CN110102083B

CN110102083B - Multifunctional oil-water separation material and preparation method and application thereof

Info

Publication number: CN110102083B
Application number: CN201910464118.2A
Authority: CN
Inventors: 程丝; 徐澄; 曹蕴哲
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2019-05-30
Filing date: 2019-05-30
Publication date: 2021-09-28
Anticipated expiration: 2039-05-30
Also published as: CN110102083A

Abstract

The invention discloses a preparation method of a multifunctional oil-water separation material, which comprises the following steps: s1, pretreating the copper mesh to remove impurities on the surface; s2, soaking the pretreated copper net in a chloroauric acid solution for 1-2 hours to obtain a copper net loaded with Au/CuCl particles; s3, soaking the copper mesh obtained in the step S2 in a silver salt solution for 1-2 hours to obtain the copper mesh with Au/AgCl particles loaded on the surface; s4, performing surface modification on the copper mesh obtained in the step S3 by using PFDT to obtain the multifunctional oil-water separation material. The invention also discloses the multifunctional oil-water separation material prepared by the method and application thereof. The multifunctional oil-water separation material prepared by the invention can separate an oil-water mixture, can detect low-concentration pollutants in an oil-water mixed solution, and can effectively photolyze the pollutants.

Description

Multifunctional oil-water separation material and preparation method and application thereof

Technical Field

The invention relates to the technical field of water treatment, in particular to a multifunctional oil-water separation material and a preparation method and application thereof.

Background

In recent years, an oil-water separation material based on surface wettability has been attracting attention, and a material having surface super wettability has been widely used for oil-water separation. The main basis for realizing oil-water separation is that the material interface has opposite wettability to an oil phase and a water phase, wherein the super-hydrophobic super-oleophylic interface material is a type of oil-water separation material which is more researched at present. The preparation method mainly comprises the steps of constructing a rough micro-nano structure on the surface of a substrate and modifying low surface chemical energy, wherein when an oil-water mixed solution contacts the super-hydrophobic super-oleophilic substrate, an oil phase can be quickly soaked and passes through the substrate, and a water phase cannot penetrate through the substrate.

However, much of the previous research has focused on the separation of oil from the aqueous phase, and has ignored further detection and removal of water-soluble contaminants. At present, oil-water separation is frequently carried out in the oil-water separation process of a factory, pollutant detection and pollutant photodegradation are carried out step by step, the operation is complex, and the cost consumption is high. Although Surface Enhanced Raman Scattering (SERS) has been widely used for the detection of various contaminants, the detection of low concentrations of contaminants in oil-water mixtures remains a challenge because the SERS signals of contaminants in oil-water mixtures can be difficult to distinguish due to mutual interference of the signals.

Feng et al reported a surface-supported double-layer titanium dioxide multifunctional copper mesh, which has super-hydrophobic/super-oleophilic characteristics, not only can separate oil-water mixtures, but also has photocatalytic degradation properties imparted to the copper mesh by titanium dioxide, so that the substrate can efficiently degrade pollutants in water. However, titanium dioxide can only generate catalytic activity under ultraviolet light, can only absorb ultraviolet light with a low content in sunlight, and has no light response under visible light, so that the low utilization efficiency of solar energy limits the practical application of the ultraviolet light type catalyst. In addition, the prior art lacks of Raman detection of pollutants in a water phase, only removes organic solvents and ignores water-soluble pollutants, and cannot meet the requirement of completely purifying water.

Therefore, the development of a novel material which can separate an oil-water mixture, detect low-concentration pollutants in the oil-water mixture and effectively photolyze the pollutants is of great significance.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a multifunctional oil-water separation material and a preparation method thereof, wherein the multifunctional oil-water separation material can separate an oil-water mixture, can detect low-concentration pollutants in an oil-water mixed solution, and can effectively photolyze the pollutants.

The invention aims to provide a preparation method of a multifunctional oil-water separation material, which comprises the following steps:

s1, pretreating the copper mesh to remove impurities on the surface;

s2, soaking the pretreated copper net in a chloroauric acid solution for 1-2 hours to obtain a copper net loaded with Au/CuCl particles;

s3, soaking the copper mesh obtained in the step S2 in a silver salt solution for 1-2 hours to obtain the copper mesh with Au/AgCl particles loaded on the surface;

s4, performing surface modification on the copper net obtained in the step S3 by using a low-surface-energy fluorine-containing substance perfluorodecyl mercaptan (PFDT) to reduce the surface energy of the copper net, and thus obtaining the multifunctional oil-water separation material.

Further, in step S1, the preprocessing specifically includes: and ultrasonically cleaning the copper mesh by using dilute hydrochloric acid, acetone and water in sequence.

Further, in step S2, the concentration of the chloroauric acid solution was 0.01M.

Further, in step S3, the silver salt solution is silver nitrate solution with concentration of 0.005-0.2M.

Further, the method comprises the step of rinsing the surface of the copper mesh with ultrapure water after the copper mesh is taken out from the chloroauric acid solution or the silver salt solution.

Further, in step S4, the surface modification specifically is: and (4) soaking the copper mesh obtained in the step S3 in a PFDT/ethanol solution for 6-12h to enable the mercapto groups on the PFDT molecules to be combined on the surface of the copper mesh to form stable chemical bonds.

Further, the concentration of the PFDT/ethanol solution is 10-20 mM.

Further, in step S4, after the surface modification, the copper mesh is taken out, and the non-adsorbed PFDT molecules on the surface are washed with ethanol, and then dried in a vacuum drying oven for use.

The invention also provides the multifunctional oil-water separation material prepared by any one of the methods.

In addition, the invention also provides application of the multifunctional oil-water separation material in industrial oil-water separation.

The invention has the beneficial effects that:

1. the method adopts a solution soaking method to grow Au/CuCl particles on the surface of the copper mesh in situ, constructs a micro-nano structure to improve the roughness of the surface of the copper mesh, and then modifies PFDT molecules of a low-surface-energy substance on the surface of the copper mesh so as to realize the super-hydrophobic effect of the surface of the copper mesh, wherein the surface contact angle reaches 158 degrees. The copper mesh oil-water separation efficiency is as high as more than 97%, and the separation rate is high.

2. The substrate combines the super-hydrophobic characteristic and the surface plasmon resonance characteristic of noble metal particles, can be applied to separation and concentration detection of oil-water mixed phase pollutants, can eliminate interference of the oil-phase pollutants on signals during Raman detection, and can improve the Raman detection sensitivity of a water-phase object to be detected by the surface super-hydrophobic characteristic to realize high-sensitivity detection.

3. According to the invention, the AgCl particles endow the copper mesh with excellent photodegradability, and the copper mesh can carry out photodegradation on water-phase pollutants after the oil-water mixed liquid is separated, so that the sewage can be efficiently purified. And relative to the semiconductor material TIO₂The copper mesh can be in the visible light regionThe light degradation is carried out, and the sunlight is fully utilized. Compared with the traditional mode of dispersing the photocatalyst in a solution to degrade pollutants, the in-situ supported photocatalyst can be well recycled, and meanwhile, the secondary pollution caused by the dispersion of the photocatalyst in a water body is avoided.

4. One of the raw materials of the invention is cheap and easy to obtain, the step operation is simple and convenient, and the preparation cost is reduced.

Drawings

FIG. 1 is a flow chart of the preparation of the present invention;

FIG. 2 shows a surface image (a) and SEM images (b-d) of a copper mesh supporting Au/CuCl particles;

FIG. 3 is a surface image (d) and SEM image (e-f) of Au/AgCl loaded copper mesh;

FIG. 4 is a contact angle image of the copper mesh prepared in example 1;

FIG. 5 is a SERS spectrum of a mixture of Sudan III and methylene blue on a silicon wafer (a) and a copper mesh prepared in example 1 (b);

FIG. 6 is a graph showing the UV absorption curves of 10mL of methylene blue solution with a concentration of 10mg/L, which is photodegraded by the copper mesh prepared in example 1, under the irradiation of a 300W xenon lamp as a visible light source.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Example 1: preparation of copper mesh integrating three functions of oil-water separation, dye detection and photodegradation

(1) Pretreating the copper mesh: sequentially ultrasonically cleaning impurities on the surface of the copper mesh by using a hydrochloric acid solution, an acetone solution and deionized water respectively, soaking the copper mesh in a 0.01M chloroauric acid solution for 1-2 hours after treatment, taking out the copper mesh, and washing away the impurities on the surface by using ultrapure water to obtain an Au/CuCl particle-loaded copper mesh;

(2) soaking the copper net loaded with the Au/CuCl particles in silver nitrate solution with the concentration of 0.01M for 1-2 hours, then taking out the copper net, and washing the surface of the copper net with ultrapure water to obtain the copper net loaded with the Au/AgCl particles on the surface;

(3) and then modifying the surface of the material by using a low-surface-energy fluorine-containing substance perfluorodecyl mercaptan (PFDT) to reduce the surface energy of the copper mesh. And (3) putting the copper net with the Au/AgCl particles loaded on the surface into a PFDT/ethanol solution with the concentration of 15mM for soaking for 6h, taking out and drying.

Fig. 2 and 3 are a surface photograph and SEM image of the copper mesh loaded with Au/CuCl particles and Au/AgCl particles, respectively. As can be seen, the fine particles are densely and uniformly distributed on the surface of the copper mesh, and the pores of the copper mesh are reduced to about 7um in FIG. 3.

Fig. 4 is a contact angle image of the prepared copper mesh. As can be seen from the figure, the contact angle of the copper mesh reaches 158 degrees, which shows that the copper mesh prepared in the embodiment has super-hydrophobicity and high oil-water separation efficiency.

Example 2: performing oil-water separation and dye detection on oil-water mixed solution containing methylene blue in water phase and Sudan red in oil phase

Referring to fig. 5, due to the super-hydrophobic and super-oleophilic property of the surface, Sudan iii molecules in the organic solvent penetrate through the copper mesh along with the organic solvent, oil-water separation is firstly performed, and a water phase containing methylene blue molecules is remained on the surface of the copper mesh to keep a droplet shape, and is finally concentrated in a precious metal hot zone with a small area along with volatilization of the droplet, so that interference of oil phase pollutants is finally eliminated, and only raman signals of the methylene blue molecules are remained.

And carrying out photodegradation on the water phase after oil-water separation on the oil-water mixed liquid containing methylene blue and Sudan red in the oil phase. Under the irradiation of a 300W xenon lamp as a visible light source, 10mL of methylene blue solution with the concentration of 10mg/L is obtained after oil-water separation through photodegradation. Referring to fig. 6, when the light source was irradiated for 3 minutes, the absorbance at 665nm was decreased by about 33% as compared with the original reaction solution, and the absorbance was almost decreased to zero after 12 minutes. This shows that the copper mesh prepared by the invention has strong visible light area photodegradation capability.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims

1. The preparation method of the multifunctional oil-water separation material is characterized by comprising the following steps:

s1, pretreating the copper mesh to remove impurities on the surface;

s3, soaking the copper net obtained in the step S2 in silver nitrate solution with the concentration of 0.005-0.2M for 1-2 hours to obtain the copper net with Au/AgCl particles loaded on the surface;

s4, soaking the copper mesh obtained in the step S3 in a PFDT/ethanol solution for 6-12 hours to obtain the multifunctional oil-water separation material.

2. The method for preparing the multifunctional oil-water separation material according to claim 1, wherein in step S1, the pretreatment specifically comprises: and ultrasonically cleaning the copper mesh by using dilute hydrochloric acid, acetone and water in sequence.

3. The method for preparing the multifunctional oil-water separating material according to claim 1, wherein the concentration of the chloroauric acid solution in step S2 is 0.01M.

4. The method for preparing the multifunctional oil-water separation material of claim 1, wherein the concentration of the PFDT/ethanol solution is 10-20 mM.

5. The multifunctional oil-water separation material prepared by the method of any one of claims 1 to 4.

6. The multifunctional oil-water separation material of claim 5, which is used for industrial oil-water separation.