CN113750965A - Preparation method of carbon dot-coated cerium dioxide material and application of carbon dot-coated cerium dioxide material in fluoride ion adsorption and detection - Google Patents
Preparation method of carbon dot-coated cerium dioxide material and application of carbon dot-coated cerium dioxide material in fluoride ion adsorption and detection Download PDFInfo
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 57
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims description 23
- 239000000463 material Substances 0.000 title abstract description 32
- -1 fluorine ions Chemical class 0.000 claims abstract description 25
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 19
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 19
- 229940033123 tannic acid Drugs 0.000 claims abstract description 19
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 19
- 229920002258 tannic acid Polymers 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
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- 102000003992 Peroxidases Human genes 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
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- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 3
- 238000000862 absorption spectrum Methods 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 4
- 235000013824 polyphenols Nutrition 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 102000019197 Superoxide Dismutase Human genes 0.000 abstract description 3
- 108010012715 Superoxide dismutase Proteins 0.000 abstract description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 235000013024 sodium fluoride Nutrition 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention provides a preparation method of a carbon dot-coated cerium dioxide material with a cubic phase structure and application of the carbon dot-coated cerium dioxide material in simultaneous adsorption and quantitative detection of fluorine ions. The natural polyphenol tannic acid is used as a raw material, and the natural polyphenol tannic acid and a cerium source are subjected to simple hydrothermal reaction to prepare the carbon dot-coated cerium dioxide with the cubic crystal phase structure, and the material can efficiently adsorb fluorine ions. Further, the inventors have found that the superoxide dismutase activity of the carbon dot-coated ceria material is improved after adsorbing fluorine ions, so that the adsorption amount of the fluorine ions can be detected while adsorbing the fluorine ions by the carbon dot-coated ceria with the cubic phase structure.
Description
The invention relates to the field of fluoride ion adsorption, in particular to a preparation method of a cubic phase structure carbon point coated cerium dioxide material and application of the cubic phase structure carbon point coated cerium dioxide material in simultaneous adsorption and quantitative detection of fluoride ions.
Technical Field
With the rapid development of modern society, environmental pollution is increasingly serious, and excessive fluoride ions are more and more concerned by society as common pollution of water pollution. Fluoride ion (F)-) As an element commonly found in nature, it plays a very important role in the life activities of animals and plants, but excessive fluoride inhibits metabolism, respiration and photosynthesis of plants, and excessive F-Can also affect the health of human body, and China is due to F-The problem of environmental pollution caused by the method is very serious. Therefore, there is an urgent need to develop a highly efficient and simple F-Clearing and detection techniques.
There are many methods for fluoride ion detection, conventional methods including chromatography, electrochemistry and F-NMR analysis, but these methods all require complicated instruments, highly skilled operators and complicated sample pretreatment procedures. The ultraviolet-spectrophotometer technology is simple to operate, free of complex sample pretreatment process and high in sensitivity, and is a promising alternative technology.
At present, there are many methods for adsorbing fluorine ions, such as ion exchange, membrane filtration, adsorption and chemical precipitation, and the methods are used in the treatment of fluorine ion contamination, and the adsorption technology is the simplest and the most rapid and is widely concerned. F in the waste water commonly used at present-The most promising of the removal technology belongs to chemical adsorption, and has the advantages of simple operation, low price, strong universality and the like. Cerium, a rare earth element that is abundant and inexpensive, has been reported in the literature as CeO2Has excellent F-Active by adsorption, but CeO2The poor dispersibility in water and the low content of active groups on the surface limit the use of the composition for F-The effective adsorption of (1).
Disclosure of Invention
The invention aims to provide a preparation method of carbon point-coated cerium dioxide, which has low raw material cost and relatively simple preparation and can be used for mass production, and a method for simultaneously adsorbing and quantitatively detecting fluorine ions in a water body by using the prepared carbon point-coated cerium dioxide with a cubic phase structure, aiming at the defects in the prior art. The natural polyphenol tannic acid is used as a raw material, and the natural polyphenol tannic acid and a cerium source are subjected to simple hydrothermal reaction to prepare the carbon dot-coated cerium dioxide with the cubic crystal phase structure, and the material can efficiently adsorb fluorine ions. Further, the inventors have found that the superoxide dismutase activity of the carbon dot-coated ceria material is improved after adsorbing fluorine ions, so that the adsorption amount of the fluorine ions can be detected while adsorbing the fluorine ions by the carbon dot-coated ceria with the cubic phase structure.
A preparation method of carbon dot-coated cerium dioxide is characterized by comprising the following steps:
(1) mixing tannic acid and a cerium source under an alkaline condition to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1);
(3) and (3) filtering, dialyzing and freeze-drying the product obtained in the step (2) to obtain the carbon point-coated cerium dioxide with the cubic phase structure.
Preferably, the cerium source in step (1) is one or more of cerium chloride, cerium nitrate and cerium sulfate.
Preferably, the mass ratio of the tannic acid to the cerium source in the step (1) is 200-300: 10 to 20.
Preferably, the alkaline condition in the step (1) is provided by ammonia water, hydrazine hydrate and absolute ethyl alcohol, and the volume ratio is (100-1000) muL: (3-5) mL.
Preferably, in the step (1), the tannic acid and the cerium source are dissolved in deionized water, and the dosage ratio of the tannic acid to the deionized water is (200-300) mg: (10-20) mL.
Preferably, the hydrothermal reaction temperature in the step (2) is 140-200 ℃, and the hydrothermal reaction time is 6-12 h.
Preferably, in step (3), the filtration is carried out with a 0.22. mu.M membrane filter, and the dialysis time is 8 to 12 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) ce is a rare earth element with abundant and cheap contents, and its oxide has excellent adsorption property and is well known in the literatureReport CeO2Has excellent performance of adsorbing fluorinion, but has poor water solubility and low surface group content, greatly influences the adsorption performance, and the carbon dot is used as a novel zero-dimensional carbon material, has good water solubility and rich surface groups, can be used as a surface modifier for solving CeO (CeO) problem2Adsorption of F-Provides an effective way.
(2) The method comprises the steps of taking natural tannic acid and a cerium source as raw materials, preparing carbon dot-coated cerium oxide by a simple hydrothermal method, polymerizing the tannic acid on the surface of the cerium source in a hydrothermal process after the tannic acid is coordinated with the cerium source under an alkaline condition, then carbonizing, growing cerium source nucleation under the alkaline condition to gradually form cerium dioxide, and finally forming the material of the carbon dot-coated cerium dioxide.
(3) Because tannic acid has abundant hydroxyl groups, the surface of the carbon dot formed by the tannic acid has abundant hydroxyl groups, and the formed carbon dot is coated with the cerium dioxide, and the hydroxyl groups are hydrophilic groups, so that the water solubility of the cerium dioxide is improved, and the problem that the cerium dioxide is difficult to dissolve in water can be solved.
(4) After the carbon dots are coated with the cerium dioxide, the specific surface area of the material is increased, and the combined action of the carbon dots and the hydroxyl functional groups rich in tannic acid is more favorable for adsorption; meanwhile, the conventional cerium oxide having an uncoated structure is agglomerated, thereby causing a decrease in the surface hydroxyl group content thereof and deterioration in the fluorine ion adsorption effect.
(5) Further, the inventors of the present application have found that the ability of the carbon dot-coated ceria material to scavenge radicals is further enhanced after adsorbing fluorine ions, so that we can quantitatively detect the adsorbed fluorine ions using an ultraviolet-spectrophotometer technique while adsorbing fluorine ions.
Drawings
FIG. 1 is an SEM image of carbon dot-coated ceria prepared in example 1 of the present invention;
FIG. 2 is a TEM image of carbon dot-coated ceria prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of carbon dot-coated ceria prepared according to example 1 of the present invention;
FIG. 4 is a Qe-t graph showing fluorine ion adsorption at 25 ℃ of carbon dot-coated ceria prepared in example 1 of the present invention;
FIG. 5 is a thermodynamic diagram of the adsorption of fluorine ions at 25 ℃ of carbon-point-coated ceria prepared in example 1 of the present invention;
FIG. 6 is a UV-VIS absorption spectrum of fluorine ion detection of carbon dot-coated ceria prepared in example 1 of the present invention;
FIG. 7 is a Qe-t graph showing fluorine ion adsorption at 25 ℃ of carbon dot-coated ceria prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: 204mg of tannic acid and 11.83mg of anhydrous cerium chloride are dissolved in 10mL of deionized water, and after ultrasonic dissolution, 500 μ L of ammonia water, 625 μ L of hydrazine hydrate and 3.875mL of anhydrous ethanol are added to obtain a mixed solution.
Step two: and (3) adding the mixed solution obtained in the step one into a liner of a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sleeving a high-pressure tank of the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into a drying oven at 180 ℃ for reaction for 10 hours.
Step three: and cooling to room temperature after the reaction is finished, transferring the solution into a 50mL centrifuge tube, filtering with a 0.22 mu M filter membrane, transferring the filtered solution into a 1000D dialysis bag, transferring the solution into a 2L beaker filled with deionized water, dialyzing for 8 hours, transferring the solution in the dialysis bag into the 50mL centrifuge tube after the dialysis is finished, freezing with liquid nitrogen, and then putting the centrifuge tube into a freeze dryer for freeze drying to obtain the final product of the cerium dioxide coated with carbon dots.
SEM and TEM characterization were performed on the carbon dot-coated ceria material prepared in example one.
As shown in fig. 1, the carbon dot-coated ceria material prepared in the first example is in a pellet shape as seen in the SEM, and as shown in fig. 2, the black carbon dots are coated on the surface of ceria as seen in the TEM, and the particle size distribution obtained after counting the particle sizes is 40 to 50 nm.
XRD crystal structure analysis was performed on the carbon dot-coated ceria material prepared in example one, as shown in fig. 3, the prepared carbon dot-coated ceria material was in a cubic crystal structure.
The nature that natural peroxidase (HRP) can turn TMB blue in the presence of hydrogen peroxide is utilized, the blue color of the solution becomes light after the carbon dot-coated cerium dioxide material prepared in the first example is added, which indicates that the carbon dot-coated cerium dioxide material prepared in the first example has the capability of scavenging free radicals (namely has superoxide dismutase activity, also called SOD enzyme), and the blue color becomes lighter after the fluorine ion solution is added, which indicates that the addition of fluorine ions can enhance the capability of scavenging free radicals of the carbon dot-coated cerium dioxide material prepared in the first example (so that the SOD enzyme activity of the carbon dot-coated cerium dioxide material is enhanced), so that the fluorine ions can be quantitatively detected by using an ultraviolet-spectrophotometer technology.
Fluoride ion adsorption experiment: 100mL of the initial concentration was 10-3.5In mol/L sodium fluoride solution, 300mg of the carbon dot-coated ceria material prepared in example one was taken, the material concentration was controlled at 0.3g/100mL, and the pH of the solution was adjusted to 3, at which time the acidic environment of the solution was beneficial for adsorption. Then, the time intervals are 1min, 5min, 10min, 30min, 60min, 180min and 300min, after 10mL of the solution is placed in a 50mL beaker and is kept still for 10min, the supernatant is filtered by a 0.22 μ M filter membrane, the fluorine ion concentration in the filtrate is detected by a fluorine ion detector, and the adsorption capacity of the carbon dot-coated ceria material prepared in the first embodiment on the fluorine ions can be calculated by the following formula:
Qe＝V*(Ci-Ce)/m
qe is adsorption capacity (mg/g)
V is the total volume of the solution (L)
Ci is initial fluoride ion concentration (mg/L)
Ce is equilibrium concentration (mg/L)
m is the amount (g) of adsorbent
As shown in fig. 4, it can be seen that the adsorption amount was almost saturated at the adsorption time of 1h, at which the adsorption efficiency was 92%.
Initial concentration of 10-2、10-2.5、10-3、10-3.5、10-4Putting 10mL of sodium fluoride solution into a 50mL beaker, adding 45mg of the carbon dot-coated cerium dioxide material prepared in the first embodiment, controlling the material concentration at 0.3g/100mL, mixing, adjusting the pH of the mixed solution to 3, transferring the mixed solution into a 50mL centrifugal tube, putting a proper small magnet, carrying out water bath at 25 ℃ for 12 hours, centrifuging at 10000R/min for 15min, transferring the supernatant into a 3Kd 50mL ultrafiltration tube for ultrafiltration, centrifuging at 7000R/min for 15min, transferring the ultrafiltered supernatant into a 50mL beaker, detecting the residual fluorine ion concentration, and making a thermodynamic curve at the temperature of 25 ℃, as shown in FIG. 5, a Freund thermodynamic model of the carbon dot-coated cerium dioxide material prepared in the first embodiment, and performing a thermodynamic curve according to R2The adsorption was judged to conform to the Freundlich thermodynamic model.
Fluoride ion detection experiment: 10. mu.L of 1. mu.g/mL natural peroxidase diluted in PBS buffer was used, 50. mu.L of 1mg/mL carbon-coated ceria material prepared in example I was used, 50. mu.L of 20mM TMB was used, the three were put into a 2mL centrifuge tube, a predetermined amount of HAc-NaAc buffer solution having a pH of 4 was added, 10mM NaF solutions (0 to 440. mu.L, 40. mu.L at intervals) were added, the total volume of the mixture was controlled to 1980. mu.L, and the natural peroxidase concentration in the mixture was controlled to 0.005. mu.g/mL. The carbon dot-coated ceria material prepared in example one was incubated in a water bath at 25 ℃ for 5min with a gradient of 25. mu.g/mL, 0.5mM of TMB and 0.2mM of fluoride ion in a concentration of 10mM after mixing, and then 20. mu.L of 1M hydrogen peroxide was added thereto. After water bath for 1min, the liquid in the 2mL centrifuge tube was transferred to a cuvette and placed in an ultraviolet-spectrophotometer to measure the absorption spectrum curve of the solution, the result of which is shown in FIG. 6. As can be seen from FIG. 6, the characteristic absorption peak of TMB (i.e., oXTMB) after oxidation in the range of 200-800 nm is at 652nm, and as the fluoride ion concentration increases, the characteristic absorption peak at 652nm decreases in sequence, and as the fluoride ion concentration increases in a larger range, the absorption peak at 652nm shows a linear relationship.
Example 2
The method comprises the following steps: 204mg of tannic acid and 5.915mg of anhydrous cerium chloride are dissolved in 10mL of deionized water, and after ultrasonic dissolution, 500 μ L of ammonia water, 625 μ L of hydrazine hydrate and 3.875mL of anhydrous ethanol are added to obtain a mixed solution.
Step two: and (3) adding the mixed solution obtained in the step one into a liner of a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sleeving a high-pressure tank of the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into a drying oven at 180 ℃ for reaction for 10 hours.
Step three: and cooling to room temperature after the reaction is finished, transferring the solution into a 50mL centrifuge tube, filtering with a 0.22 mu M filter membrane, transferring the filtered solution into a 1000D dialysis bag, transferring the solution into a 2L beaker filled with deionized water, dialyzing for 8 hours, transferring the solution in the dialysis bag into the 50mL centrifuge tube after the dialysis is finished, freezing with liquid nitrogen, and then putting the centrifuge tube into a freeze dryer for freeze drying to obtain the final product of the cerium dioxide coated with carbon dots.
The fluorine ion adsorption experiment of example 1 was repeated using the material obtained in example 2 to obtain a Qe-t chart, as shown in FIG. 7.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of carbon dot-coated cerium dioxide with a cubic phase structure is characterized by comprising the following steps:
(1) mixing tannic acid and a cerium source under an alkaline condition to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1);
(3) and (3) filtering, dialyzing and freeze-drying the product obtained in the step (2) to obtain the carbon point-coated cerium dioxide with the cubic phase structure.
2. The method according to claim 1, wherein the cerium source in step (1) is one or more of cerium chloride, cerium nitrate and cerium sulfate.
3. The method according to claim 1, wherein the mass ratio of the tannic acid to the cerium source in the step (1) is 200 to 300: 10 to 20.
4. The method of claim 1, wherein in the step (1), the tannic acid and the cerium source are dissolved in deionized water in a ratio of (200 to 300) mg: (10-20) mL.
5. The preparation method according to claim 1, wherein the hydrothermal reaction temperature in the step (2) is 140 ℃ to 200 ℃ and the hydrothermal reaction time is 6h to 12 h.
6. The method according to claim 1, wherein the filtration is performed with a 0.22 μ M membrane filter in the step (3) and the dialysis time is 8 to 12 hours.
7. A carbon dot-coated ceria having a cubic structure prepared by the method according to any one of claims 1 to 6.
8. Use of the carbon dot-coated ceria with cubic phase structure according to claim 7 for simultaneous adsorption and quantitative detection of fluorine ions in a water body.
9. The method as claimed in claim 8, wherein the cubic phase structure carbon dot-coated ceria is mixed with natural peroxidase diluted by PBS buffer, TMB, buffer and a series of fluoride ion solutions with different concentrations (concentration is 0-2.2 mM, concentration gradient is 0.2mM), and after the reaction is finished, all samples are put into an ultraviolet-spectrophotometer to measure the absorption spectrum curve of the solution.
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