CN113274978A - Reduced graphene oxide @ zirconium dioxide composite material and application thereof - Google Patents
Reduced graphene oxide @ zirconium dioxide composite material and application thereof Download PDFInfo
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- CN113274978A CN113274978A CN202110539670.0A CN202110539670A CN113274978A CN 113274978 A CN113274978 A CN 113274978A CN 202110539670 A CN202110539670 A CN 202110539670A CN 113274978 A CN113274978 A CN 113274978A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000005562 Glyphosate Substances 0.000 claims abstract description 27
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229940097068 glyphosate Drugs 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 16
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- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims abstract description 15
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
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- 238000005406 washing Methods 0.000 claims abstract description 9
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
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- 238000003756 stirring Methods 0.000 claims abstract description 3
- 241001122767 Theaceae Species 0.000 claims abstract 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
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- 239000003480 eluent Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000009795 derivation Methods 0.000 claims description 2
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- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 238000001819 mass spectrum Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000004451 qualitative analysis Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 3
- 244000269722 Thea sinensis Species 0.000 description 24
- 235000013616 tea Nutrition 0.000 description 23
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 16
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 238000000967 suction filtration Methods 0.000 description 3
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- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960001948 caffeine Drugs 0.000 description 2
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 2
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- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 239000005561 Glufosinate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 210000003734 kidney Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/20—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
Abstract
A reduced graphene oxide @ zirconium dioxide composite material and application thereof belong to the technical field of novel adsorption purification materials. The material is prepared by the following steps: adding graphene oxide into deionized water for ultrasonic stripping to obtain uniformly dispersed graphene oxide dispersion liquid; adding an aqueous solution of zirconium oxychloride octahydrate into the graphene oxide dispersion liquid, continuously stirring, and fully mixing the aqueous solution and the zirconium oxychloride; adjusting the pH value of the solution to be alkaline by ammonia water; carrying out hydrothermal reaction on the mixed solution; and after the mixture is cooled to room temperature, washing and drying to obtain the reduced graphene oxide @ zirconium dioxide composite material. The material synthesis method has simple operation steps and no special requirements on instruments and equipment; the material has specific adsorption on glyphosate and amino methyl phosphonic acid containing phosphate groups, and has high adsorption efficiency and large adsorption quantity, and the tea matrix effect can be obviously reduced; the adsorbent can be widely applied to other samples with complex matrixes and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of novel adsorption purification materials, and particularly relates to a reduced graphene oxide @ zirconium dioxide composite material and application thereof.
Background
Glyphosate is a non-selective, systemic, conductive, foliar-treatment herbicide, and is widely used to remove weeds in crops due to its characteristics of high efficiency and broad spectrum. To date, glyphosate is the largest and most widely used herbicide in the world. Glyphosate is registered for use in 51 crops including tea in our country. Because of good water solubility and strong systemic property, the pollution of water and soil and the systemic absorption of plants can be caused by using the composition in a large amount, and then the composition enters a food chain to cause risks to human health. It has been reported that glyphosate has side effects on liver and kidney due to malformation of reproductive development. Therefore, the national standard GB2763 of the government of China stipulates that the limit of glyphosate in tea is 1 mg kg-1. In order to guarantee the rights and interests of consumers, the government continuously increases the detection strength of the pesticide residues in the tea leaves. The most commonly used glyphosate detection method in the laboratory at present is the pre-column derivatization-LC-MS/MS analytical method. However, the tea matrix is quite complex and contains a large amount of tea polyphenols, caffeine, pigments and the like. The large amount of matrix components severely interferes with the derivatization efficiency. Chinese patent CN201410125103.0 discloses a pretreatment method of glyphosate and glufosinate pesticide in tea. In the patent, an HLB solid phase extraction column is used for purifying the tea extract. The HLB solid phase extraction column adsorbs tea matrix, but does not adsorb glyphosate pesticide, and has limited purification effect. The development of a novel glyphosate-specific adsorption purification material in tea is urgently needed.
Zirconium dioxide (ZrO)2) Is an important oxide of transition metal zirconium, has strong acting force with phosphate groups in the structures of glyphosate and aminomethylphosphonic acid pesticides, and can realize the specific adsorption of glyphosate and aminomethylphosphonic acid. But ZrO obtained by hydrolysis of a zirconium source2Aggregation tends to occur easily to obtain large-particle ZrO2So that the adsorption efficiency is low and the requirement is difficult to meet. Graphene oxide (Gr)aphene oxide, GO), as a novel carbon material, has excellent physicochemical properties such as good stability and large specific surface area, and oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy on the surface and edge thereof are ideal adsorbing materials. The ZrO is compounded by the graphene oxide and the zirconium dioxide2The nano particles are well dispersed on the surface of the graphene, so that ZrO is prevented2The particles are not easy to accumulate between graphene layers while being aggregated, so that the adsorption performance of the graphene is greatly improved
The reduced graphene oxide @ zirconium dioxide composite material is synthesized by utilizing zirconium oxychloride octahydrate and graphene oxide through a one-step hydrothermal synthesis method under the action of ammonia water. The synthesis method is simple, controllable in experimental conditions and free of special complex equipment. The prepared reduced graphene oxide @ zirconium dioxide composite material can be used as a specific efficient adsorbent for glyphosate and aminomethylphosphonic acid, and can be used for pretreatment of analysis of pesticide residues in tea. Meanwhile, the material is also suitable for pretreatment of other complex matrix samples, and has good practical application value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a reduced graphene oxide @ zirconium dioxide composite material and an application technical scheme thereof. The reduced graphene oxide @ zirconium dioxide composite material obtained by the invention can specifically adsorb glyphosate and aminomethyl phosphonic acid in tea, so that removal of interference components glyphosate and aminomethyl phosphonic acid in a tea matrix can be realized, and the purpose of detection of glyphosate and aminomethyl phosphonic acid in tea is finally realized.
The invention is realized by adopting the following technical scheme:
the reduced graphene oxide @ zirconium dioxide composite material is characterized by being prepared through the following steps:
(1) adding graphene oxide into deionized water for ultrasonic stripping to obtain uniformly dispersed graphene oxide dispersion liquid;
(2) adding an aqueous solution of zirconium oxychloride octahydrate into the graphene oxide dispersion liquid obtained in the step (1), continuously stirring, and fully mixing the aqueous solution and the zirconium oxychloride;
(3) adjusting the pH value of the solution in the step (2) to be alkaline by using ammonia water;
(4) carrying out hydrothermal reaction on the mixed solution obtained in the step (3);
(5) and (4) cooling the mixture obtained in the step (4) to room temperature, washing and drying to obtain the reduced graphene oxide @ zirconium dioxide composite material.
The reduced graphene oxide @ zirconium dioxide composite material is characterized in that the mass ratio of the graphene oxide to the zirconium oxychloride octahydrate in the step (2) is 0.001-0.5.
The reduced graphene oxide @ zirconium dioxide composite material is characterized in that the pH value is adjusted to 10-12 in the step (3).
The reduced graphene oxide @ zirconium dioxide composite material is characterized in that the hydrothermal reaction condition in the step (4) is that the temperature is 180-200 ℃, and the solvothermal time is 10-15 hours.
The application of the reduced graphene oxide @ zirconium dioxide composite material in pretreatment of pesticide residues in tea is provided.
The application is characterized in that the pesticide residue is glyphosate and aminomethyl phosphonic acid.
The application method is characterized by comprising the following steps:
1) filling the reduced graphene oxide @ zirconium dioxide composite material and diatomite in series to form a solid-phase extraction purification column;
2) adding an alkaline solution into the crushed tea leaves for extraction, performing vortex, ultrasonic treatment and centrifugation to obtain a supernatant 1, adding hydrochloric acid into the supernatant 1 to adjust the pH value to acidity, and performing centrifugation to obtain a supernatant 2;
3) and (3) passing the supernatant 2 through the solid-phase extraction purification column in the step 1), eluting and eluting to obtain an eluent, deriving by using chloroformate-9-fluorenylmethyl ester, and performing qualitative and quantitative analysis by using a liquid chromatography tandem mass spectrum after derivation.
The application method is characterized in that in the step 1), diatomite is arranged on the lower layer, the reduced graphene oxide @ zirconium dioxide composite material is arranged on the upper layer, and the filling amount of the diatomite is 0.5-1.5 cm.
The application method is characterized in that the solid phase extraction purification column in the step 1) also comprises other acceptable materials in the pretreatment process of agricultural products.
The synthesis method of graphene oxide in the invention is not limited to Hummers method, and graphene oxide materials which are obtained by other methods and can react with zirconium dioxide are all suitable for the invention.
The invention has the beneficial effects that: the material synthesis method has simple operation steps and no special requirements on instruments and equipment; the material has specific adsorption on glyphosate and amino methyl phosphonic acid containing phosphate groups, and has high adsorption efficiency and large adsorption quantity, and the tea matrix effect can be obviously reduced; the adsorbent can be widely applied to other samples with complex matrixes and has wide application prospect.
Drawings
FIG. 1: a synthesis scheme of reduced graphene oxide-zirconium dioxide.
FIG. 2: a solid phase extraction column diagram taking the reduced graphene oxide-zirconium dioxide composite material as a filler.
FIG. 3: and (3) purifying the reduced graphene oxide-zirconium dioxide composite material to obtain a liquid chromatogram.
Detailed Description
In order to better understand the preparation method and application of the reduced graphene oxide @ zirconium dioxide composite material and the diatomite series-connected packed solid phase extraction purification cartridge in the present invention, the present invention is further illustrated by the following examples, but the application of the present invention is not limited to the following specific examples.
Example 1
Carrying out ultrasonic dispersion on 2 mg of graphene oxide material in 30mL of deionized water, wherein the ultrasonic power is 500W, and the ultrasonic time is 2 h; 2000 mg of zirconium oxychloride octahydrate is dissolved in 30mL of deionized water to prepare a zirconium oxychloride octahydrate solution, and the zirconium oxychloride octahydrate solution is added into the graphene oxide dispersion liquid and is continuously stirred for 2 hours. 7mL (25% -28%) of aqueous ammonia was added to the mixed solution, stirred for 10 minutes, and the pH was adjusted to 11. The mixture was poured into a 100mL autoclave, andis placed at 180 deg.CoAnd C, performing hydrothermal reaction for 12 hours in an oven. And (3) washing the graphene oxide and zirconium dioxide composite material to be neutral by using deionized water in a suction filtration mode, then washing the graphene oxide and zirconium dioxide composite material by using 50mL of absolute ethyl alcohol, and freeze-drying the graphene oxide and zirconium dioxide composite material to obtain the reduced graphene oxide and zirconium dioxide composite material. The synthetic scheme is shown in figure 1.
Example 2
Taking 80 mg of graphene oxide material, and carrying out ultrasonic dispersion in 30mL of deionized water, wherein the ultrasonic power is 500W, and the ultrasonic time is 2 h; 160 mg of zirconium oxychloride octahydrate is dissolved in 30mL of deionized water to prepare a zirconium oxychloride octahydrate solution, and the zirconium oxychloride octahydrate solution is added into the graphene oxide dispersion liquid and is continuously stirred for 2 hours. 7mL (25% -28%) of aqueous ammonia was added to the mixed solution, stirred for 10 minutes, and the pH was adjusted to 12. The mixture was poured into a 100mL autoclave and placed at 200%oAnd C, performing hydrothermal reaction for 12 hours in an oven. And (3) washing the graphene oxide and zirconium dioxide composite material to be neutral by using deionized water in a suction filtration mode, then washing the graphene oxide and zirconium dioxide composite material by using 50mL of absolute ethyl alcohol, and freeze-drying the graphene oxide and zirconium dioxide composite material to obtain the reduced graphene oxide and zirconium dioxide composite material.
Example 3
Carrying out ultrasonic dispersion on 20 mg of graphene oxide material in 30mL of deionized water, wherein the ultrasonic power is 500W, and the ultrasonic time is 2 h; 993 mg of zirconium oxychloride octahydrate is dissolved in 30mL of deionized water to prepare a zirconium oxychloride octahydrate solution, and the zirconium oxychloride octahydrate solution is added into the graphene oxide dispersion liquid and is continuously stirred for 2 hours. 8 mL (25% -28%) of aqueous ammonia was added to the mixed solution, stirred for 10 minutes, and the pH was adjusted to 10. The mixture was poured into a 100mL autoclave and placed at 200%oAnd C, performing hydrothermal reaction for 12 hours in an oven. And (3) washing the graphene oxide and zirconium dioxide composite material to be neutral by using deionized water in a suction filtration mode, then washing the graphene oxide and zirconium dioxide composite material by using 50mL of absolute ethyl alcohol, and freeze-drying the graphene oxide and zirconium dioxide composite material to obtain the reduced graphene oxide and zirconium dioxide composite material.
Example 4
Preparing a solid phase extraction column: a3 mL syringe was filled with the lower pad, 50mg of diatomaceous earth was weighed into the 3mL syringe, the amount of diatomaceous earth filled was about 1cm, and the pad was added. 150 mg of the reduced graphene oxide @ zirconium dioxide composite material obtained in examples 1, 2 and 3 was weighed in a 3mL syringe, and then a gasket was added to obtain a solid-phase extraction purification column filled with the reduced graphene oxide @ zirconium dioxide composite material, as shown in fig. 2.
Example 5
Placing 2.0 g of ground tea into a 50mL centrifuge tube, adding 0.05M NaOH20mL, vortexing, performing ultrasonic treatment for 10 minutes, centrifuging at 5000 rpm for 10 minutes to obtain supernatant 1, adding 6M HCl into the supernatant 1, and centrifuging to obtain tea matrix extract 2 with pH of about 3.
1mL of tea substrate extract 2 was passed through a solid phase extraction column prepared from the reduced graphene oxide @ zirconium dioxide composite material of example 1 at a rate of 1 drop/s, then rinsed with 1mL of acetonitrile, and finally eluted with 1mL of 1M NaOH to obtain glyphosate and aminomethylphosphonic acid. FIG. 3 shows a liquid chromatogram of changes in the matrix components of green tea leaves in an extract solution before and after purification by solid phase extraction. As can be seen from figure 3, after the tea leaves are purified by the solid phase extraction purification column, the contents of high-content components, namely catechin and caffeine, in the tea leaf matrix are greatly reduced, and the purification effect is good.
Example 6
2.0 g of ground tea leaf sample is put into a 50ml centrifuge tube, and the standard solutions of glyphosate and aminomethylphosphonic acid are added to the tube at the concentrations of 1 mg L-1And 0.5 mg L-1Standing for 30min, adding 20mL of 0.05M NaOH solution, uniformly mixing by vortex, performing ultrasonic treatment for 10min, and centrifuging at 5000 rpm for 10min to obtain a supernatant 1. The pH was adjusted with 6M HCl solution and centrifuged at 5000 rpm for 10min to obtain supernatant 2.
Taking 2mL of the supernatant 2, passing through a solid phase extraction column prepared from the reduced graphene oxide @ zirconium dioxide composite material in the embodiment 2, then leaching with 1mL of acetonitrile, finally eluting with 1mL of 1M NaOH solution, filtering the eluent after derivatization through a 0.22-micrometer microporous filter membrane, transferring to a sample injection bottle, and analyzing by high performance liquid chromatography tandem mass spectrometry. Under the condition of standard concentration, the addition recovery rates of glyphosate and aminomethylphosphonic acid are 79.71% and 79.80%, 76.68% and 81.02% respectively; the Relative Standard Deviation (RSD) is divided into 1.59% and 3.35%, and the minimum detection Limit (LOD) and quantification Limit (LOQ) of glyphosate and aminomethylphosphonic acid are respectively 1.7-4.4 mu gkg calculated by 3 times or 10 times signal-to-noise ratio (S/N)-1And 5.8-14.6 mu gkg-1。
Example 7
2.0 g of the ground tea sample was placed in a 50ml centrifuge tube, and a standard glyphosate solution was added thereto at a concentration of 2 mg L-1Standing for 30min, adding 20mL of 0.05M NaOH solution, uniformly mixing by vortex, performing ultrasonic treatment for 10min, and centrifuging at 5000 rpm for 10min to obtain a supernatant 1. The pH was adjusted with 6M HCl solution and centrifuged at 5000 rpm for 10min to obtain supernatant 2.
The reduced graphene oxide/nano zirconium dioxide composite adsorbent prepared by the method of example 1 in patent CN 201510395972.X is packed into a solid phase extraction purification column by the method of example 4.
2mL of the supernatant 2 was subjected to solid-phase extraction column prepared from the reduced graphene oxide @ zirconium dioxide composite material of example 2 and solid-phase extraction column prepared from patent CN 201510395972.X, and the content of glyphosate in the effluent was measured, and it was found that the adsorption capacities of the solid-phase extraction purification column prepared by the present invention and the solid-phase extraction column prepared by the comparative patent CN 201510395972.X to glyphosate were 92% and 74%, respectively. Experimental results show that the reduced graphene oxide @ zirconium dioxide composite material prepared by the invention has stronger adsorption capacity on glyphosate.
Claims (9)
1. The reduced graphene oxide @ zirconium dioxide composite material is characterized by being prepared through the following steps:
(1) adding graphene oxide into deionized water for ultrasonic stripping to obtain uniformly dispersed graphene oxide dispersion liquid;
(2) adding an aqueous solution of zirconium oxychloride octahydrate into the graphene oxide dispersion liquid obtained in the step (1), continuously stirring, and fully mixing the aqueous solution and the zirconium oxychloride;
(3) adjusting the pH value of the solution in the step (2) to be alkaline by using ammonia water;
(4) carrying out hydrothermal reaction on the mixed solution obtained in the step (3);
(5) and (4) cooling the mixture obtained in the step (4) to room temperature, washing and drying to obtain the reduced graphene oxide @ zirconium dioxide composite material.
2. The reduced graphene oxide @ zirconium dioxide composite material as claimed in claim 1, wherein the mass ratio of the graphene oxide to the zirconium oxychloride octahydrate in the step (2) is 0.001-0.5.
3. The reduced graphene oxide @ zirconium dioxide composite material as claimed in claim 1, wherein the pH in step (3) is adjusted to 10-12.
4. The reduced graphene oxide @ zirconium dioxide composite material as claimed in claim 1, wherein the hydrothermal reaction conditions in step (4) are 180 ℃ to 200 ℃ and 10 to 15 hours of solvothermal time.
5. The use of a reduced graphene oxide @ zirconium dioxide composite material as claimed in any one of claims 1 to 4 for the pre-treatment of a pesticide residue in tea.
6. The use of claim 5, wherein the pesticide residue is glyphosate and aminomethylphosphonic acid.
7. The method of application of claim 5, comprising the steps of:
1) filling the reduced graphene oxide @ zirconium dioxide composite material and diatomite in series to form a solid-phase extraction purification column;
2) adding an alkaline solution into the crushed tea leaves for extraction, performing vortex, ultrasonic treatment and centrifugation to obtain a supernatant 1, adding hydrochloric acid into the supernatant 1 to adjust the pH value to acidity, and performing centrifugation to obtain a supernatant 2;
3) and (3) passing the supernatant 2 through the solid-phase extraction purification column in the step 1), eluting and eluting to obtain an eluent, deriving by using chloroformate-9-fluorenylmethyl ester, and performing qualitative and quantitative analysis by using a liquid chromatography tandem mass spectrum after derivation.
8. The application method of claim 7, wherein in step 1), the diatomite is at the lower layer, the reduced graphene oxide @ zirconium dioxide composite material is at the upper layer, and the filling amount of the diatomite is 0.5-1.5 cm.
9. The method of claim 7, wherein the solid phase extraction column of step 1) further comprises other materials acceptable for use in pre-treatment of agricultural products.
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