CN110327872B - Functional graphite-phase carbon nitride material and preparation method and application thereof - Google Patents
Functional graphite-phase carbon nitride material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a functional graphite-phase carbon nitride material, which is a polymer compound which is constructed by taking sodium ions as doping ions and takes coplanar tris-s-triazine with a layered cavity structure with the aperture of 2-30 nm as a basic structural unit. The invention also discloses a preparation method and application of the material. The invention has the function of the radioactive element90Strong Sr adsorptivity and good selectivity.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a functional graphite-phase carbon nitride material and a preparation method and application thereof.
Background
In recent years, the world energy problem is increasingly prominent, and nuclear energy faces new development opportunities. However, nuclear reactors produce large quantities of "spent fuel" containing large quantities of unspent fertile material during use238U and232th newly formed fissile Material239Pu、235U and233u, transuranic elements such as neptunium, americium and curium generated in the irradiation process, and high exothermic nuclides90Sr、137Cs and99tc, etc., which can seriously affect human health after entering the environment. In addition, the nuclear leakage problem is also receiving wide attention at present, and especially the radionuclides (including about 630000-90Sr、131I、134Cs and137cs, etc.) into the external environment, resulting in serious contamination of the surrounding soil, air and water.
90The radioactive half-life of Sr is as long as 29 years, and Sr has strong biological toxicity, is easy to gather in bones of organisms and is difficult to be excreted out of the bodies.90Sr enters bone tissues, accumulates in inorganic substances close to a bone marrow cavity, irradiates the bone marrow, causes remarkable reduction of white blood cells, red blood cells and platelets, generates regenerative disorder, and causes leukemia and osteosarcoma after being irradiated by strontium for a long time. Therefore, the radioactive nuclide in food and environmental water samples90The pretreatment and trace detection of Sr samples have been widely paid attention to, and have very important significance in the adsorption, extraction and detection research of Sr samples (P.J. Reddy, V. Pulhani,J Radioanal Nucl. Chem.,2017 (314), 359–370) 。
due to radioactive nuclide in environmental water sample or food90Sr has the characteristics of complex system, low radioactive concentration, various nuclide existing forms, lack of standard reference substances and the like, so the radionuclide90Sr is usually detected only after sample pretreatment. At present, the radioactive nuclide in environmental water sample or food is concerned90The main methods for the pretreatment of the Sr sample comprise: chemical precipitation, solvent extraction, membrane distillation, chromatographic column methods, and the like. The methods have the defects of easy interference of complex matrixes, complex pretreatment process, poor selectivity, serious damage to instruments and equipment caused by acid solution used in the elution process, secondary pollution and the like. Therefore, the development and establishment of a sample pretreatment material and a method which are green in preparation, good in selectivity and integrated with extraction and detection are significant (M, Khayet,Desalination, 2013(321), 60-66; R. Kamaraj, S. Vasudevan , Chem. Eng. Res. Des., 2015(93), 522-530) 。
the graphite phase carbon nitride material is a hot material for the current research due to low price, easy obtaining, energy saving, environmental protection, excellent physical properties and stable chemical properties. In recent years, researches show that the graphite phase carbon nitride material, especially the metal-doped graphite phase carbon nitride material has good photocatalytic activity and has wide application prospects in the fields of environmental pollution treatment, clean energy and the like. Research shows that the metal element is doped in the graphite phase carbon nitride material, so that the specific surface area of the material can be increased, the thermal stability of the material is enhanced, and the composite material with a special cavity structure is formed. However, to date, there have been no reports of the application of metal-doped graphite phase carbon nitride materials to radioactive element extraction.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a radioactive element90Sr is strong in adsorbability and good in selectivity.
Another technical problem to be solved by the present invention is to provide a method for preparing the functional graphite-phase carbon nitride material.
The third technical problem to be solved by the invention is to provide the application of the functional graphite-phase carbon nitride material.
In order to solve the above problems, the present invention provides a functionalized graphite-phase carbon nitride material, comprising: the material is a polymer compound which is constructed by taking sodium ions as doping ions, has a layered cavity structure with the aperture of 2-30 nm, and takes coplanar tris-s-triazine as a basic structural unit.
The preparation method of the functionalized graphite-phase carbon nitride material comprises the following steps:
the preparation method comprises the steps of taking a triazine structure compound as a precursor, mixing the triazine structure compound with a sodium ion compound, dissolving the mixture in ultrapure water which is 1-3 times of the mass of the mixture, and stirring at room temperature to fully dissolve the mixture to obtain a triazine structure compound solution containing sodium ions; the mass ratio of the precursor to the sodium ion compound is 5: 1-35: 1;
drying the triazine structural compound solution containing sodium ions until the solution is anhydrous to obtain a white solid;
transferring the white solid into a crucible, and placing the crucible in a muffle furnace for high-temperature calcination; cooling to room temperature after the reaction is finished to obtain light yellow solid powder;
fourth, the light yellow solid powder is prepared from the following components in percentage by weight of 1: adding an acid solution according to the mass-to-volume ratio of 5-20, eluting by 4000W ultrasound for 10-20 min, and centrifuging at 4000rpm for 20min to obtain solid powder;
and fifthly, washing the solid powder with ultrapure water for three times, and drying to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The precursor in the step is any one of urea, melamine, cyanamide, thiourea and dicyandiamide.
Sodium ion compounds in the step are sodium chloride (NaCl) and sodium nitrate (NaNO)3) Sodium sulfate (Na)2SO4) And sodium acetate (NaCOOH).
The step II and the drying condition in the step are all that the temperature is 60-80 ℃.
The high-temperature calcination condition in the step three is that the heating rate is 4 ℃/min, the temperature is 500-580 ℃, and the time is 3-5 h.
The acid solution in the step four is any one of nitric acid, hydrochloric acid, phosphoric acid, and acetic acid having a concentration of 0.1 to 1.0 mol/L.
The application of the functionalized graphite-phase carbon nitride material is characterized in that: the functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr.
Use of a functionalized graphitic carbon nitride material as described above, comprising the steps of:
putting 1.0-10.0 mg of a functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator for oscillation for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 10-20 min to enable the target nuclide90Desorbing Sr from the adsorbent; repeating the above operation for 3 times, mixing desorption solutions, and purifying at 40 deg.CEvaporating the solution to dryness at the temperature of 75 ℃ to dryness, dissolving the solution by using 30-90 mu L of 0.5 mol/L nitric acid solution, measuring the concentration of the solution by using an inductively coupled plasma emission spectrometer according to GB5009.268-2016, and finally calculating target nuclide in the solution to be measured90Sr content.
Compared with the prior art, the invention has the following advantages:
1. the invention has good chemical and physical stability, and the transmission electron microscope test shows that the blank graphite phase carbon nitride has obvious layered structure (see figure 2 (a)), and Na+The doped graphitic carbon nitride material is a two-dimensional single-layer folded structure (see fig. 2 (b)), with no metal nanoparticles on the surface of the material, indicating Na+The doping is performed by a chemical complexing mode instead of simple physical mixing, and the graphite-phase carbon nitride material eluted by the acid solution has a two-dimensional single-layer structure and a pore structure of about 30nm on the surface of the material (see fig. 2 (c)); in addition, the energy spectrum analysis map shows that the blank graphite phase carbon nitride only has C, N two elements (Cu element is from copper net), Na+The doped graphite phase carbon nitride material contains C, N and Na elements, and Na is also illustrated+The Na element in the material does not exist after the material is successfully doped and eluted by the acid solution, which indicates that the functional graphite phase carbon nitride material is successfully prepared (see fig. 2(d) -2 (f)).
2. By examining the selectivity of the invention (see FIG. 3), the common metal ions [ Na (I), K (I), Cs (I), Ca (II), Ce (II), Ba (II), Co (II), Mg (II), Sr (II), Mn (II), Ni (II), Zn (II) and Fe (III) are selected]As interfering ions, the concentrations were all (30. mu.g/mL), 5.0 mg of the functionalized graphitic carbon nitride material was placed in 5mL of the above solution, respectively, sonicated for 20min, followed by placing the mixed solution in a shaker for 60 min of shaking, followed by centrifugation (4000 rpm, 20 min) to obtain the separated adsorbent material and aqueous phase, respectively. The concentration of each metal ion in the aqueous phase was determined according to GB 5009.268-2016. The experimental result shows that compared with the blank graphite phase carbon nitride, the functional graphite phase carbon nitride material of the invention is used for targeting nuclide90Sr has good adsorption performance and is hardly interfered by other metal ions.
3. The invention combines the advantages of the graphite phase carbon nitride material with the ion imprinting method, not only increases the specific surface area and the effective adsorption sites of the material, but also improves the selectivity of the material, and combines the material with ICP-OES, establishes an analysis and determination method with high sensitivity and wide application range, and realizes the analysis and determination of radioactive elements in the sample90Determination of trace amount of Sr.
4. The method is simple, the cost is low, the raw materials are green, no pollution is caused, and the obtained functional graphite-phase carbon nitride material fills in domestic radionuclide90The blank of Sr enrichment materials changes the monopoly status of foreign materials, and provides a new material, a new method and a related theoretical basis for sample pretreatment and analysis and detection of radionuclides.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a schematic view of a process for preparing a functionalized graphite-phase carbon nitride material according to the present invention.
Fig. 2 is a graph representing the morphology and structure of the functionalized graphitic carbon nitride material according to the present invention. Wherein: (a) a transmission electron microscope representation picture of the blank graphite phase carbon nitride material; (b) is Na+A transmission electron microscope representation of the graphite phase-doped carbon nitride material; (c) is Na eluted by acid solution+A transmission electron microscope representation of the graphite phase-doped carbon nitride material; (d) an energy spectrum analysis map of the blank graphite phase carbon nitride material; (e) is Na+An energy spectrum analysis map of the doped graphite phase carbon nitride material; (f) is Na eluted by acid solution+And (3) an energy spectrum analysis map of the doped graphite phase carbon nitride material.
FIG. 3 is a graph showing the measurement of the selective adsorption performance of the functionalized carbon nitride graphite phase material of the present invention and the comparison of the adsorption performance with that of a blank carbon nitride graphite phase material.
Detailed Description
A functional graphite-phase carbon nitride material is a polymer compound which is constructed by taking sodium ions as doping ions, has a layered cavity structure with the aperture of 2-30 nm and coplanar tris-s-triazine as a basic structural unit.
Example 1 as shown in fig. 1, a method for preparing a functionalized graphite-phase carbon nitride material includes the steps of:
first, 15g of urea and 1g of NaCl were mixed, dissolved in 32 mL of ultrapure water, and stirred at room temperature to be sufficiently dissolved, thereby obtaining a triazine structure compound solution containing sodium ions.
Putting the triazine structural compound solution containing sodium ions into a vacuum drying oven, and drying at 60 ℃ until no water exists to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 4 hours at the temperature rise rate of 4 ℃/min and at the temperature of 540 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 20mL of nitric acid solution with the concentration of 0.5 mol/L, the mixture is subjected to 4000W ultrasonic elution for 20min and then is centrifuged at 4000rpm for 20min, supernatant liquid is discarded, the process is repeated three times, and doped ions (Na) in the graphite phase carbon nitride material are removed+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry at 80 ℃ to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method comprises the following steps:
firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Putting 1.0 mg of the functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator to oscillate for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② according to GB5009.268-2016 target nuclide in water phase90The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 10min to ensure that the target nuclide90Desorbing Sr from the adsorbent; repeating the above operations for 3 times, combining desorption solutions, evaporating to dryness at-60 ℃, dissolving with 30 mu L of 0.5 mol/L nitric acid solution, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be detected90Sr content.
Embodiment 2 a method for preparing a functionalized graphite-phase carbon nitride material, comprising the steps of:
mixing 5g of melamine and 1g of sodium acetate, dissolving the mixture in 18 mL of ultrapure water, and stirring the mixture at room temperature to fully dissolve the mixture to obtain a triazine structure compound solution containing sodium ions.
Putting the triazine structural compound solution containing sodium ions into a vacuum drying oven, and drying at 80 ℃ until anhydrous to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 3 hours at a heating rate of 4 ℃/min and at a temperature of 500 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 5mL of nitric acid solution with the concentration of 0.1 mol/L, the mixture is subjected to ultrasonic elution with 4000W for 10min and then is centrifuged at 4000rpm for 20min, supernatant liquid is discarded, the process is repeated three times, and doped ions (Na) in the graphite phase carbon nitride material are removed+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry at 60 ℃ to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method is as follows：
Firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Putting 10.0 mg of the functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator to oscillate for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 20min to ensure that the target nuclide90Desorbing Sr from the adsorbent; repeating the above operations for 3 times, combining desorption solutions, evaporating to dryness at 40 deg.C, dissolving with 0.5 mol/L nitric acid solution 90 μ L, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be measured90Sr content.
Embodiment 3 a method for preparing a functionalized graphite-phase carbon nitride material, comprising the steps of:
mixing 35g of cyanamide and 1g of sodium nitrate, dissolving the mixture in 36mL of ultrapure water, and stirring the mixture at room temperature to fully dissolve the mixture to obtain a triazine structure compound solution containing sodium ions.
Putting the triazine structural compound solution containing sodium ions in a vacuum drying oven, and drying at 70 ℃ until the triazine structural compound solution is anhydrous to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 5 hours at a heating rate of 4 ℃/min and at a temperature of 520 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 10mL of 1.0mol/L nitric acid solution, the mixture is subjected to 4000W ultrasonic elution for 15min and then is centrifuged at 4000rpm for 20min, supernatant is discarded, the process is repeated three times, and the steps are omittedDoping ion (Na) in graphite phase removed carbon nitride material+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry the solid powder to constant weight at 70 ℃, so as to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method comprises the following steps:
firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Placing 5.0 mg of the functional graphite-phase carbon nitride material in 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then placing the mixed solution in an oscillator for oscillation for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 15min to ensure that the target nuclide90Desorbing Sr from the adsorbent; repeating the above operation for 3 times, combining desorption solutions, evaporating to dryness at 50 deg.C, dissolving with 0.5 mol/L nitric acid solution 60 μ L, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be measured90Sr content.
Embodiment 4 a method of preparing a functionalized graphite-phase carbon nitride material, comprising the steps of:
first, 25g of thiourea and 1g of sodium sulfate were mixed and dissolved in 39 mL of ultrapure water, and the mixture was stirred at room temperature to be sufficiently dissolved, thereby obtaining a triazine structure compound solution containing sodium ions.
Putting the triazine structural compound solution containing sodium ions into a vacuum drying oven, and drying at 65 ℃ until anhydrous to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 3.5 hours at a heating rate of 4 ℃/min and a temperature of 580 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 15mL of hydrochloric acid solution with the concentration of 1.0mol/L, the mixture is subjected to 4000W ultrasonic 10min elution and then is centrifuged at 4000rpm for 20min, the supernatant is discarded, the process is repeated three times, and doped ions (Na) in the graphite phase carbon nitride material are removed+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry at 75 ℃ to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method comprises the following steps:
firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Placing 2.0 mg of the functional graphite-phase carbon nitride material in 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then placing the mixed solution in an oscillator for oscillation for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 10min to ensure that the target nuclide90Desorbing Sr from the adsorbent; repeating the above operation for 3 times, combining desorption solutions, evaporating to dryness at 45 deg.C, dissolving with 0.5 mol/L nitric acid solution 50 μ L, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be measured90Of SrAnd (4) content.
Embodiment 5 a method of preparing a functionalized graphite-phase carbon nitride material, comprising the steps of:
first, 15g of dicyandiamide and 1g of NaCl are mixed and dissolved in 40 mL of ultrapure water, and the mixture is stirred at room temperature to be sufficiently dissolved, so that a triazine structure compound solution containing sodium ions is obtained.
Putting the triazine structure compound solution containing sodium ions into a vacuum drying oven, and drying at 75 ℃ until no water exists to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 4.5 hours at a heating rate of 4 ℃/min and at a temperature of 540 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 10mL of phosphoric acid solution with the concentration of 0.5 mol/L, the mixture is subjected to 4000W ultrasonic elution for 15min and then is centrifuged at 4000rpm for 20min, supernatant liquid is discarded, the process is repeated three times, and doped ions (Na) in the graphite phase carbon nitride material are removed+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry at 65 ℃ to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method comprises the following steps:
firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Putting 8.0 mg of the functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator to oscillate for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② according to GB5009.268-2016 to make water phaseTarget nuclide of90The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 20min to ensure that the target nuclide90Desorbing Sr from the adsorbent; repeating the above operations for 3 times, combining desorption solutions, evaporating to dry at 75 deg.C, dissolving with 0.5 mol/L nitric acid solution 70 μ L, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be measured90Sr content.
Embodiment 6 a method of preparing a functionalized graphite-phase carbon nitride material, comprising the steps of:
first, 15g of urea and 1g of NaCl were mixed, dissolved in 32 mL of ultrapure water, and stirred at room temperature to be sufficiently dissolved, thereby obtaining a triazine structure compound solution containing sodium ions.
Putting the triazine structural compound solution containing sodium ions into a vacuum drying oven, and drying at 60 ℃ until no water exists to obtain a white solid.
Transferring the white solid into a crucible, placing the crucible into a muffle furnace, calcining the crucible at a high temperature for 4 hours at a heating rate of 4 ℃/min and at a temperature of 560 ℃, and preparing the graphite-phase carbon nitride material doped with sodium ions in a thermal polycondensation mode; after the reaction was completed, it was cooled to room temperature to obtain a pale yellow solid powder.
Fourthly, 1.0g of light yellow solid powder is added with 20mL of acetic acid solution with the concentration of 0.8 mol/L, the mixture is subjected to 4000W ultrasonic elution for 20min and then is centrifuged at 4000rpm for 20min, supernatant liquid is discarded, the process is repeated three times, and doped ions (Na) in the graphite phase carbon nitride material are removed+) A solid powder was obtained.
Fifthly, washing the solid powder with ultrapure water for three times, removing the acid solution on the surface of the solid powder, and then putting the solid powder into a vacuum drying oven to dry at 80 ℃ to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
The functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapid extraction and trace detection of Sr. The specific method comprises the following steps:
firstly, preparing an environmental water sample or a food sample subjected to pretreatment such as drying and ashing to obtain a sample solution to be detected.
Putting 1.0 mg of the functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator to oscillate for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 15min to enable the target nuclide90Desorbing Sr from the adsorbent; repeating the above operation for 3 times, combining desorption solutions, evaporating to dry at 70 deg.C, dissolving with 0.5 mol/L nitric acid solution 80 μ L, determining the concentration by inductively coupled plasma emission spectrometer (ICP-OES) according to GB5009.268-2016, and calculating target nuclide in the solution to be measured90Sr content.
Claims (5)
1. The application of the functionalized graphite-phase carbon nitride material is characterized in that: the functional graphite-phase carbon nitride material is used as an adsorbent applied to radionuclide in food or environmental water samples90Rapidly extracting Sr and detecting trace amount; the functional graphite-phase carbon nitride material is a polymer compound which is constructed by taking sodium ions as doping ions, has a layered cavity structure with the aperture of 2-30 nm and takes coplanar tris-s-triazine as a basic structural unit;
the preparation method of the material comprises the following steps:
the preparation method comprises the steps of taking a triazine structure compound as a precursor, mixing the triazine structure compound with a sodium ion compound, dissolving the mixture in ultrapure water which is 1-3 times of the mass of the mixture, and stirring at room temperature to fully dissolve the mixture to obtain a triazine structure compound solution containing sodium ions; the mass ratio of the precursor to the sodium ion compound is 5: 1-35: 1; the precursor is any one of urea, melamine, cyanamide and thiourea; the sodium ion compound is any one of sodium chloride, sodium nitrate, sodium sulfate and sodium acetate;
drying the triazine structural compound solution containing sodium ions until the solution is anhydrous to obtain a white solid;
transferring the white solid into a crucible, and placing the crucible in a muffle furnace for high-temperature calcination; cooling to room temperature after the reaction is finished to obtain light yellow solid powder;
fourth, the light yellow solid powder is prepared from the following components in percentage by weight of 1: adding an acid solution according to the mass-to-volume ratio of 5-20, eluting by 4000W ultrasound for 10-20 min, and centrifuging at 4000rpm for 20min to obtain solid powder;
and fifthly, washing the solid powder with ultrapure water for three times, and drying to constant weight to obtain the functionalized graphite-phase carbon nitride composite material.
2. Use of a functionalized graphitic carbon nitride material according to claim 1, wherein: the step II and the drying condition in the step are all that the temperature is 60-80 ℃.
3. Use of a functionalized graphitic carbon nitride material according to claim 1, wherein: the high-temperature calcination condition in the step three is that the heating rate is 4 ℃/min, the temperature is 500-580 ℃, and the time is 3-5 h.
4. Use of a functionalized graphitic carbon nitride material according to claim 1, wherein: the acid solution in the step four is any one of nitric acid, hydrochloric acid, phosphoric acid, and acetic acid having a concentration of 0.1 to 1.0 mol/L.
5. Use of a functionalized graphitic carbon nitride material according to claim 1, comprising the steps of:
putting 1.0-10.0 mg of a functional graphite-phase carbon nitride material into 5mL of solution to be detected, performing ultrasonic treatment for 20min to uniformly disperse the material in the solution to be detected, and then putting the mixed solution into an oscillator for oscillation for 60 min to achieve extraction balance; centrifuging at 4000rpm for 20min to obtain separated adsorbing material and water phase;
② to target nuclide in water phase according to GB5009.268-201690The Sr concentration is measured;
thirdly, transferring the separated adsorbing material into a centrifuge tube, adding 200 mu L of 0.5 mol/L nitric acid solution, and carrying out ultrasonic treatment at 4000W for 10-20 min to enable the target nuclide90Desorbing Sr from the adsorbent; repeating the above operations for 3 times, combining desorption solutions, evaporating the solutions to dryness at 40-75 ℃, dissolving the solutions by using 30-90 mu L of 0.5 mol/L nitric acid solution, measuring the concentration of the solutions by using an inductively coupled plasma emission spectrometer according to GB5009.268-2016, and finally calculating target nuclides in the solutions to be measured90Sr content.
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