CN111484644A - Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel - Google Patents
Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel Download PDFInfo
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Abstract
The invention discloses a method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel, which is characterized by comprising the following steps of firstly, axially cutting a multiwalled carbon nanotube by a potassium permanganate oxidation method to prepare a graphene oxide nanoribbon; then adding the mixture into a mixed solution of acrylonitrile and ammonium persulfate which are fully mixed, and preliminarily preparing polyacrylonitrile/graphene nanoribbon composite hydrogel by adopting a solvothermal polymerization method; and converting the cyano group into an amidoxime group by utilizing the reaction between the cyano group and hydroxylamine under an alkaline condition to obtain the polyamidoxime/graphene nanoribbon composite hydrogel, and finally freezing and drying at a low temperature to prepare the polyamidoxime/graphene nanoribbon composite aerogel. The polyamidoxime/graphene nanoribbon composite aerogel prepared by the method disclosed by the invention is high in grafting rate, uniform in density distribution, stable in structural performance, rich in uranium-containing special functional groups, capable of effectively and selectively removing uranium from different uranium-containing water bodies, capable of quickly separating and recycling the adsorbed aerogel from a solid-liquid system, and free of pollution to the environment.
Description
The technical field is as follows:
the invention belongs to the field of material synthesis and radioactive wastewater treatment, and relates to a method for preparing polyamidoxime/graphene nanoribbon composite aerogel and separating and enriching uranium-containing wastewater.
Background art:
uranium is an important nuclear fuel and one of the preconditions for the development of nuclear power. In addition, uranium is also a potential radioactive poison, and if a large amount of uranium is accumulated in the environment, not only the environmental background radiation is improved, but also species gene variation is caused by chemical toxicity, so that potential threats are formed to the survival and development of human beings, and high attention should be paid to the uranium and corresponding measures should be taken. Therefore, the uranium is separated, enriched and recovered from different uranium-containing aqueous phase media, and the method has very important significance for improving the utilization efficiency of uranium, realizing sustainable development of nuclear energy, protecting environment and protecting human health. The adsorption method has the characteristics of wide material source, low cost, high selectivity, simplicity in operation, low energy consumption, high speed, large capacity and the like, and thus, the adsorption method becomes one of the most promising methods for separating and enriching uranium in an aqueous solution. The key and basis for realizing efficient uranium separation are to obtain the adsorbent with high separation efficiency, excellent selectivity and good chemical and irradiation stability.
Carbon aerogel, particularly graphene aerogel, has a wide application prospect in the field of adsorption of uranium-containing wastewater due to the advantages of a typical nanoporous network structure, a high specific surface area, a high porosity, a low density, high adsorbability, a high mechanical strength and easiness in solid-liquid separation, for example, CN108816187A, "a L-arginine-modified graphene oxide sponge and uranium adsorption method" discloses that a L-arginine-modified graphene oxide sponge adsorbent having a three-dimensional structure is prepared by using graphene oxide as a precursor and L-arginine as a cross-linking agent through a hydrothermal method and a freeze-drying method, has a good adsorption effect on uranium, and has a maximum adsorption amount of 202.43mg/g, and further, "z.zhang, z.dong, x.wang, y.dai, x.cao, y.wang, r.hua, h.feng, j.chen, y. L iu, Synthesis of graphene oxide sponge, h.cheng, j.chen, y. L iu, and g, and the maximum adsorption amount of graphene oxide in water is achieved by using a graphene skeleton-based adsorbent under the conditions of" c. zhuchi-alumina gel ".
Graphene nanoribbons are defined as graphene with a width of tens of nanometers, and simultaneously keep an aspect ratio greater than 10, and are another quasi-one-dimensional carbon-based nanomaterial following carbon nanotubes, which has more flexible and adjustable properties and greater application value than graphene, and have excellent properties of both carbon nanotubes and graphene, compared with graphene, graphene nanoribbons are more suitable as a structural material of a functional material, and can be widely applied to the fields of electrochemistry, energy storage, sensing and adsorption, while graphene nanoribbons aerogel prepared with graphene nanoribbons as a substrate has excellent properties of flexibly adjustable internal structural dimensions, more abundant surface functional groups, and the like, in addition to a series of characteristics of the above graphene aerogel, a preparation method of N and S double-doped graphene nanoribbons aerogel discloses a preparation method of N and S double-doped graphene nanoribbons aerogel, which has a great potential for being inserted into graphene aerogel layers such as cheuchen, graphene nanoribbons, graphene nano aerogel, graphene nano gel, graphene nano aerogel, and so on.
Meanwhile, in order to further improve the adsorption capacity and selectivity of the material, functional components with stronger coordination capacity to target nucleic are often grafted on a general solid-phase substrate material. Amidoxime (H)2N-C ═ N-OH) is an excellent polydentate ligand, and the C-N and N-O bonds on the oxime group have strong coordination ability for various types of metal ions (such as actinide, lanthanide, transition metal and noble metal ions). Amidoxime is a functional group with high adsorption rate, high selectivity and affinity to uranium, can perform complexation on uranium under the condition of small uranium concentration, and can extract uranium from seawater and salt lake water with complex components. For example CN109954484AThe invention firstly dissolves polyacrylonitrile and a pore-making agent in a solvent to prepare polyacrylonitrile solution, then coats the polyacrylonitrile solution on the surface of mesoporous silica gel particles by a negative pressure permeation method to prepare mesoporous silica gel particles with the surface loaded with the polyacrylonitrile, and then carries out amidoximation reaction on the mesoporous silica gel particles by hydroxylamine hydrochloride solution to obtain the mesoporous silica gel particles loaded with the amidoxime polymer, the mesoporous silica gel particles are oscillated for 6 hours under the conditions that the dosage of an adsorbent is 30mg and the uranyl ion concentration is 100 mg/L, and the adsorption amount of the mesoporous silica gel particles is 107 mg/g.
In view of the above, the polyamidoxime/graphene nanoribbon composite aerogel is prepared by effectively combining an amidoxime functional group with exclusive selectivity on uranium and a graphene nanoribbon aerogel with a high specific area and strong adsorption capacity by using a solvothermal polymerization method, so that the adsorption capacity and selectivity on uranium are improved. The method for grafting amidoxime groups onto the graphene nanoribbon aerogel framework by utilizing a solvothermal polymerization method and the research for separating and enriching uranium are not reported at present.
Disclosure of Invention
The invention provides a preparation method and application of a polyamidoxime/graphene nanoribbon composite aerogel, aiming at solving the technical problems that the grafting rate is low and the distribution is not uniform or the grafting rate is high and the material structure is easy to damage in the existing amidoxime functionalization method, and on the other hand, aiming at solving the defects of complex preparation process, low adsorption capacity and low selectivity of carbon aerogel.
The invention adopts one of the technical schemes:
a preparation method of a polyamidoxime/graphene nanoribbon composite aerogel comprises the following steps: firstly, axially cutting a multi-walled carbon nanotube by a potassium permanganate oxidation method to prepare a graphene oxide nanobelt; then adding the mixture into a mixed solution of acrylonitrile and ammonium persulfate which are fully mixed, and preliminarily preparing polyacrylonitrile/graphene nanoribbon composite hydrogel by adopting a solvothermal polymerization method; and converting the cyano group into an amidoxime group by utilizing the reaction between the cyano group and hydroxylamine under an alkaline condition to obtain the polyamidoxime/graphene nanoribbon composite hydrogel, and finally freezing and drying at a low temperature to prepare the polyamidoxime/graphene nanoribbon composite aerogel.
Further, the graphene oxide nanobelt is prepared by a modified Hummers method, and the mass of the potassium permanganate is 500% of the mass of the carbon tube.
Further, preparing the acrylonitrile monomer and the graphene nanoribbon into polymer functionalized graphene nanoribbon aerogel by adopting a one-step solvent thermal polymerization method.
Further, a liquid form of acrylonitrile monomer is polymerized to the material backbone using a one-step solvent thermal polymerization process. Further, acrylonitrile monomers in liquid form are all or nearly all polymerized to the material backbone using a one-step solvent thermal polymerization process.
Furthermore, the preparation process comprises the following steps:
(1) axially cutting the multi-walled carbon nanotube by using a potassium permanganate oxidation method to prepare a graphene oxide nanobelt, wherein the graphene oxide nanobelt is prepared by adopting a modified Hummers method, and the mass of potassium permanganate is 500% of that of the multi-walled carbon nanotube;
(2) preparing an acrylonitrile monomer and a graphene nanoribbon into polymer functionalized graphene nanoribbon aerogel by adopting a one-step solvent thermal polymerization method, and polymerizing the acrylonitrile monomer in a liquid form to a material framework by adopting the one-step solvent thermal polymerization method; adding the graphene oxide nanoribbon into a fully mixed solution of acrylonitrile and ammonium persulfate, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain polyacrylonitrile/graphene nanoribbon composite hydrogel; wherein the mass ratio of the graphene oxide nanobelt to the acrylonitrile to the ammonium persulfate is 1: 2-6: 0.02-0.6;
(3) converting cyano groups into amidoxime groups by utilizing the reaction between the cyano groups and hydroxylamine under an alkaline condition to obtain the polyamidoxime/graphene nanoribbon composite hydrogel, and then freezing and drying at a low temperature to prepare the polyamidoxime/graphene nanoribbon composite aerogel.
Furthermore, in the step (3), the dosage of each substance in the preparation of the polyamidoxime/graphene nanoribbon composite aerogel is based on 1g of polyacrylonitrile/graphene nanoribbon composite hydrogel, and is changed in proportion with the change of the dosage of the polyacrylonitrile/graphene nanoribbon composite hydrogel, while the pH, time and temperature parameters of the solution are not changed, and the preparation method comprises the specific steps of weighing 1g of polyacrylonitrile/graphene nanoribbon composite hydrogel, weighing 1.5g of hydroxylammonium hydrochloride, adding the hydroxylammonium hydrochloride into ethanol and water solution with the volume ratio of 50m L of 1: 1, and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; mixing the polyacrylonitrile/graphene nanoribbon composite hydrogel with a hydroxylammonium hydrochloride alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for a plurality of times, and freeze-drying at-50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel.
Further, the method comprises the following specific steps:
(1) preparation of graphene oxide nanoribbons
Adding 1g of multi-walled carbon nano-tube into a three-neck flask filled with 150m L mass percent concentrated sulfuric acid with the concentration of 98 percent, stirring for 6 hours at room temperature, weighing 500 percent potassium permanganate relative to the mass of the carbon tube into a mixed solution, stirring for 1 hour at room temperature, heating the mixture to 55 ℃, reacting for 30 minutes, raising the temperature to 70 ℃, stabilizing for 5 minutes, stopping the reaction, cooling to room temperature, pouring the mixture into 400m L ice containing 5m L hydrogen peroxide, filtering by using a 5.0 mu m polytetrafluoroethylene membrane, dissolving solids in 120m L deionized water, carrying out ultrasonic treatment for 30 minutes, dialyzing for more than one week in a dialysis bag with the molecular weight cutoff of 3.5K, and finally vacuum-filtering the mixed solution, and vacuum-drying the solids for 24 hours at 60 ℃ for later use.
In other implementations, the above substance dosage is based on the multi-walled carbon nanotube, and is changed in proportion with the change of the multi-walled carbon nanotube dosage, and other parameters are unchanged;
(2) preparation of polyacrylonitrile/graphene nanoribbon composite hydrogel
Adding 0.1-0.5 g of graphene oxide nanobelt, 0.1-0.3 g of ammonium persulfate and 1-3 m of L acrylonitrile into 15m of L deionized water, stirring for 1-5 h at 25 ℃, adding the solution into a 20m L hydrothermal reaction kettle, reacting for 24h at 100-180 ℃, taking out, cooling to room temperature, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain polyacrylonitrile/graphene nanobelt composite hydrogel;
(3) preparation of polyamidoxime/graphene nanoribbon composite aerogel
Adding 0.5-1.5 g NH2Adding OH & HCl to 50m L ethanol and water solution (1: 1), and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; soaking 1-2 g of polyacrylonitrile/graphene nanoribbon composite hydrogel into the alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for a plurality of times, and freeze-drying at-50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel.
The second technical scheme of the invention is as follows: an application of a polyamidoxime/graphene nanoribbon composite aerogel as an adsorbent for separating and enriching uranium.
According to the third technical scheme, the method for separating and enriching uranium from the polyamidoxime/graphene nanoribbon composite aerogel comprises the steps of adjusting the pH value of a uranium-containing solution to be treated to be 1-7, adding an adsorbent, oscillating and adsorbing, wherein the concentration of the uranium-containing solution is 20-300 mg/L, the mass ratio of the volume of the uranium-containing solution to the mass of the adsorbent is 50m L: 0.010g, the adsorption temperature is 5-45 ℃, the adsorption time is 0.5-24 h, and the oscillation speed is 120 r/min.
Further, the pH was 4.5, the temperature was 25 ℃ and the adsorption time was 1 hour.
The invention has the advantages of
(1) The polyamidoxime/graphene nanoribbon composite aerogel prepared by the method is high in grafting rate, uniform in density distribution and stable in structural performance; as in examples 1-3, the grafting ratio of amidoxime in the polyamidoxime/graphene nanoribbon composite aerogel is as high as 40% -50%;
(2) the polyamidoxime/graphene nanoribbon composite aerogel prepared by the method has the advantages of simple and direct preparation method, easiness in operation, reusability and the like;
(3) for uranyl ions in an aqueous solution, as shown in examples 4 to 7, 0.01g of the adsorbent A-1 can achieve adsorption balance by adsorbing uranium for 1 hour, the adsorption amounts of uranium under different parameters are 341.5mg/g, 402.1mg/g and 478.8mg/g respectively, and the selectivity is as high as 65%; compared with the existing CN108816187A (adsorption equilibrium time of arginine modified graphene sponge to uranium is 9h, the highest adsorption capacity is 202.43mg/g), CN109954484A (adsorption equilibrium time of mesoporous silica gel particle loaded amidoxime polymer to uranium is 6h, the highest adsorption capacity is 107mg/g) uranium adsorption material, the adsorption of the polyamidoxime/graphene nanoribbon composite aerogel to uranium has the characteristics of high adsorption speed, high adsorption capacity and good selectivity, and uranyl ions in an aqueous solution can be effectively adsorbed and recovered. After adsorption, the aerogel can be quickly separated and recovered from a solid-liquid system, and the environment is not polluted.
The invention is mainly embodied in the following aspects:
(1) the technical concept of the invention is that compared with N or (and) S doped aerogel in CN 109003826B and the paper "Three-dimensional nitro-graphene nanogels as a high-level effective catalyst for the oxidative reduction reaction", poly amidoxime/graphene nanoribbon aerogel is adopted; the process method is mainly different from the method disclosed by the invention and the paper, pyrrole and thiophene are grafted to the surfaces of graphene and graphene nanoribbons by a two-step hydrothermal and one-step high-temperature cracking method to prepare the N and S doped aerogel, and the acrylonitrile monomer and the graphene nanoribbons can be prepared into the polymer functionalized graphene nanoribbon aerogel by a one-step solvothermal polymerization method; the technical creativity is that N and O are grafted to the graphene nanoribbon framework in the form of polymer instead of N or S is embedded into the graphene nanoribbon layer in the form of atom as described in the above patents and papers.
(2) Loading an amidoxime polymer on mesoporous silica gel particles of CN109954484A, and adopting polyamidoxime/graphene nanobelt aerogel; the main difference of polyamidoxime is that in CN109954484A, polyacrylonitrile powder is dissolved in a solvent, and polyacrylonitrile is coated on the surface of mesoporous silica gel by a negative pressure permeation method, which is a method for directly coating polyacrylonitrile on the surface of a material, the grafted functional groups have the disadvantages of low density and uneven distribution, so that the concentration of the functional groups in the adsorbent is not high, and the adsorption performance of the adsorbent to uranium is reduced. In the invention, a one-step solvent thermal polymerization method is utilized to fully polymerize the liquid acrylonitrile monomer to the material framework, so that the content of amidoxime functional groups in the prepared aerogel is high, the grafting rate is as high as 40-50%, and the adsorption performance of the aerogel on uranium is greatly improved.
(3) With respect to carbon aerogel prepared in CN108816187A and the article "Synthesis of ultra light phosphated carbon aerogel for effective removal of U (VI): batch and fixed-bed columns", polyamidoxime/graphene nanoribbon aerogel was used; the invention is mainly distinguished in that the invention and the paper mainly use a cross-linking agent or a method for synthesizing carbon aerogel through wet chemical post-modification, the grafting rate of functional groups is low due to the existence of the cross-linking agent or the defect of post-grafting, the functional groups are not uniformly distributed in a framework, and the adsorption capacity of the functional groups to uranium is not high.
Drawings
Fig. 1 is a photograph of a polyamidoxime/graphene nanoribbon composite aerogel prepared in example 1;
FIG. 2 is a scanning electron micrograph of the polyamidoxime/graphene nanoribbon composite aerogel prepared in example 1;
fig. 3 is a case that the polyamidoxime/graphene nanoribbon composite aerogel block prepared in example 1 is in a uranium solution;
fig. 4 is a loading diagram of a polyamidoxime/graphene nanoribbon composite aerogel block prepared in example 1.
FIG. 5 is a graph of the adsorption amount of the polyamidoxime/graphene nanoribbon composite aerogel prepared in example 1 as an adsorbent in example 4 as a function of time;
fig. 6 is a selective adsorption diagram of the polyamidoxime/graphene nanoribbon composite aerogel prepared in example 1 as an adsorbent in example 4.
Detailed Description
The invention is further illustrated below with reference to specific examples. The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination between the specific embodiments.
Example 1
The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to the embodiment comprises the following steps:
(1) preparation of graphene oxide nanoribbons
Adding 1g of multi-walled carbon nanotube into a three-neck flask filled with 150m L mass percent concentrated sulfuric acid with the concentration of 98 percent, stirring for 6h at room temperature, then weighing 5g of potassium permanganate into the mixed solution, stirring for 1h at room temperature, heating the mixture to 55 ℃, reacting for 30min, raising the temperature to 70 ℃, stabilizing for 5min, stopping the reaction, cooling to room temperature, pouring the mixture into 400m L ice containing 5m L hydrogen peroxide, filtering by using a 5.0 mu m polytetrafluoroethylene membrane, dissolving the solid in 120m L deionized water, carrying out ultrasonic treatment for 30min, dialyzing for more than one week in a dialysis bag with the molecular weight cutoff of 3.5K, finally, carrying out vacuum filtration on the mixed solution, and carrying out vacuum drying on the solid for 24h at 60 ℃.
(2) Preparation of polyacrylonitrile/graphene nanoribbon composite hydrogel
Adding 0.25g of graphene oxide nanobelt, 1g of acrylonitrile and 0.1g of ammonium persulfate into 15m L deionized water, stirring for 2h at 25 ℃, adding the solution into a reaction kettle, carrying out solvothermal reaction for 24h at 120 ℃, taking out, cooling to room temperature, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain the polyacrylonitrile/graphene nanobelt composite hydrogel.
(3) Preparation of polyamidoxime/graphene nanoribbon composite aerogel
Weighing 2g polyacrylonitrile/graphene nanoribbon composite hydrogel, weighing 3g hydroxylammonium hydrochloride, adding into 100m L ethanol and water solution (1: 1), and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; mixing the polyacrylonitrile/graphene nanoribbon composite hydrogel with a hydroxylammonium hydrochloride alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for a plurality of times, and freeze-drying at-50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel A-1.
The polyamidoxime/graphene nanoribbon composite aerogel prepared in this embodiment is prepared by taking acrylonitrile as a monomer through a solvothermal polymerization method, and is a composite aerogel obtained by grafting a polymer taking an amidoxime group as a functional group onto a graphene oxide nanoribbon substrate, wherein the mass percentage of the polyamidoxime contained in the composite aerogel is 41.6%.
The polyamidoxime/graphene nanoribbon composite aerogel prepared in this example is a bulk material, the photo of which is shown in fig. 1, and the scanning electron microscope photo of which is shown in fig. 2, and as can be seen from fig. 2, the composite aerogel is a porous structure and has a large specific surface area, and the BET specific surface area is 276.1m2/g。
The polyamidoxime/graphene nanoribbon composite aerogel prepared in this embodiment has a low density, can float in water, is in a state in a uranium solution as shown in fig. 3, but has a good strength, is not fragile, and can be used repeatedly, and 5 unitary coins are placed on a composite aerogel with a diameter of about 10mm as shown in fig. 4, so that the composite aerogel cannot be damaged, which indicates that the polyamidoxime/graphene nanoribbon composite aerogel prepared in this embodiment has a good strength.
Example 2
The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to the embodiment comprises the following steps:
(1) preparation of graphene oxide nanoribbons
Same as in step (1) of example 1.
(2) Preparation of polyacrylonitrile/graphene nanoribbon composite hydrogel
Adding 0.5g of graphene oxide nanobelt, 2.5g of acrylonitrile and 0.3g of ammonium persulfate into 15m L deionized water, stirring for 2h at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24h at 120 ℃, taking out, cooling to room temperature, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain the polyacrylonitrile/graphene nanobelt composite hydrogel.
(3) Preparation of polyamidoxime/graphene nanoribbon composite aerogel
Weighing 1g polyacrylonitrile/graphene nanoribbon composite hydrogel, weighing 1.5g hydroxylammonium hydrochloride, adding into 50m L ethanol and water solution (1: 1), and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; mixing the polyacrylonitrile/graphene nanoribbon composite hydrogel with a hydroxylammonium hydrochloride alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for a plurality of times, and freeze-drying the solid at the temperature of minus 50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel A-2.
The polyamidoxime/graphene nanoribbon composite aerogel prepared in this embodiment is prepared by taking acrylonitrile as a monomer through a solvothermal polymerization method, and is a composite aerogel obtained by grafting a polymer taking an amidoxime group as a functional group onto a graphene oxide nanoribbon substrate, wherein the mass percentage of the polyamidoxime contained in the composite aerogel is 43.9%.
Example 3
The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to the embodiment comprises the following steps:
(1) preparation of graphene oxide nanoribbons
Same as in step (1) of example 1.
(2) Preparation of polyacrylonitrile/graphene nanoribbon composite hydrogel
Adding 0.2g of graphene oxide nanobelt, 1.2g of acrylonitrile and 0.1g of ammonium persulfate into 15m L of deionized water, stirring for 2 hours at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 20 hours at 180 ℃, taking out, cooling to room temperature, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain the polyacrylonitrile/graphene nanobelt composite hydrogel.
(3) Preparation of polyamidoxime/graphene nanoribbon composite aerogel
Weighing 0.5g polyacrylonitrile/graphene nanoribbon composite hydrogel, weighing 0.75g hydroxylammonium hydrochloride, adding into 25m L ethanol and water solution (1: 1), and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; mixing the polyacrylonitrile/graphene nanoribbon composite hydrogel with a hydroxylammonium hydrochloride alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for a plurality of times, and freeze-drying at-50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel A-3.
The polyamidoxime/graphene nanoribbon composite aerogel prepared in this embodiment is prepared by taking acrylonitrile as a monomer through a solvothermal polymerization method, and is a composite aerogel obtained by grafting a polymer taking an amidoxime group as a functional group onto a graphene oxide nanoribbon substrate, wherein the mass percentage of the polyamidoxime contained in the composite aerogel is 48.2%.
Example 4
The polyamidoxime/graphene nanoribbon composite aerogel A-1 prepared in example 1 is used as uranium in an adsorbent adsorption solution, and the specific operation is as follows, 50m L, 100 mg/L of pure uranium standard solution and UO-containing standard solution are respectively transferred2 2+、Ba2+、Ce3+、Co2+、Gd3 +、La3+、Mn2+、Nd3+、Ni2+、Sm3+、Sr2+、U(VI)、Zn2+、Cs+These 13 kinds of hetero ion solutions were put in a 100m L conical flask, the pH of the solution was adjusted with 0.1 mol/L nitric acid, 5 mol/L nitric acid, 0.1 mol/L NaOH solution and 5 mol/L NaOH solution so that the pH of the solution became 4.5, 0.010g of adsorbent A-1 was added, respectively, at 25 ℃,adsorbing on a constant temperature oscillator with the rotation speed of 120r/min, sampling, filtering and separating after adsorbing for a certain time, measuring the concentration of uranyl ions and competitive ions in the filtrate by using an ICP-OES (inductively coupled plasma optical emission spectroscopy) analytical method, and calculating the adsorption quantity of the adsorbent A-1 to uranium by combining the formula (1) and the selectivity by combining the formula (2).
The adsorption quantity and selectivity of the uranyl ions are respectively calculated according to the following formulas:
in the formula: q. q.seAdsorption in mg/g, volume of V-uranyl solution L, CeEquilibrium concentration of uranyl ion solution, mg/L C0Initial concentration of uranyl ion solution, mg/L, m-mass of adsorbent, g, SU-selectivity,%; q. q.sU-amount of uranium adsorbed in the competition solution, mg/g; q. q.sGeneral assembly-the amount of total ions adsorbed in the competition solution, mg/g;
the change of the adsorption amount with time is plotted in the graph, as shown in fig. 5, as can be seen from fig. 5, the adsorption equilibrium is approached after adsorption for 40min, and the adsorption speed is high.
According to calculation, after the polyamidoxime/graphene nanoribbon composite aerogel prepared in the embodiment is used as an adsorbent, and the adsorption amount of the polyamidoxime/graphene nanoribbon composite aerogel to uranium is 341.5mg/g after the polyamidoxime/graphene nanoribbon composite aerogel is adsorbed for 1 hour; the selectivity to uranium was 65.1% in the 13 hetero-ionic solutions, as shown in fig. 6.
Example 5
The method comprises the following steps of accurately transferring 50m L and 200 mg/L uranium standard solution into a 100m L conical flask, adjusting the pH value of the solution by using 0.1 mol/L nitric acid, 5 mol/L nitric acid, 0.1 mol/L NaOH solution and 5 mol/L NaOH solution to be 4.5, adding 0.010g of adsorbent A-1, adsorbing the solution on a constant temperature oscillator at 25 ℃ and 120r/min for 1 hour, filtering and separating, measuring the concentration of uranyl ions in the filtrate by using an ICP-OES (inductively coupled plasma optical spectroscopy) spectrum method, and calculating the adsorption amount to be 402.1mg/g by combining the formula (1).
Example 6
The polyamidoxime/graphene nanoribbon composite aerogel A-1 prepared in example 1 is used as uranium in an adsorbent adsorption solution, and the specific operation is that 50m L, 300 mg/L of a uranium standard solution is accurately transferred into a 100m L conical flask, the pH value of the solution is adjusted by using 0.1 mol/L nitric acid, 5 mol/L nitric acid, 0.1 mol/L NaOH solution and 5 mol/L NaOH solution, so that the pH value of the solution is 4.5, 0.010g of the adsorbent A-1 is added, the solution is adsorbed on a constant temperature oscillator at 25 ℃ and 120r/min for 1h, after filtration and separation, the concentration of uranyl ions in the filtrate is measured by using an ICP-OES spectroscopy, and the adsorption amount is calculated to be 478.8mg/g by combining the formula (1) analysis.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel is characterized by comprising the following steps: firstly, axially cutting a multi-walled carbon nanotube by a potassium permanganate oxidation method to prepare a graphene oxide nanobelt; then adding the mixture into a mixed solution of acrylonitrile and ammonium persulfate which are fully mixed, and preliminarily preparing polyacrylonitrile/graphene nanoribbon composite hydrogel by adopting a solvothermal polymerization method; and converting the cyano group into an amidoxime group by utilizing the reaction between the cyano group and hydroxylamine under an alkaline condition to obtain the polyamidoxime/graphene nanoribbon composite hydrogel, and finally freezing and drying at a low temperature to prepare the polyamidoxime/graphene nanoribbon composite aerogel.
2. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 1, wherein the graphene oxide nanoribbon is prepared by a modified Hummers method, and the mass of potassium permanganate is 500% of the mass of the carbon tube.
3. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 1, wherein a one-step solvothermal polymerization method is adopted to prepare the polymer functionalized graphene nanoribbon aerogel from acrylonitrile monomers and graphene nanoribbons.
4. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 1, wherein a liquid form acrylonitrile monomer is polymerized to the material framework by a one-step solvent thermal polymerization method.
5. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 1, wherein the preparation process comprises the following steps:
(1) axially cutting the multi-walled carbon nanotube by using a potassium permanganate oxidation method to prepare a graphene oxide nanobelt, wherein the graphene oxide nanobelt is prepared by adopting a modified Hummers method, and the mass of potassium permanganate is 500% of that of the multi-walled carbon nanotube;
(2) preparing an acrylonitrile monomer and a graphene nanoribbon into polymer functionalized graphene nanoribbon aerogel by adopting a one-step solvent thermal polymerization method, and polymerizing the acrylonitrile monomer in a liquid form to a material framework by adopting the one-step solvent thermal polymerization method; adding the graphene oxide nanoribbon into a fully mixed solution of acrylonitrile and ammonium persulfate, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain polyacrylonitrile/graphene nanoribbon composite hydrogel; wherein the mass ratio of the graphene oxide nanobelt to the acrylonitrile to the ammonium persulfate is 1: 2-6: 0.02-0.6;
(3) converting cyano groups into amidoxime groups by utilizing the reaction between the cyano groups and hydroxylamine under an alkaline condition to obtain the polyamidoxime/graphene nanoribbon composite hydrogel, and then freezing and drying at a low temperature to prepare the polyamidoxime/graphene nanoribbon composite aerogel.
6. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 5, wherein in the step (3), the dosage of each substance in the preparation of the polyamidoxime/graphene nanoribbon composite aerogel is based on 1g of polyacrylonitrile/graphene nanoribbon composite hydrogel, and changes proportionally with the change of the dosage of the polyacrylonitrile/graphene nanoribbon composite hydrogel, while the pH, time and temperature parameters of the solution are unchanged, and the preparation method specifically comprises the steps of weighing 1g of polyacrylonitrile/graphene nanoribbon composite hydrogel, weighing 1.5g of hydroxylammonium hydrochloride, adding the weighed 1: 1 ethanol and water solution into 50m L, and adding saturated K into the ethanol and water solution at a volume ratio of 1: 12CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; mixing the polyacrylonitrile/graphene nanoribbon composite hydrogel with a hydroxylammonium hydrochloride alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for several times, and freeze-drying at the temperature of minus 50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel.
7. The preparation method of the polyamidoxime/graphene nanoribbon composite aerogel according to claim 1, which is characterized by comprising the following specific steps:
(1) preparation of graphene oxide nanoribbons
Adding 1g of multi-walled carbon nanotubes into a three-neck flask filled with 98% concentrated sulfuric acid with the mass percentage concentration of 150m L, stirring for 6 hours at room temperature, weighing 500% of potassium permanganate relative to the mass of the carbon tubes into a mixed solution, stirring for 1 hour at room temperature, heating the mixture to 55 ℃, reacting for 30 minutes, raising the temperature to 70 ℃, stabilizing for 5 minutes, stopping the reaction, cooling to room temperature, pouring the mixture into 400m L ice containing 5m L hydrogen peroxide, filtering with a 5.0-micron polytetrafluoroethylene membrane, dissolving solids in 120m L deionized water, performing ultrasonic treatment for 30 minutes, dialyzing for more than one week in a dialysis bag with the molecular weight cutoff of 3.5K, finally, performing vacuum filtration on the mixed solution, and performing vacuum drying for 24 hours at 60 ℃ for standby application, wherein the dosage of the substances is based on the multi-walled carbon nanotubes, and changes proportionally with the dosage of the multi-walled carbon nanotubes, and other parameters are unchanged;
preparation of polyacrylonitrile/graphene nanoribbon composite hydrogel
Adding 0.1-0.5 g of graphene oxide nanobelt, 0.1-0.3 g of ammonium persulfate and 1-3 m of L acrylonitrile into 15m of L deionized water, stirring for 1-5 h at 25 ℃, adding the solution into a 20m L hydrothermal reaction kettle, reacting for 24h at 100-180 ℃, taking out, cooling to room temperature, immersing the solid in methanol for soaking, and repeatedly washing with deionized water to obtain polyacrylonitrile/graphene nanobelt composite hydrogel;
preparation of polyamidoxime/graphene nanoribbon composite aerogel
Adding 0.5-1.5 g NH2Adding OH & HCl to 50m L ethanol and water solution (1: 1), and adding saturated K2CO3Adjusting the pH value of the alcoholic solution to 8.0, and stirring at room temperature for 30 min; soaking 1-2 g of polyacrylonitrile/graphene nanoribbon composite hydrogel into the alcohol solution, and reacting for 4 hours at 80 ℃; and after the reaction is finished, soaking and washing the solid by using deionized water and ethanol for several times, and freeze-drying at the temperature of minus 50 ℃ for 24 hours to obtain the polyamidoxime/graphene nanoribbon composite aerogel.
8. An application of a polyamidoxime/graphene nanoribbon composite aerogel as an adsorbent for separating and enriching uranium.
9. The method for separating and enriching uranium from the polyamidoxime/graphene nanoribbon composite aerogel is characterized by adjusting the pH value of a uranium-containing solution to be treated to 1-7, adding an adsorbent, oscillating and adsorbing, wherein the concentration of the uranium-containing solution is 20-300 mg/L, the mass ratio of the volume of the uranium-containing solution to the adsorbent is 50m L: 0.010g, the adsorption temperature is 5-45 ℃, the adsorption time is 0.5-24 h, and the oscillation speed is 120 r/min.
10. The method for separating and enriching uranium by using the polyamidoxime/graphene nanoribbon composite aerogel according to claim 9, wherein the pH is 4.5, the temperature is 25 ℃, and the adsorption time is 1 h.
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