CN111389372B - Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof - Google Patents
Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a special graphene oxide aerogel solid-phase extraction column for a perfluorinated acid compound and a preparation method thereof. The solid-phase extraction column adopts graphene oxide aerogel, and the preparation method comprises the steps of firstly obtaining graphene oxide, then obtaining aminated graphene oxide hydrogel, then preparing aminated graphene oxide aerogel, and finally preparing the solid-phase extraction column. The graphene oxide aerogel prepared by the method does not need other polymer supporting materials, has excellent adsorption performance, can adsorb more perfluorinated acid compounds, has higher adsorption capacity and good adsorption effect, can quickly absorb target substances, and enables the detection to be more sensitive and quicker.
Description
Technical Field
The invention relates to the technical field of solid-phase extraction, in particular to a special graphene oxide aerogel solid-phase extraction material for a perfluorinated acid compound and a preparation method thereof.
Background
Solid Phase Extraction (SPE) is a sample pretreatment technology developed from the middle of the 80 th century, is established on the basis of traditional liquid-liquid extraction, and is gradually developed by combining a similar phase solution principle of substance interaction and stationary phase basic knowledge in HPLC/GC widely applied at present, most of SPE is used for processing liquid samples, extracting, concentrating and purifying semi-volatile and non-volatile compounds in the liquid samples, and mainly aims to reduce sample matrix interference and improve detection sensitivity.
Perfluoro compounds (PFCs), represented by perfluorooctane carboxylic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are widely used in consumer goods for daily use and industrial production, and can enter the environment in large quantities through various routes, and the presence of PFCs has been widely detected in various environmental media and organisms around the world.
At present, PFCs distribution and fate research in water environment mainly aims at PFOS, PFOA and long-chain homologues thereof. With the disablement of PFOS and PFOA, a series of short chain homologs have entered the production and application areas, and eventually the environment, as substitutes. However, the traditional AAO process in the existing municipal sewage treatment plant has low removal efficiency of the pollutants, so that the perfluoroalkyl carboxylic acid is accumulated in the water environment, thereby becoming a difficult point for controlling water pollution.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a special graphene oxide aerogel solid-phase extraction column for a perfluorinated acid compound and a preparation method thereof. The adsorbent obtained by the method can effectively enrich the perfluoroalkyl carboxylic acid in the water body; has the advantages of high adsorption efficiency and easy separation.
The core of the graphene oxide aerogel solid-phase extraction column is that the graphene oxide aerogel solid-phase extraction column comprises aminated graphene oxide aerogel.
The preparation method of the graphene oxide aerogel solid-phase extraction column comprises the following four steps, wherein in the first step, graphene oxide is prepared; secondly, preparing aminated graphene oxide hydrogel; step three, preparing aminated graphene oxide aerogel; and fourthly, preparing a solid phase extraction column. The method is represented by a flow chart as attached figure 1, and comprises the following specific steps:
step one, preparing graphene oxide: natural graphite is used as a raw material, an improved Hummers method is adopted for synthesis, and graphene oxide is prepared through the stages of feeding, low-temperature reaction, medium-temperature reaction, high-temperature reaction, washing and drying;
step two, preparing an aminated graphene oxide hydrogel: carrying out ultrasonic dispersion on the graphene oxide obtained in the first step to obtain a first dispersion liquid; adding a diethylenetriamine solution into the dispersion liquid and stirring to obtain a second dispersion liquid; adding N, N-methylene bisacrylamide and ammonium persulfate into the second dispersion liquid, and then carrying out hydrothermal reaction; after the reaction is finished, cooling to room temperature to obtain aminated graphene oxide hydrogel;
step three, preparing an aminated graphene oxide aerogel: soaking the aminated graphene oxide hydrogel obtained in the second step in ethanol, and freeze-drying the obtained solid product to obtain aminated graphene oxide aerogel;
and fourthly, loading the aminated graphene oxide aerogel obtained in the third step into a separation column, adding a proper amount of quartz sand or silica gel as a supporting agent, placing the separation column on a shaking table for shaking, and compacting the aminated graphene oxide aerogel to obtain the solid-phase extraction column.
Further, in the above technical solution, in the second step, the volume fraction of diethylenetriamine is 0.45%.
Further, in the above technical solution, in the second step, every 10mL of the solution contains 7.5mg of N, N-methylenebisacrylamide (BIS for short) and 30mg of ammonium persulfate (APS for short).
Further, in the above technical scheme, in the second step, the second mixed dispersion solution is placed in a water bath kettle at 95 ℃ for 24 hours in a water bath, so as to prepare the aminated graphene oxide hydrogel.
Further, in the above technical scheme, in the third step, the prepared aminated graphene oxide hydrogel is soaked in a 20% ethanol solution for 6 hours.
Further, in the above technical scheme, in the third step, after freezing the hydrogel, freeze-drying the hydrogel by using a freeze dryer to obtain the aminated graphene oxide aerogel, wherein during freeze-drying, the freeze dryer maintains a vacuum degree of less than 10Pa, and the freeze-drying treatment is carried out for 24-48h.
The graphene oxide aerogel solid-phase extraction column prepared by the method is applied to extraction of the perfluoroacid compound.
Further, in the above technical solution, the perfluoro acid compound is selected from perfluorooctane carboxylic acid (PFOA) or perfluorooctane sulfonic acid (PFOS).
Advantageous effects of the invention
The material synthesized by the method can be applied to high-efficiency enrichment and measurement of perfluoroacid compounds (two typical PFOA and PFOS in the perfluoroacid compounds are listed in the United states water quality standard in 2020), and is beneficial to improving the enrichment efficiency by more than 3 times and improving the lower detection limit. For a high-concentration water sample, the enrichment efficiency of the method is higher than that of the conventional solid-phase extraction column by more than 50%.
Drawings
Fig. 1 shows a preparation process of aminated graphene oxide gel.
FIG. 2 shows a solid-phase extraction column (photograph of an embodiment of the present invention) of aminated graphene oxide.
FIG. 3 adsorption curves of different EDA-GO doses for the same PFOS concentration.
Figure 4 adsorption isotherms of EDA-GO gel for PFOS at different temperatures.
Figure 5 adsorption of PFOA by EDA-GO gel.
Detailed Description
EXAMPLE 1 preparation of solid phase extraction column
Step one, preparing graphene oxide:
a charging stage: preparing a water bath, accurately measuring 110mL of concentrated sulfuric acid, placing the concentrated sulfuric acid in a 500mL three-neck round-bottom flask, carrying out ice bath for 15min, and controlling the temperature to be between-5 ℃ and 0 ℃. Then 5g of natural graphite and 2.5g of sodium nitrate are slowly added into concentrated sulfuric acid (in the feeding process, a weighing paper roll forming funnel plug can be used to plug in the rightmost mouth of a three-mouth bottle, so that the added graphite can be completely added into the concentrated sulfuric acid to prevent the graphite from sticking to the wall of the bottle and not completely reacting with the concentrated sulfuric acid), and after stirring for 30min under ice bath, 15g of potassium permanganate is slowly added (which must be slowly and uniformly added).
And (3) low-temperature stage: after the reagents were added, the apparatus was stirred at 5-10 ℃ for 2h.
A medium temperature stage: the device is transferred to a water bath with the temperature of 35-40 ℃ for reaction, and the reaction is continuously stirred for 2.5-4h (when the temperature is moderate, the rotation speed can be adjusted to be faster, so that the oxidizing agent and the graphite are oxidized more uniformly) until the solution becomes yellowish-brown viscous solution and finally becomes pasty and can not be stirred. (the low-temperature reaction and the medium-temperature reaction show dark green color, and concentrated sulfuric acid molecules are mainly inserted between the graphite in the two reaction stages to carry out primary oxidation on the graphite together with potassium permanganate)
And (3) high-temperature stage: after the medium temperature reaction, a water bath was prepared, the apparatus was transferred to the water bath until the temperature dropped to 30 ℃ and 230mL of water was added, slowly as the first stage water was added. Note that during the addition of water, the temperature is controlled below 70 ℃. After the water addition, the device was placed in the water bath again and the warm reaction was carried out at 95 ℃ for 15min.
Washing and drying: after the high-temperature reaction, the device is transferred to the room temperature, the temperature is reduced to 40 ℃, 30% hydrogen peroxide is added, the reaction is stopped after stirring for 15min, and at the moment, the solution turns from earthy yellow to golden yellow. Then, the solution is centrifuged at 40000 rpm for 5 minutes, washed 3 times with 7% hydrochloric acid to remove metal ions in the solution and remove sulfate ions and permanganate ions. Followed by another wash with pH =7 (10000 rpm). And (5) putting the obtained product into a vacuum drying oven for drying.
Step two, preparing aminated graphene oxide hydrogel: and adding the graphene oxide obtained in the first step into deionized water, and performing ultrasonic dispersion for 1h until no particulate matter exists. Adding a diethylenetriamine solution, and stirring for 10min, wherein the volume fraction of the diethylenetriamine is 0.45%, so as to prepare an aminated graphene oxide aqueous solution; adding N, N-methylene Bisacrylamide (BIS) and Ammonium Persulfate (APS) into the amination graphene oxide aqueous solution, stirring for 5min, and controlling the BIS to be 7.5mg and the APS to be 30mg in each 10mL of solution to prepare a second mixed dispersion solution; putting the second mixed dispersion solution into a water bath kettle at the temperature of 95 ℃, and carrying out water bath for 24 hours to prepare aminated graphene oxide hydrogel;
step three, soaking the aminated graphene oxide hydrogel obtained in the step two in a 20% ethanol solution for 6 hours; and then carrying out freeze drying by a freeze dryer to obtain the aminated graphene oxide aerogel, wherein during freeze drying, the freeze dryer keeps the vacuum degree below 10Pa, and the aminated graphene oxide aerogel is obtained after freeze drying treatment for 24-48h.
And fourthly, filling the aminated graphene oxide aerogel obtained in the third step into a separation column (the separation column consists of a column tube, a sintering pad and an aminated graphene oxide stationary phase), adding a proper amount of quartz sand or silica gel as a propping agent (the ratio is 1.5 to 2), filling the aminated graphene oxide aerogel into the separation column, placing the separation column on a shaking table for shaking for 3min, and compacting the aminated graphene oxide aerogel to obtain the solid-phase extraction column. The material object is shown in figure 2.
Example 2: adsorption of PFOS
Preparing 600mg/L PFOS solution, weighing 1-10mg aminated graphene oxide aerogel obtained in the third step in example 1, and adsorbing at 25 ℃ for 12 hours at 140 r/min; the maximum adsorption capacity is 3702 mg/g, the maximum removal rate is 97%, the adsorption capacity is far higher than that of the traditional activated carbon material (1208 mg/g), and the adsorption effect is shown in figure 3. According to the adsorption isotherms of the EDA-GO gel for PFOS at different temperatures, the maximum adsorption capacity of the material is 3500mg/g, which is far larger than the adsorption capacity of the activated carbon material 263mg/g, and the adsorption isotherm is shown in figure 4.
Example 3: adsorption of PFOA
Preparing 10, 100 and 1000 mg/LPFOA solutions, weighing 1mg of aminated graphene oxide aerogel obtained in the third step in embodiment 1, and adsorbing at 25 ℃ and 140r/min for 12h; the maximum adsorption capacity is 1560 mg/g, the maximum removal rate is 99.95 percent, the adsorption capacity is far higher than the adsorption capacity (277 to 434.8mg/g) of the traditional activated carbon material, and the adsorption effect is shown in figure 5.
Example 4: perfluorocompound analysis experiment using the solid phase extraction column of example 1
Activation- -to remove impurities in the small column and create a certain solvent environment. First, 5-10mL of methanol was added for activation, and when the filtration was completed, 5mL of pure water was added for rinsing at a flow rate of 1mL/min.
Loading- -dissolve the sample in a solvent, transfer to the column and leave the components on the column. The flow rate is preferably 0.5 to 1mL/min, the maximum flow rate is not more than 5mL/min, and 5 percent of methanol is added into the sample, so that the sample is favorably kept in the column.
Leaching- -to remove water-soluble interferents to the maximum extent. After the process is finished, the small column is completely drained for more than 15-30 minutes, and 20% methanol aqueous solution is used for the experiment, preferably 1ml/min.
Elution- -elution of the test substance with a small volume of solvent and collection. The flow rate is preferably 0.5-1mL/min, and 5mL of methanol is used for elution.
An Agilent1200-TOF6224 liquid chromatography mass spectrometer (HPLC-MS) was used, the column was Eclipse Plus C18 (150X 4.6mm,3.5 μm), and the mobile phase was V (acetonitrile): v (water) =95:5, flow rate of 0.5mL/min, ionization mode of APCI (Negative), scan time of 50min, atomizer pressure (NEB) of 30psig, drying gas flow rate of 12.0L/min, drying gas Temperature (TEMP) of 350 deg.C, capillary voltage of 4000V.
The extraction experiment is carried out for 3 times in parallel, the sample recovery rate is 70% -97%, and the specific experiment result is shown in table 1; the result shows that the solid phase extraction column is suitable for enrichment analysis of the perfluoroacid compounds and is superior to the extraction effect of the traditional C18 and HLB solid phase extraction column.
TABLE 1 comparison of recovery of the present invention with conventional solid phase extraction column (unit:%)
The foregoing embodiments have described the general principles, major features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (5)
1. The application of the graphene oxide aerogel solid-phase extraction column in extracting the perfluoroacid compounds is characterized in that: the graphene oxide aerogel solid-phase extraction column comprises aminated graphene oxide aerogel, and the perfluoro acid compound is selected from perfluorooctane carboxylic acid or perfluorooctane sulfonic acid; the graphene oxide aerogel solid-phase extraction column is prepared by the following steps:
step one, preparing graphene oxide: natural graphite is used as a raw material, an improved Hummers method is adopted for synthesis, and graphene oxide is prepared through the stages of feeding, low-temperature reaction, medium-temperature reaction, high-temperature reaction, washing and drying;
step two, preparing aminated graphene oxide hydrogel: carrying out ultrasonic dispersion on the graphene oxide obtained in the first step to obtain a first dispersion liquid; adding a diethylenetriamine solution into the dispersion liquid and stirring to obtain a second dispersion liquid; adding N, N-methylene bisacrylamide and ammonium persulfate into the second dispersion liquid, and then carrying out hydrothermal reaction; after the reaction is finished, cooling to room temperature to obtain aminated graphene oxide hydrogel;
step three, preparing an aminated graphene oxide aerogel: soaking the aminated graphene oxide hydrogel obtained in the second step in ethanol, and freeze-drying the obtained solid product to obtain aminated graphene oxide aerogel;
and fourthly, loading the aminated graphene oxide aerogel obtained in the third step into a separation column, adding a proper amount of quartz sand or silica gel as a supporting agent, placing the separation column on a shaking table for shaking, and compacting the aminated graphene oxide aerogel to obtain the solid-phase extraction column.
2. The application of the graphene oxide aerogel solid-phase extraction column according to claim 1 in extracting perfluoroacid compounds is characterized in that: in the second step, the volume fraction of diethylenetriamine was 0.45%.
3. The application of the graphene oxide aerogel solid-phase extraction column according to claim 1 in extracting perfluoroacid compounds is characterized in that: in the second step, every 10mL of the solution, the BIS was 7.5mg and the APS was 30mg.
4. The application of the graphene oxide aerogel solid-phase extraction column according to claim 1 in extracting perfluoroacid compounds is characterized in that: in the second step, the hydrothermal reaction temperature was 95 ℃.
5. The application of the graphene oxide aerogel solid-phase extraction column according to claim 1 in extracting perfluoroacid compounds is characterized in that: in the fourth step, the ratio of quartz sand or silica gel as a propping agent to aminated graphene oxide aerogel is 1:0.5 to 2.
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| CN112229938A (en) * | 2020-11-13 | 2021-01-15 | 上海市农业科学院 | Solid phase extraction column for detecting perfluorinated compounds and manufacturing method and application thereof |
| CN114832777B (en) * | 2022-05-11 | 2023-03-28 | 浙江大学 | Modification method for removing perfluorocarboxylic acid in water by using enhanced activated carbon and prepared modified activated carbon |
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