4) the aerogel is subjected to high-temperature carbonization treatment or surface hydrophilic modification to realize high-efficiency adsorption of different organic solvents or fluorine ions. The method is simple and rapid, has mild reaction conditions, excellent physical and chemical properties and mechanical properties, high adsorption capacity, can efficiently treat the high-fluoride ion wastewater and the wastewater containing insoluble oil or organic solvent, can be repeatedly used for many times, and has good practical application prospect.
Description
Technical Field
The invention relates to the field of adsorption materials, and particularly relates to a graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel.
Background
In recent years, with rapid development of economy and rapid increase of population, the problem of water pollution becomes more severe, which causes serious harm to aquatic organisms and human health, and has become a great threat affecting human survival and sustainable development. In addition, the types of water pollutants are also more and more extensive, the components are more and more complex, besides the most common oil (such as crude oil and the like) or organic solvent pollutants, a large amount of pollutants which are difficult to degrade (such as fluorine ions, heavy metals, pesticides, dyes and the like) are discharged into the water body, and serious persistent pollution is caused to the ground surface and underground water. How to scientifically and efficiently remove a plurality of pollutants in water has become one of the hot spots of the research of academic and engineering circles at home and abroad.
The method for removing the pollutants in the water mainly comprises adsorption, filtration, biodegradation, photodegradation and the like, wherein the adsorption method has the advantages of high efficiency, environmental protection, low cost and the like, and becomes a preferred method for treating the water pollution. The traditional adsorbing materials such as activated carbon, clay and the like have low adsorption efficiency and capacity and are easy to cause secondary pollution, so that a novel adsorbing material with high adsorption capacity, high selectivity and excellent cyclic usability is urgently needed. At present, although many three-dimensional (3D) porous materials such as polymer-based foams and sponges can adsorb organic solvents such as oils, the three-dimensional (3D) porous materials have the disadvantages of single function, low adsorption capacity and selectivity and the like. Ge et al (Ge, J., et al.,. ACS Appl Mater Interfaces,2018.10(46): p.40274-40285.) use melamine sponges for adsorption of organic solvents in oil-water mixtures in amounts of only 46-96 times their weight. In contrast, the graphene-based aerogel serving as a novel 3D porous material has unique performances such as excellent hydrophobicity/lipophilicity, low density, high specific surface area, good chemical stability and thermal stability, and has a wide application prospect in the field of advanced adsorption. Bi et al ((Bi, H., et al.,. Advanced Functional Materials,2012.22: p.4421-4425.) adopt graphene oxide as a raw material, obtain graphene hydrogel by a hydrothermal reduction method, and freeze-dry the graphene hydrogel to obtain a graphene-based sponge, which can realize the adsorption of various organic solvents such as toluene, chloroform and the like, but the adsorption rate is lower by 20-86 times of the self weight, and in addition, the recycling of the material by a combustion treatment method has the problems of large energy consumption and easy secondary pollution, mainly because the mechanical properties of pure graphene aerogel are poor, the recovery mode of adsorbates of the graphene-based gel material is limited, and it is worth noting that one-dimensional nano Materials (such as carbon nano tubes, nano fibers and the like), polymers (such as polyvinyl alcohol, polyvinylpyrrolidone and the like) or chemical cross-linking agents (such as glutaraldehyde and the like) are added to effectively improve the mechanical strength and compression resilience of the graphene-based aerogel, and further realizes the effective desorption and cyclic adsorption performance of the gel material through a simple physical extrusion mode. For example, Zhan et al (Zhan, w., et al.,. ACS Applied Materials & Interfaces,2017.10(1): p.1093-1103.) introduced one-dimensional PDA functionalized multi-walled carbon nanotubes (MWCNT-PDA) into a graphene aerogel network, synthesized a robust graphene/carbon nanotube composite aerogel, which could be recycled 10 times by a simple "adsorption-extrusion" method. Xiao et al (Xiao, J., et al.,. Carbon,2017.123: p.354-363.) synthesize a reduced graphene oxide/polyvinyl alcohol aerogel by a hydrothermal in-situ reduction method, and the aerogel subjected to hydrophobic modification can adsorb common grease and organic solvents on water surface, and the adsorption rate can reach 67-155 times of the self weight. Nevertheless, the graphene-based aerogels described above still have some problems in preparation and adsorption applications as follows: (1) the preparation process of the one-dimensional carbon nano tube is complex and has high cost; (2) the hydrothermal method requires high-temperature and high-pressure conditions and a special reaction device, so that the difficulty of practical application is increased; (3) the graphene aerogel has single functionality, and generally, the graphene aerogel can only realize the adsorption of partial organic solvents or oils, so that the treatment of complex water pollutants (such as fluorine ions and the like) is difficult to realize.
It is worth noting that Hydroxyapatite (HAP) is a main component of human and animal bones, belongs to the hexagonal system, has a special crystal structure, surface properties and excellent biocompatibility, and is therefore often used as an inorganic ion and organic matter adsorption and exchange material with excellent performance in the fields of wastewater treatment, treatment of polluted soil and the like. For example, patent CN104289181A discloses a magnetic hydroxyapatite/graphene oxide adsorbent, which is prepared by in-situ growing a magnetic hydroxyapatite in a graphene oxide system to obtain a magnetic hydroxyapatite/graphene oxide powder, and is used for adsorbing heavy metal ions in water. Although the patent prepares the magnetic hydroxyapatite/graphene oxide adsorbent, the patent has the following obvious problems: (a) the used hydroxyapatite is common hydroxyapatite with small specific surface area; (b) the obtained composite material is in a powder form, does not form a three-dimensional structure, and has low porosity; (c) the adsorbed material is difficult to recover and cannot be reused.
In view of the above problems, in the present invention, we use one-dimensional Hydroxyapatite (HAP) nanowires having good biocompatibility, excellent thermal and chemical stability, high flexibility, low cost, and a large number of surface active adsorption sites as an efficient second synergistic component of graphene-based aerogel networks. The introduction of HAP imparts several significant advantages to graphene-based aerogels: (a) the synthesized ultralong hydroxyapatite nanowire can realize effective adhesion and enhancement effects on the 2D graphene sheet layer in the graphene aerogel by utilizing the strong hydrogen bonding effect between the synthesized ultralong hydroxyapatite nanowire and the graphene oxide, so that the mechanical property of the graphene-based aerogel can be obviously improved. (b) The hexagonal crystal structure of HAP enables the graphene-based aerogel to have strong ion exchange capacity, and the nanoscale apatite has the advantages of larger specific surface area, high activity and the like, so that the graphene-based aerogel can be endowed with good fluoride ion adsorption capacity, and excellent multifunctional adsorption characteristics are realized. (c) Compared with the traditional one-dimensional reinforced components (such as carbon nano tubes) and other raw materials, the preparation method of the hydroxyapatite nano-wire has the advantages of easy obtainment of raw materials, simple preparation process and low cost, so that the composite aerogel shows good practical application prospect. It should be noted that, studies on enhancing the mechanical properties of graphene oxide aerogel and endowing the graphene oxide aerogel with multifunctional adsorption characteristics by using hydroxyapatite nanowires have not been reported so far.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and the preparation method thereof, and solves the problems that the graphene-based aerogel in the prior art is high in preparation cost and needs a complex reaction device; the mechanical property of the pure graphene-based aerogel is poor, and the recycling efficiency of the material is influenced; the two-dimensional membrane material or the powder material has low adsorption capacity and selectivity; the graphene-based aerogel has single adsorption function and other troublesome problems.
The invention relates to a graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and a preparation method thereof, and the preparation method has the advantages of low raw material cost, simple steps and short time consumption; the mechanical property of the graphene-based aerogel is enhanced by adopting the high-flexibility ultralong hydroxyapatite nanowire; the excellent wetting selectivity enables the adsorbent to have high adsorption selectivity; the introduction of hydroxyapatite endows the graphene-based aerogel with high adsorption capacity for fluoride ions and the like besides an oil phase adsorption function, so that the graphene oxide/hydroxyapatite nanowire aerogel shows multifunctional adsorption properties.
The technical scheme of the invention is as follows:
a preparation method of graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel comprises the following steps:
1) mixing the GO water dispersion, the HAP nanowire water dispersion and a chemical reducing agent according to a certain proportion, stirring and ultrasonically dispersing the mixture uniformly;
2) carrying out mild reduction-freeze thawing-deep reduction process self-assembly on the blending dispersion liquid to obtain rGO/HAP hydrogel;
3) sequentially freezing and drying the hydrogel to obtain rGO/HAP aerogel;
4) and carrying out high-temperature carbonization treatment or surface hydrophilic modification on the aerogel.
Furthermore, the diameter of the hydroxyapatite nanowire is 10-500 nm, the length of the hydroxyapatite nanowire is 1-100 microns, the thickness of the graphene oxide is 1-10 nm, the size of a lamella is 1-10 microns, and the hydroxyapatite nanowire/graphene oxide enables a mixed water phase suspension of the hydroxyapatite nanowire and the graphene oxide to have good dispersibility through hydrogen bonding.
The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel comprises the following steps of 1), preparing graphene oxide in the step 1) by adopting a Hummers method, wherein the concentration of a graphene oxide aqueous dispersion is 1-20 mg/mL; the hydroxyapatite nanowire is prepared by adopting a calcium oleate precursor-solvothermal method, and the concentration of the hydroxyapatite nanowire water dispersion is 1-15 mg/mL; the mass ratio of the hydroxyapatite to the graphene oxide is 1/15-5; the chemical reducing agent is one or a mixture of more of vitamin C, hydrogen iodide, tannic acid, citric acid, ethylenediamine, dopamine, sodium ascorbate, hydrazine hydrate, ammonia water, thiourea, glucose, chitosan, cyclodextrin, sodium bisulfite, sodium sulfide and hydroquinone, and the mass ratio of the chemical reducing agent to the graphene oxide is 1/15-10; performing magnetic stirring on the mixed dispersion liquid under the condition of 150-1500 rpm/30-180 min; the ultrasonic treatment condition is 200-750W/25-500 kHz/1-120 min.
The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel comprises the following steps of 2), wherein the mild-moderate reduction condition is 50-90 ℃/20 min-48 h; the freezing condition is-5 ℃ to-196 ℃/5min to 48 h: the deep reduction condition is 50-90 ℃/20 min-48 h.
The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel comprises the following steps of 3), wherein the vacuum freezing-drying conditions are as follows: the temperature is-30 to-55 ℃, the vacuum degree is 5.0 to 55Pa, and the time is 6 to 72 hours.
The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel comprises the following steps of 4), wherein the high-temperature carbonization conditions are as follows: the highest temperature is 400-1000 ℃, the heating rate is 5-20 ℃/min, the constant temperature time is 30-180 min, and the required inert atmosphere is one of nitrogen, argon, helium and neon. The hydrophilic modification component can be one or mixture of tetraethyl orthosilicate, chitosan, dopamine, tannic acid, polyethyleneimine, etc.; the hydrophilic modification mode can adopt dip coating, spray coating and the like; the concentration of the hydrophilic modification solution is 0.2-40 mg/mL, the volume is 0.1-50mL, and the modification time is 2-24 h.
The graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel can be used for adsorbing an organic solvent or insoluble oil in water after high-temperature carbonization treatment; the aerogel subjected to surface hydrophilic modification treatment can be used for adsorbing fluorine ions in water.
The invention has the following beneficial effects: 1) the prepared graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel is easy to obtain raw materials, simple in steps and low in cost; 2) compared with pure graphene aerogel, the graphene oxide/hydroxyapatite nanowire aerogel disclosed by the invention has better mechanical properties, so that the graphene oxide/hydroxyapatite nanowire aerogel has good compression resilience; 3) compared with the traditional oil removal material in water, the graphene-based aerogel disclosed by the invention has super-wetting selectivity, and can realize selective adsorption of an organic solvent in water; 4) compared with a two-dimensional membrane material or a powder material, the three-dimensional aerogel disclosed by the invention has high specific surface and porosity and high adsorption capacity which can be hundreds of times of the self weight; 5) compared with the traditional adsorption material which realizes the reutilization through combustion or distillation, the graphene aerogel disclosed by the invention can realize the recycling of the material through simple 'extrusion-adsorption', and has good compression resilience performance even after being soaked in an organic solvent; 6) the graphene oxide/hydroxyapatite nanowire aerogel disclosed by the invention can realize the multifunctional adsorption characteristics of insoluble oil/organic solvent and fluoride ions in water, and has stronger universality.
Drawings
Fig. 1 is a preparation route diagram of graphene oxide/hydroxyapatite nanowire aerogel in example 1.
Fig. 2 is a digital photo of the graphene oxide/hydroxyapatite nanowire aerogel prepared in example 1.
Fig. 3 is a water contact angle test chart of the reduced graphene oxide/hydroxyapatite nanowire aerogel in air after carbonization in example 1.
Fig. 4 is a graph of a test of an oil contact angle of the reduced graphene oxide/hydroxyapatite nanowire aerogel in air after carbonization in example 1.
Fig. 5 is a digital photo of the compression rebound test of the reduced graphene oxide/hydroxyapatite nanowire aerogel after carbonization in example 1.
Fig. 6 shows that the reduced graphene oxide/hydroxyapatite nanowire aerogel obtained in example 1 cyclically adsorbs n-hexane in an adsorption-extrusion manner.
Fig. 7 is a water contact angle test chart of the reduced graphene oxide/hydroxyapatite nanowire aerogel subjected to hydrophilic modification in air in example 1.
Detailed Description
The invention provides a graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: a preparation route of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel is shown in fig. 1, and specifically, 6mL of hydroxyapatite nanowire/graphene oxide dispersion liquid (where the concentration of graphene oxide is 3mg/mL, and the concentration of hydroxyapatite nanowire is 3mg/mL) is prepared as follows: taking 1mL of graphene oxide (18mg/mL) into a beaker, adding 2mL of hydroxyapatite nanowire (9mg/mL), adding 0.9mL of sodium ascorbate (100mg/mL), adding 2.1mL of deionized water, and performing ultrasonic dispersion (300W/250kHz/5min) and magnetic stirring (600rpm/90min) treatment on the mixed solution to obtain a uniformly dispersed mixed dispersion solution. Taking the dispersion liquid into a flat-bottom small bottle, and carrying out mild reduction assembly for 2h at the temperature of 60 ℃; after cooling, putting the mixture into the lower layer of a refrigerator to be frozen for 12 hours at (-18 ℃); after melting, reducing the mixture in an oil bath kettle at 60 ℃ for 10 hours to obtain reduced graphene oxide/hydroxyapatite nanowire hydrogel; dialyzing with deionized water for 3 days; and (3) freezing the dialyzed hydrogel in a freezing layer (-18 ℃) of a refrigerator for 15 hours at the temperature of minus 48 ℃ and the vacuum degree of 10.0Pa, and freeze-drying for 48 hours to obtain the reduced graphene oxide/hydroxyapatite nanowire aerogel.
Carbonizing the graphene aerogel at 800 ℃ for 1h (under the protection of nitrogen) to obtain the graphene-based aerogel. As shown in FIG. 2, the aerogel has better overall formability; meanwhile, the contact angle of the aerogel to water reaches 148 degrees (figure 3), oil drops can rapidly permeate into the aerogel (figure 4), and therefore the aerogel has super-hydrophobicity and super-lipophilicity, can adsorb oil pollutants in water at high selectivity, achieves treatment of oily wastewater, has high compression-resilience (figure 5) and can achieve desorption and cyclic adsorption capacity of adsorbing an oil phase by simple extrusion, and the oil phase is n-hexane.
In addition, the reduced graphene oxide/hydroxyapatite nanowire aerogel is soaked in 2mg/mL dopamine hydrochloride buffer solution for 6 hours and then dried in a vacuum oven at 50 ℃ for 5 hours to obtain the polydopamine surface modified reduced graphene oxide/hydroxyapatite nanowire aerogel, which shows super-hydrophilicity (fig. 7, water contact angle is 0 °), has high adsorbability to fluoride ions in water, and the adsorption capacity can be as high as 78 mg/g.
Example 2: preparing 6mL of hydroxyapatite nanowire/graphene oxide dispersion liquid (wherein the concentration of the graphene oxide is 5mg/mL, and the concentration of the hydroxyapatite nanowire is 1 mg/mL): taking 2mL of graphene oxide (15mg/mL) in a beaker, adding 1mL of hydroxyapatite nanowire (6mg/mL), adding 0.3mL of sodium ascorbate (100mg/mL), adding 2.7mL of deionized water, and performing ultrasonic dispersion (300W/250kHz/8min) and magnetic stirring (600rpm/60min) treatment on the mixed solution to obtain a uniformly dispersed mixed dispersion solution. Taking the dispersion liquid into a flat-bottom small bottle, and carrying out mild reduction assembly for 20min at the temperature of 85 ℃; after cooling, putting the mixture into the lower layer of a refrigerator to be frozen for 12 hours at (-18 ℃); after melting, reducing the mixture in an oil bath kettle at 50 ℃ for 15 hours to obtain reduced graphene oxide/hydroxyapatite nanowire hydrogel; dialyzing with deionized water for 3 days; and (3) freezing the dialyzed hydrogel in a freezing layer of a refrigerator at (-18 ℃) for 24 hours, then freezing and drying for 48 hours at-48 ℃ under the vacuum degree of 10.0Pa to obtain the reduced graphene oxide/hydroxyapatite nanowire aerogel.
Carbonizing the graphene aerogel at 400 ℃ for 2.5h (under the protection of nitrogen) to obtain the graphene-based aerogel. The aerogel has better integral formability; simultaneously this aerogel reaches 145 to the contact angle of water, can realize absorbing fast when the contact oil drops, has super oleophylic super hydrophobicity, can the selective adsorption aquatic waste oil, realizes the processing of oily waste water, reaches 117 times of self weight to the adsorption capacity of hexadecane to can realize circulation adsorption efficiency through simple extrusion.
And in addition, soaking the reduced graphene oxide/hydroxyapatite nanowire aerogel in 4mg/mL tannic acid solution for 24 hours, and then drying the soaked reduced graphene oxide/hydroxyapatite nanowire aerogel in a 50 ℃ vacuum oven for 5 hours to obtain the hydrophilic surface modified reduced graphene oxide/hydroxyapatite nanowire aerogel, wherein the reduced graphene oxide/hydroxyapatite nanowire aerogel has super-hydrophilicity, high adsorbability to fluorine ions in water, and adsorption capacity of 60 mg/g.
Example 3: preparing 6mL of hydroxyapatite nanowire/graphene oxide dispersion liquid (wherein the concentration of the graphene oxide is 5mg/mL, and the concentration of the hydroxyapatite nanowire is 1 mg/mL): taking 2mL of graphene oxide (15mg/mL) in a beaker, adding 1mL of hydroxyapatite nanowire (6mg/mL), adding 0.3mL of sodium ascorbate (100mg/mL), adding 2.7mL of deionized water, and performing ultrasonic dispersion (200W/50kHz/120min) and magnetic stirring (1000rpm/30min) treatment on the mixed solution to obtain a uniformly dispersed mixed dispersion solution. Taking the dispersion liquid into a flat-bottom small bottle, and carrying out mild reduction assembly for 20min at the temperature of 85 ℃; rapidly freezing with liquid nitrogen for 10 min; after melting, reducing the mixture in an oil bath kettle at 70 ℃ for 5 hours to obtain reduced graphene oxide/hydroxyapatite nanowire hydrogel; dialyzing with deionized water for 3 days; and (3) rapidly freezing the dialyzed hydrogel for 15min by using liquid nitrogen, then freezing and drying for 48h at the temperature of-48 ℃ and the vacuum degree of 20.0Pa to obtain the reduced graphene oxide/hydroxyapatite nanowire aerogel.
Carbonizing the graphene aerogel at 600 ℃ for 1.5h (under the protection of nitrogen) to obtain the graphene-based aerogel. The aerogel has better integral formability; simultaneously, the aerogel has a contact angle to water of 140 degrees, can realize quick absorption to oil, has super-oleophylic and super-hydrophobic properties, can selectively adsorb waste oil in water, realizes the treatment of oily wastewater, has an adsorption capacity to chloroform of 110 times of the self weight, and can realize the circulating adsorption capacity through simple extrusion.
And soaking the reduced graphene oxide/hydroxyapatite nanowire aerogel in 5mg/mL tetraethyl orthosilicate/ethanol mixed solution for 6h, and then drying the soaked reduced graphene oxide/hydroxyapatite nanowire aerogel in a vacuum oven at 35 ℃ for 10h to obtain the reduced graphene oxide/hydroxyapatite nanowire aerogel with the surface modified by hydrophilicity, wherein the reduced graphene oxide/hydroxyapatite nanowire aerogel has hydrophilicity, high adsorbability on fluorine ions in water and adsorption capacity of 55 mg/g.
Example 4: preparing 6mL of hydroxyapatite nanowire/graphene oxide dispersion liquid (wherein the concentration of the graphene oxide is 3mg/mL, and the concentration of the hydroxyapatite nanowire is 1 mg/mL): 1mL of graphene oxide (18mg/mL) is put into a beaker, 1mL of hydroxyapatite nanowire (6mg/mL) is added, 0.3mL of hydrazine hydrate (100mg/mL) is added, 3.7mL of deionized water is added, and the mixed solution is subjected to ultrasonic dispersion (400W/100kHz/60min) and magnetic stirring (1000rpm/30min) to obtain a uniformly dispersed mixed dispersion solution. Taking the dispersion liquid into a flat-bottom small bottle, and carrying out mild reduction assembly for 2h at the temperature of 60 ℃; rapidly freezing with liquid nitrogen for 10 min; after melting, reducing the mixture in an oil bath kettle at 50 ℃ for 10 hours to obtain reduced graphene oxide/hydroxyapatite nanowire hydrogel; dialyzing with deionized water for 3 days; and (3) rapidly freezing the dialyzed hydrogel for 15min by using liquid nitrogen, then freezing and drying for 48h at the temperature of-48 ℃ and under the vacuum degree of 10.0Pa to obtain the reduced graphene oxide/hydroxyapatite nanowire aerogel.
Carbonizing the graphene aerogel at 600 ℃ for 2h (under the protection of argon) to obtain the graphene-based aerogel. The aerogel has better integral formability; simultaneously this aerogel reaches 140 to the contact angle of water, just can realize quick absorption to oil, has super oleophylic super hydrophobicity, can the selective adsorption aquatic waste oil, realizes the processing of oily waste water, reaches 107 times of self weight to the adsorption capacity of n-hexane to can realize circulation adsorption efficiency through simple extrusion.
And in addition, soaking the reduced graphene oxide/hydroxyapatite nanowire aerogel in 10mg/mL chitosan solution for 24 hours, and then drying the soaked reduced graphene oxide/hydroxyapatite nanowire aerogel in a vacuum oven at 50 ℃ for 5 hours to obtain the surface-hydrophilically-modified reduced graphene oxide/hydroxyapatite nanowire aerogel, wherein the surface-hydrophilically-modified reduced graphene oxide/hydroxyapatite nanowire aerogel has super-hydrophilicity, high adsorbability on fluoride ions in water, and adsorption capacity of 75 mg/g.
Finally, it should be noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel is characterized by comprising the following steps:
1) mixing the GO water dispersion, the HAP nanowire water dispersion and a chemical reducing agent according to a certain proportion, stirring and ultrasonically dispersing the mixture uniformly;
2) carrying out mild chemical reduction-freeze thawing-deep reduction process self-assembly on the blended dispersion liquid to obtain rGO/HAP hydrogel;
3) sequentially freezing and drying the hydrogel to obtain rGO/HAP aerogel;
4) carry out high temperature carbonization treatment or surface hydrophilic modification to above-mentioned aerogel, the aerogel through high temperature carbonization treatment can be used for the absorption of aquatic organic solvent or insoluble oil, and the aerogel through surface hydrophilic modification treatment can be used for the absorption of aquatic fluorine ion.
2. The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel according to claim 1, wherein the diameter of the hydroxyapatite nanowire is 10-500 nm, the length of the hydroxyapatite nanowire is 1-100 μm, the thickness of the graphene oxide is 1-10 nm, the size of a lamella is 1-10 μm, and the hydroxyapatite nanowire and the graphene oxide have good dispersibility in a mixed aqueous suspension through a hydrogen bond effect.
3. The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel according to claim 1, wherein the graphene oxide in the step 1) is prepared by a Hummers method, and the concentration of the graphene oxide aqueous dispersion is 1-20 mg/mL; the hydroxyapatite nanowire is prepared by adopting a calcium oleate precursor-solvothermal method, and the concentration of the hydroxyapatite nanowire water dispersion is 1-15 mg/mL; the mass ratio of the hydroxyapatite to the graphene oxide is 1/15-5; the chemical reducing agent is one or a mixture of more of vitamin C, hydrogen iodide, tannic acid, citric acid, ethylenediamine, dopamine, sodium ascorbate, hydrazine hydrate, ammonia water, thiourea, glucose, chitosan, cyclodextrin, sodium bisulfite, sodium sulfide and hydroquinone, and the mass ratio of the chemical reducing agent to the graphene oxide is 1/15-10; performing magnetic stirring on the mixed dispersion liquid under the condition of 150-1500 rpm/30-180 min; the ultrasonic treatment condition is 200-750W/25-500 kHz/1-120 min.
4. The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel according to claim 1, wherein the mild reduction condition in the step 2) is 50-90 ℃/20 min-48 h; the freezing condition is-5 ℃ to-196 ℃/5min to 48 h: the deep reduction condition is 50-90 ℃/20 min-48 h.
5. The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel according to claim 1, wherein the vacuum freeze-drying conditions in the step 3) are as follows: the temperature is-30 to-55 ℃, the vacuum degree is 5.0 to 55Pa, and the time is 18 to 72 hours.
6. The preparation method of the graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel according to claim 1, wherein the high-temperature carbonization conditions in the step 4) are as follows: the highest temperature is 400-1000 ℃, the heating rate is 5-20 ℃/min, the constant temperature time is 30-180 min, and the required inert atmosphere is one of nitrogen, argon, helium and neon; the hydrophilic modification component can be one or mixture of tetraethyl orthosilicate, chitosan, dopamine, tannic acid, polyethyleneimine, etc.; the hydrophilic modification mode can adopt dip coating, spray coating and the like; the concentration of the hydrophilic modification solution is 0.2-40 mg/mL, the volume is 0.1-50mL, and the modification time is 2-24 h.
7. The graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel prepared by the method of any one of claims 1 to 6.
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