CN107697997B - Hydrophobic metal trapping agent and preparation method thereof - Google Patents
Hydrophobic metal trapping agent and preparation method thereof Download PDFInfo
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- CN107697997B CN107697997B CN201711001968.6A CN201711001968A CN107697997B CN 107697997 B CN107697997 B CN 107697997B CN 201711001968 A CN201711001968 A CN 201711001968A CN 107697997 B CN107697997 B CN 107697997B
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- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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Abstract
The invention discloses a hydrophobic metal trapping agent and a preparation method thereof, wherein the method comprises the following steps: first, aminopropyl isobutyl silsesquioxane (NH) was added2POSS), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing and stirring 3-mercaptopropionic acid (MPA) and absolute ethyl alcohol to fully dissolve to obtain a mixed solution b; then, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, and continuing stirring for reaction after the dripping is finished to obtain a generated solution; finally, the resulting solution is purified to obtain a hydrophobic metal capture agent (MPA-POSS for short). The hydrophobic metal trapping agent can remove heavy metal pollution in a water phase without adding any flocculating agent, can realize enrichment determination of trace or trace heavy metals, has no residue in a water body, does not cause secondary pollution, and meets the requirement of environmental protection.
Description
Technical Field
The invention relates to the technical field of metal trapping agents, in particular to a hydrophobic metal trapping agent and a preparation method thereof.
Background
Heavy metal pollution is always a key object for water environment treatment, and pollution sources of the heavy metal pollution are mainly put into the water environment from industrial wastewater, agricultural wastewater, domestic pollution and the like. Heavy metals can enter the human body through direct environmental contact, food chains, etc., and accumulate in the human body, thereby causing harm. Therefore, the timely and effective treatment means has important significance for preventing and treating heavy metal pollution.
Currently, many collectors such as Dithiocarbamates (DTCs), sodium thiotriazines (TMTs), and sodium thiotri-carbonates (STCs) having S atoms as coordinating atoms, and modified products using these as chelating groups have been studied. Most of the trapping agents have good water solubility and good removal effect on metal ions, so that the trapping agents are greatly developed and applied. However, due to its good water solubility, when it is used to treat heavy metals in water, it often causes residues and forms secondary pollution, especially when it is used to treat trace heavy metal pollution, its pollution capability is not as good as its removal capability.
In addition, when the trapping agent is used for treating heavy metals, a certain amount of flocculating agent needs to be added to form a cluster so as to achieve the purpose of aggregation and sedimentation, and the addition of the flocculating agent undoubtedly increases the cost and operation and simultaneously brings new pollution to a water body; in addition, when the pollution of trace or trace heavy metals is faced, the pollution is removed, and meanwhile, the enrichment effect on metal ions is expected, so that the content of the pollutants can be measured by the enrichment method, which cannot be achieved by the traditional metal trapping agent.
In the prior art, the chinese patent publication No. CN105858852A discloses a method for synthesizing and applying a polymeric metal trapping agent. In the patent, the metal trapping agent has dithiocarbamic acid group and amide group, is a high molecular polymer, and the synthesis method comprises the following steps: adding 67.12g of ethylenediamine into 250mL of distilled water at 20 ℃ under continuous stirring; then 71.08g of acrylamide was added, and the temperature was controlled at 30 ℃; then 147.78g of trimethylamine alkaline solution with the content of 40 percent is added, and the temperature is controlled to be 20 ℃; then 170.24g of carbon disulfide is dripped, the carbon disulfide is added within 30min, and the mixture is continuously stirred and reacts for 20min to obtain a mixture; and carrying out suction filtration, washing, dehydration and drying on the mixture to obtain the high-molecular heavy metal trapping agent. The metal trapping agent has good water solubility and flocculation precipitation effect, and can well react with various heavy metal ions in water without adding a flocculating agent. However, this method has more reaction steps and lower final yield; the metal trapping agent has better water solubility, and is easy to cause the trapping agent to remain in a water phase in the treatment process to cause secondary pollution; the enrichment and the determination of trace and trace heavy metal pollution can not be realized.
The Chinese patent with the publication number of CN102531138A discloses a sulfide heavy metal trapping agent N, N' -bis (2-mercaptoethyl) -1, 3-benzenedicarboxamide and a preparation method thereof. The preparation method comprises the following steps: at the temperature of minus 5 ℃ and under the protection of nitrogen, 4.94g of mercaptoethylamine hydrochloride and 3.05g of isophthaloyl dichloride are dissolved in 65mL of chloroform, 5mL of triethylamine is added as an acid-binding agent, and the mixture is stirred and reacted for 5 hours to obtain the N, N' -bis (2-mercaptoethyl) -1, 3-benzenedicarboxamide. The metal trapping agent has the advantages of simple preparation method, good treatment effect and short settling time, and can be matched with other water treatment agents according to different types of treated metal ions. However, the reaction yield of the method is low, and can only reach 78.6 percent at most; flocculation sedimentation can be realized only by adding a flocculating agent, so that new pollution is brought to a water body; in addition, the metal trapping agent has better water solubility, is easy to cause the trapping agent to remain in a water phase in the treatment process, causes secondary pollution, and cannot realize the enrichment and determination of trace and trace heavy metal pollution.
Disclosure of Invention
The invention aims to provide a hydrophobic metal trapping agent and a preparation method thereof, the hydrophobic metal trapping agent can remove heavy metal pollution in a water phase without adding any flocculating agent, can realize enrichment determination of trace or trace heavy metals, has no residue in a water body, does not cause secondary pollution, and meets the requirement of environmental protection.
In order to achieve the above object, the present invention provides a hydrophobic metal trapping agent, which has a structural formula:
wherein R is isobutyl.
The invention also provides a preparation method of the hydrophobic metal trapping agent, which comprises the following steps: first, aminopropyl isobutyl silsesquioxane (NH) was added2POSS), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing and stirring 3-mercaptopropionic acid (MPA) and absolute ethyl alcohol to fully dissolve to obtain a mixed solution b; then, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, and continuing stirring for reaction after the dripping is finished to obtain a generated solution; finally, the resulting solution is purified to obtain a hydrophobic metal capture agent (MPA-POSS for short).
Further, the aminopropyl isobutyl silsesquioxane (NH)2POSS, Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and 3-mercaptopropionic acid (MPA) in a molar ratio of 1 (1-1.5) to 0.05-0.10 (1-1.5).
Preferably, the aminopropyl isobutyl silsesquioxane (NH)2POSS, Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and 3-mercaptopropionic acid (MPA) in a molar ratio of 1 (1.0-1.2) to 0.05-0.08 (1.0-1.2).
Optimally, the aminopropyl isobutyl silsesquioxane (NH)2-POSS), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP), 3-mercaptopropionic acid (MPA) in a molar ratio of 1:1.2:0.05: 1.2.
Further, the solid-to-liquid ratio of aminopropyl isobutyl silsesquioxane to dichloromethane is 1: (6-12) g/mL.
Preferably, the solid-to-liquid ratio of aminopropyl isobutyl silsesquioxane to dichloromethane is 1: (10-12) g/mL.
Optimally, the solid-to-liquid ratio of the aminopropyl isobutyl silsesquioxane to dichloromethane is 1: 12 g/mL.
Further, the solid-to-liquid ratio of the 3-mercaptopropionic acid (MPA) to the absolute ethyl alcohol is 1: (75-150) g/mL.
Preferably, the solid-to-liquid ratio of the 3-mercaptopropionic acid (MPA) to absolute ethyl alcohol is 1: (100-150) g/mL.
Most preferably, the solid-to-liquid ratio of the 3-mercaptopropionic acid (MPA) to absolute ethanol is 1: 150 g/mL.
Furthermore, the dropping speed of the mixed solution a to the mixed solution b is 0.8-1.6 mL/min.
Preferably, the dropping speed of the mixed solution a to the mixed solution b is 1.0-1.2 mL/min.
Optimally, the dropping speed of the mixed liquid a to the mixed liquid b is 1.0 mL/min.
Further, the reaction temperature of the stirring reaction is 20-25 ℃, and the reaction time is 10-15 hours.
Further, the purification treatment comprises the following specific steps: firstly, carrying out first suction filtration on a generated solution, and taking a filtrate for freezing treatment; performing suction filtration for the second time, taking filtrate, and evaporating the solvent to dryness to obtain a white solid; and finally, washing and drying the white solid in sequence to obtain a white powdery hydrophobic metal trapping agent product.
Further, the temperature of the freezing treatment is-18 to-7 ℃, and the treatment time is 2 to 4 hours; the evaporation treatment is carried out for 0.5-4 hours by adopting a rotary evaporator.
Furthermore, the washing treatment is specifically washing for 3-6 times by using deionized water, and the drying treatment is drying for 4-6 hours at the temperature of 40-50 ℃.
Compared with the prior art, the invention has the following advantages:
first, the present invention utilizes aminopropyl isobutyl silsesquioxane (NH) having a strong hydrophobic structure2POSS) as a carrier under the action of a condensing agent Dicyclohexylcarbodiimide (DCC) and a catalyst 4-Dimethylaminopyridine (DMAP) by an amidation reaction under the action of NH2The POSS surface is bonded with hydrophilic molecule 3-mercaptopropionic acid (MPA) with chelation, the novel hydrophobic heavy metal trapping agent MPA-POSS is prepared, and the simple, quick and efficient removal and enrichment determination of trace heavy metal ions such as Cu and Cd in water are realized.
Secondly, the novel hydrophobic metal trapping agent prepared by the invention has a strong hydrophobic structure due to aminopropyl isobutyl silsesquioxane (NH)2POSS) is a cage type silsesquioxane with nanometer scale, which has rigid three-dimensional structure and strong hydrophobicity; the micromolecule 3-mercaptopropionic acid (MPA) connected on the single amino group is a hydrophilic complexing group containing sulfhydryl, and mainly plays a role in complexing with metal ions in water; the hydrophobic metal capture agent (MPA-POSS) formed when two substances are bonded together exhibits hydrophobicity throughout its molecule due to its large steric structure.
Thirdly, when the MPA-POSS trapping agent is prepared into solution by adopting ethanol for removing metal ions in water, the complexing end MPA can react with the metal ions, and the hydrophobic end with a larger three-dimensional structure can rapidly and spontaneously aggregate together in the water solution to form a larger bulk hydrophobic substance so as to be convenient for separation.
Fourthly, the hydrophobic metal trapping agent MPA-POSS can respectively carry out efficient removal and enrichment determination on trace copper ions and cadmium ions. Tap water is used as a sample, and the result shows that the removal rates of the MPA-POSS metal trapping agent on copper and cadmium respectively reach 99% and 97%; the enrichment times of copper and cadmium reach 50 times, and the sample standard adding recovery rates of the copper and the cadmium respectively reach 95-100 percent and 94-97 percent through determination.
And fourthly, the MPA-POSS trapping agent has the characteristics of high efficiency and no residue, and can realize the enrichment and determination of metal ions while removing trace or trace heavy metals.
Drawings
FIG. 1 is an infrared spectrum of a hydrophobic metal trap prepared according to the present invention;
FIG. 2 is a UV detection chart of the residual amount in the aqueous phase of the hydrophobic metal collector prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
the preparation method of the hydrophobic metal trapping agent comprises the following steps:
first, 5.0mmol of aminopropyl isobutyl silsesquioxane (NH)2POSS), 6.0mmol of Dicyclohexylcarbodiimide (DCC), 0.25mmol of 4-Dimethylaminopyridine (DMAP) and 50mL of dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, 6.0mmol of 3-mercaptopropionic acid (MPA) and 100mL of absolute ethyl alcohol are mixed, stirred and fully dissolved to obtain a mixed solution b; then, controlling the temperature to be 25 ℃, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, wherein the dripping speed is 1.0-1.2 mL/min, and continuously stirring for reacting for 15 hours after finishing dripping to obtain a generated solution; then, the resultant solution was subjected to a first suction filtration treatment to remove impuritiesDissolving impurities, freezing the filtrate at-18 ℃ for more than 2 hours, carrying out suction filtration for the second time to remove impurities, taking the filtrate, evaporating the filtrate for 2 hours by using a rotary evaporator, evaporating the solvent to dryness to obtain a white solid, repeatedly washing the white solid with deionized water for at least three times, and drying at 40 ℃ for 6 hours to obtain a white powdery hydrophobic metal trapping agent (MPA-POSS) product.
Example 2:
the preparation method of the hydrophobic metal trapping agent comprises the following steps:
first, 5.0mmol of aminopropyl isobutyl silsesquioxane (NH)2POSS), 7.5mmol of Dicyclohexylcarbodiimide (DCC), 0.50mmol of 4-Dimethylaminopyridine (DMAP) and 50mL of dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing 7.5mmol of 3-mercaptopropionic acid (MPA) and 100mL of absolute ethanol, stirring and fully dissolving to obtain a mixed solution b; then, controlling the temperature to be 20 ℃, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, wherein the dripping speed is 1.2-1.5 mL/min, and continuously stirring for reacting for 10 hours after finishing dripping to obtain a generated solution; and then, carrying out first suction filtration treatment on the generated liquid to remove insoluble impurities, freezing the filtrate at the temperature of minus 7 ℃ for more than 2 hours, carrying out second suction filtration treatment to remove impurities, taking the filtrate, evaporating the filtrate for 2 hours by using a rotary evaporator to evaporate the solvent to dryness to obtain a white solid, repeatedly washing the white solid with deionized water for at least three times, and drying at the temperature of 50 ℃ for 6 hours to obtain a white powdery hydrophobic metal trapping agent (MPA-POSS) product.
Example 3:
the preparation method of the hydrophobic metal trapping agent comprises the following steps:
first, 5.0mmol of aminopropyl isobutyl silsesquioxane (NH)2POSS), 5.0mmol of Dicyclohexylcarbodiimide (DCC), 0.40mmol of 4-Dimethylaminopyridine (DMAP) and 40mL of dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, 5.0mmol of 3-mercaptopropionic acid (MPA) and 50mL of absolute ethanol were mixed, stirred and sufficiently dissolved to obtain a mixtureA liquid b; then, controlling the temperature to be 25 ℃, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, wherein the dripping speed is 0.8-1.0 mL/min, and continuously stirring and reacting for 12 hours after finishing dripping to obtain a generated solution; and then, carrying out first suction filtration treatment on the generated liquid to remove insoluble impurities, freezing the filtrate at the temperature of minus 7 ℃ for more than 2 hours, carrying out second suction filtration treatment to remove impurities, taking the filtrate, evaporating the filtrate for 2 hours by using a rotary evaporator to evaporate the solvent to dryness to obtain a white solid, repeatedly washing the white solid with deionized water for at least three times, and drying at the temperature of 50 ℃ for 4 hours to obtain a white powdery hydrophobic metal trapping agent (MPA-POSS) product.
Example 4:
the preparation method of the hydrophobic metal trapping agent comprises the following steps:
first, 5.0mmol of aminopropyl isobutyl silsesquioxane (NH)2POSS), 5.5mmol of Dicyclohexylcarbodiimide (DCC), 0.30mmol of 4-Dimethylaminopyridine (DMAP) and 30mL of dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, 5.5mmol of 3-mercaptopropionic acid (MPA) and 60mL of absolute ethyl alcohol are mixed, stirred and fully dissolved to obtain a mixed solution b; then, controlling the temperature to be 25 ℃, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, wherein the dripping speed is 1.0-1.2 mL/min, and continuously stirring and reacting for 12 hours after finishing dripping to obtain a generated solution; and then, carrying out first suction filtration treatment on the generated liquid to remove insoluble impurities, freezing the filtrate at the temperature of 18 ℃ below zero for more than 2 hours, carrying out second suction filtration treatment to remove impurities, taking the filtrate, evaporating the filtrate for 0.5 hour by using a rotary evaporator to evaporate the solvent to dryness to obtain a white solid, repeatedly washing the white solid with deionized water for at least 3 times, and drying at the temperature of 40 ℃ for 4 hours to obtain a white powdery hydrophobic metal trapping agent (MPA-POSS) product.
Example 5:
the preparation method of the hydrophobic metal trapping agent comprises the following steps:
first, 5.0mmol of aminopropyl isobutyl silsesquioxane (NH)2-POSS), 6.5mmol of Dicyclohexylcarbodiimide (DCC), 0.45mmol of 4-Dimethylaminopyridine (DMAP) and 30mL of dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing 6.5mmol of 3-mercaptopropionic acid (MPA) and 80mL of absolute ethanol, stirring and fully dissolving to obtain a mixed solution b; then, controlling the temperature to be 25 ℃, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, wherein the dripping speed is 1.4-1.6 mL/min, and continuously stirring and reacting for 12 hours after finishing dripping to obtain a generated solution; and then, carrying out first suction filtration treatment on the generated liquid to remove insoluble impurities, freezing the filtrate at the temperature of minus 7 ℃ for more than 2 hours, carrying out second suction filtration treatment to remove impurities, taking the filtrate, evaporating the filtrate for 4 hours by using a rotary evaporator to evaporate the solvent to dryness to obtain a white solid, repeatedly washing the white solid with deionized water for at least three times, and drying at the temperature of 40 ℃ for 6 hours to obtain a white powdery hydrophobic metal trapping agent MPA-POSS product.
Example of effects:
firstly, infrared characterization: before the test, the sample was dried under vacuum at 40 ℃ and subjected to an infrared spectrometer using aminopropyl isobutyl silsesquioxane (NH) as a main raw material2POSS), 3-mercaptopropionic acid (MPA) and the product MPA-POSS prepared in example 1 were subjected to infrared characterization. The infrared spectrum is shown in FIG. 1, MPA (a) at 1700cm-1Has a distinct-COOH absorption peak; and NH2POSS (b) at 1228cm-1The corresponding absorption peak of the C-N bond also appears; MPA (a) and NH2Comparison of the IR spectra of POSS (b) and MPA-POSS (c) revealed 1700cm-1The peak position disappears and 1644cm newly appears-1And 1511cm-1The peak position, which is the absorption peak position of the amide bond, indicates that the amide compound is successfully synthesized, and the product MPA-POSS is obtained.
Secondly, detecting the residual quantity of the trapping agent
The hydrophobic metal trapping agents (MPA-POSS) prepared in the examples 1 to 5 are respectively prepared into 0.2 mass percent ethanol solutions, and proportionally prepared into 0.2 mass percent solutions by adopting conventional commercial dithiocarbamate modified starch (DTCS, belonging to dithiocarbamate trapping agents), and the solutions are applied to the removal and enrichment determination experiments of trace copper and cadmium in water, the residual quantity of the hydrophobic metal trapping agents is detected by adopting an ultraviolet spectrophotometry, and the experimental results are shown in a table 1 and a figure 2.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Copper ion removal rate | 99.2％ | 98.7％ | 97.1％ | 98.0％ | 96.7％ | 95.0％ |
| Removal rate of cadmium ion | 97.1％ | 95.7％ | 97.2％ | 96.3％ | 95.0％ | 94.2％ |
| Trapping agent residual ratio | ＜0.50％ | ＜0.50％ | ＜0.50％ | ＜0.50％ | ＜0.50％ | ＞50.0％ |
MPA-POSS can respectively carry out high-efficiency removal and enrichment determination on trace copper ions and cadmium ions, tap water is taken as a sample, and the results show that the removal rates of MPA-POSS metal trapping agent on copper and cadmium respectively reach 99% and 97%, which are far higher than those of a comparative example. In addition, the enrichment times of copper and cadmium reach 50 times, and the sample standard adding recovery rates of the copper and the cadmium respectively reach 95-100% and 94-97% through determination.
As shown in FIG. 2, MPA-POSS has an obvious ultraviolet absorption peak at 205nm, and ultraviolet spectrograms before and after MPA-POSS treatment of metal ions are compared, and no obvious peak position is at 205nm, which indicates that no residue exists in a water phase after the action of the metal trapping agent.
The above description is only an embodiment of the present invention, and it should be noted that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (10)
1. A hydrophobic metal trapping agent, characterized in that the hydrophobic metal trapping agent has the structural formula:
wherein R is isobutyl;
the hydrophobic metal trapping agent is prepared by the following method: first, aminopropyl isobutyl silsesquioxane (NH) was added2POSS), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing and stirring 3-mercaptopropionic acid (MPA) and absolute ethyl alcohol to fully dissolve to obtain a mixed solution b; then, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, and continuing stirring for reaction after the dripping is finished to obtain a generated solution; and finally, purifying the generated solution to obtain the hydrophobic metal trapping agent.
2. A method of preparing the hydrophobic metal collector of claim 1, comprising the steps of: first, aminopropyl isobutyl silsesquioxane (NH) was added2POSS), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and dichloromethane are mixed, stirred and fully dissolved to obtain a mixed solution a; then, mixing and stirring 3-mercaptopropionic acid (MPA) and absolute ethyl alcohol to fully dissolve to obtain a mixed solution b; then, slowly dripping the mixed solution a into the mixed solution b under the stirring condition, and continuing stirring for reaction after the dripping is finished to obtain a generated solution; and finally, purifying the generated solution to obtain the hydrophobic metal trapping agent.
3. The process for preparing a hydrophobic metal collector according to claim 2, wherein the aminopropyl isobutyl silsesquioxane (NH) is prepared by the following method2POSS, Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and 3-mercaptopropionic acid (MPA) in a molar ratio of 1 (1-1.5) to 0.05-0.10 (1-1.5).
4. The method of claim 2, wherein the solid-to-liquid ratio of aminopropyl isobutyl silsesquioxane to dichloromethane is 1: (6-12) g/mL.
5. The method of claim 2, wherein the solid-to-liquid ratio of 3-mercaptopropionic acid (MPA) to absolute ethanol is 1: (75-150) g/mL.
6. The method for producing a hydrophobic metal collector according to claim 2, wherein the dropping speed of the mixed solution a slowly dropped into the mixed solution b is 0.8 to 1.6 mL/min.
7. The method for preparing the hydrophobic metal collector according to claim 2, wherein the stirring reaction is carried out at a reaction temperature of 20 to 25 ℃ for 10 to 15 hours.
8. The method for preparing the hydrophobic metal collector according to claim 2, wherein the purification treatment comprises the following steps: firstly, carrying out first suction filtration on a generated solution, and taking a filtrate for freezing treatment; performing suction filtration for the second time, taking filtrate, and evaporating the solvent to dryness to obtain a white solid; and finally, washing and drying the white solid in sequence to obtain a white powdery hydrophobic metal trapping agent product.
9. The method for preparing the hydrophobic metal collector according to claim 8, wherein the freezing treatment temperature is-18 to-7 ℃, and the treatment time is 2 to 4 hours; the evaporation treatment is carried out for 0.5-4 hours by adopting a rotary evaporator.
10. The preparation method of the hydrophobic metal collector as claimed in claim 8, wherein the washing treatment is washing with deionized water for 3-6 times, and the drying treatment is drying at 40-50 ℃ for 4-6 hours.
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