阅读说明：本技术 抗菌氢氧化铜纳米线膜及其制备方法及其二次利用方法 (Antibacterial copper hydroxide nanowire film, preparation method and secondary utilization method thereof ) 是由 孙金全 赫庆坤 时垌 司晋伟 王东瑞 谢鲲 魏娜 于 2020-05-09 设计创作，主要内容包括：本发明涉及一种抗菌Cu(OH)<Sub>2</Sub>纳米线膜的制备方法,其特征在于通过直接沉淀法制备了一种超长的Cu(OH)<Sub>2</Sub>纳米线。用Cu(OH)<Sub>2</Sub>纳米线溶液制备Cu(OH)<Sub>2</Sub>纳米线膜。通过调节反应温度和反应物浓度,控制Cu(OH)<Sub>2</Sub>纳米线的直径尺寸,进而控制Cu(OH)<Sub>2</Sub>纳米线膜的孔径大小,可以获得纳滤膜、超滤膜。Cu(OH)<Sub>2</Sub>纳米线膜具层层膜叠加的结构,实现对滤液的多层过滤,其在自来水净化后优于国家直饮水的标准,也可以实现印染污水的处理。同时,Cu(OH)<Sub>2</Sub>纳米线膜对金黄色葡萄球菌和大肠杆菌具有杀菌性抑菌性能,杀菌率达到95％以上,可以有效地防止了膜的生物污染和过滤介质的二次污染,提高膜的使用寿命和净化水水质。此外,失效的Cu(OH)<Sub>2</Sub>纳米线膜可以通过超声重组的方法重新制备新的Cu(OH)<Sub>2</Sub>纳米线膜,实现膜材料的可持续利用。(The invention relates to an antibacterial Cu (OH) 2 The preparation method of the nanowire film is characterized in that the method prepares the overlong Cu (OH) through a direct precipitation method 2 A nanowire. With Cu (OH) 2 Nanowire solution preparation Cu (OH) 2 A nanowire film. Controlling Cu (OH) by adjusting reaction temperature and reactant concentration 2 Diameter size of the nanowires, in turn controlling Cu (OH) 2 The pore size of the nanowire film can obtain a nanofiltration membrane and a super-filtration membraneAnd (5) filtering the membrane. Cu (OH) 2 The structure of the superposition of the layers and the films of the nanowire film realizes the multi-layer filtration of the filtrate, which is superior to the national direct drinking water standard after the tap water is purified and can also realize the treatment of the printing and dyeing sewage. Meanwhile, Cu (OH) 2 The nano-wire membrane has bactericidal and bacteriostatic properties on staphylococcus aureus and escherichia coli, the bactericidal rate reaches more than 95%, biological pollution of the membrane and secondary pollution of a filter medium can be effectively prevented, the service life of the membrane is prolonged, and the water quality of purified water is improved. In addition, failed Cu (OH) 2 The nanowire film can be used for preparing new Cu (OH) through an ultrasonic recombination method 2 The nanowire film realizes sustainable utilization of the film material.)

1. The preparation method of the antibacterial copper hydroxide nanowire film is characterized by comprising the following steps of:

step one, 2-3g of CuSO₄·5H₂O was added to 100-120ml of distilled water and stirred until completely dissolved.

Step two, quickly adding ammonia water solution with the volume of 50-70ml and the concentration of 0.2-0.3mol/L into the CuSO obtained in the step one at the constant reaction temperature a (a is more than or equal to 20 ℃ and less than or equal to 50 ℃), wherein the volume of the ammonia water solution is 50-70ml₄Stirring the solution until the reaction is completed, and taking the generated cuprammonium solution as generated Cu (OH)₂A precursor of the nanowire;

step three, continuously dripping NaOH solution with the volume of 20-30ml and the concentration of 1.0-1.2mol/L into the copper ammonia solution prepared in the step two at the constant reaction temperature a, stirring the solution after the dripping of the NaOH solution is finished, and completely reacting to prepare the overlong Cu (OH)₂A nanowire suspension;

step four, the Cu (OH) prepared in the step three₂Removing water from the nanowire suspension, washing, and completely drying to obtain Cu (OH)₂A nanowire film.

2. The method of claim 1, wherein the removing water in step four is the step of removing Cu (OH) produced in step three₂And (4) carrying out vacuum filtration on the nanowire suspension, wherein the drying in the step four is drying in a drying oven at the temperature of 30-40 ℃ for 1-2 h.

3. The method of claim 1, wherein the dropping of the NaOH solution is at a rate of 2-5 ml/min.

4. An antibacterial oxyhydrogen according to claim 1The preparation method of the copper-removing nanowire film is characterized in that the water removal component in the step four is Cu (OH) prepared in the step three₂Removing water from the nanowire suspension by using a spraying method or a coating method; the spraying method comprises the steps of mixing the Cu (OH) prepared in the step three₂The nanowire suspension is loaded into a spray gun, uniformly sprayed on the non-woven fabric, and after drying, Cu (OH) can be separated from the non-woven fabric₂A nanowire film; the coating method comprises the steps of directly adding Cu (OH)₂Coating the suspension on a non-woven fabric, and drying to obtain Cu (OH)₂A nanowire film.

5. The method for preparing an antibacterial copper hydroxide nanowire film as claimed in claim 1, wherein the PH of the solution is between 12 and 13 after the addition of the NaOH solution in step three.

6. The method of claim 2, wherein the Cu (OH) produced in step three is filtered in step four₂And placing an inorganic filter membrane in the nanowire suspension to obtain the modified copper hydroxide nanowire membrane of the existing inorganic filter membrane.

7. An antibacterial copper hydroxide nanowire film, characterized in that it is prepared by the method of claims 1-6.

8. The antimicrobial copper hydroxide nanowire film of claim 7, wherein the film comprises Cu (OH)₂The length of the nano-wire is more than 30 μm, and the diameter is between 20 nm and 500 nm.

9. The secondary utilization method of the antibacterial copper hydroxide nanowire film is characterized in that the antibacterial copper hydroxide nanowire film is Cu (OH)₂The nanowire film is a copper hydroxide nanowire film prepared by the method of claims 1-6, and is realized by the following steps:

step one, using the used Cu (OH)₂The nanowire film was placed in a beaker with distilled water, placed in an ultrasonic washer for sonication, Cu (OH)₂The nanowire film can be dispersed again under the action of ultrasound to form Cu (OH)₂A nanowire suspension;

step two, the Cu (OH) prepared in the step one₂Nanowire suspension preparation Cu (OH)₂Removing water from the nanowire film, washing to remove impurity ions, and drying to obtain Cu (OH) capable of being recycled₂A nanowire film.

10. The method of claim 9, wherein the copper hydroxide nanowire film is Cu (OH)₂And (3) carrying out ultrasonic treatment on the nanowire film in an ultrasonic washing instrument for more than 30 min.

Technical Field

The invention relates to the technical field of membrane filtration and separation, in particular to an antibacterial copper hydroxide nanowire membrane, a preparation method and a secondary utilization method thereof.

Background

In recent years, with the rapid development of industry, water resource pollution and secondary pollution become more serious, and the common filter medium is difficult to realize the purification treatment of drinking water in life. The nanofiltration and ultrafiltration membrane purification technology adopts a high-precision pure physical filtration principle, does not add any chemical substance, and screens by virtue of micropores densely distributed on the surface of the membrane to retain harmful substances, thereby realizing the effects of filtration, purification and purification. In the area with light water pollution, the water produced by the ultrafiltration water purifier can be used as drinking water. If the pollution is serious, the water produced by the nanofiltration and RO reverse osmosis water purifier can be used as drinking water and is more and more widely applied. The ultrafiltration membrane has strong filtering and purifying treatment effects, is mainly used for intercepting harmful substances in water, simultaneously keeps the pH value of produced water unchanged, but is difficult to intercept harmful heavy metals due to the limited pore size. At present, RO reverse osmosis membranes occupy a leading position in the water purification market, but the wastewater rate is high, and the contradiction between supply and demand caused by shortage of city drinking water is further aggravated. In addition, beneficial mineral elements in the pure water treated by the RO reverse osmosis membrane are all intercepted, which is not beneficial to the drinking health of people. Meanwhile, the price of the RO reverse osmosis membrane is higher, and the daily use cost is increased. With the development of nanotechnology, nanofiltration membrane technology is becoming mature day by day and begins to be applied to the field of membrane water purification, but at present, based on organic nanofiltration membrane materials, the research reports of fresh and inorganic nanofiltration membranes in the field of water purification are reported.

When the filtration membrane is used for purifying or treating filtered wastewater, the filtration membrane is easy to lose permeability due to accumulation of impurities on a membrane matrix or inside the membrane, namely membrane pollution such as particle scaling, organic scaling and the like, which limits the performance and service life of the membrane and causes secondary pollution of purified water and the like. The polluted membrane has large resistance, small flux and low separation performance in the water treatment process, and frequent cleaning not only improves the treatment cost, but also causes secondary pollution to the environment. On the other hand, most of the currently used membranes have no antibacterial or bactericidal capability, and the micropores of the membranes are also easily blocked by microorganisms in the using process, so that the membranes are degraded or decomposed, and the using efficiency of the membranes is seriously affected. The membrane is extremely easy to be damaged by microorganisms in water during storage and equipment outage, and the service life of the membrane is seriously influenced. Some films are sterilized by adding nano silver or ultraviolet irradiation, and have certain effect.

Patent CN106390777A relates to a copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane and a preparation method thereof, and compared with a pure polyvinylidene fluoride ultrafiltration membrane, the prepared copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane has the advantages of enhanced hydrophilicity, remarkably improved water flux and improved anti-pollution performance. But the production cost for preparing the copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane is high, the time consumption in the process of drying and removing the residual solvent in the production is too long, and the product competitiveness is reduced. In addition, the polymer film is easy to age under the action of chloride ions, and the service life is shortened.

Patent CN109277003A relates to a graphene ultrafiltration membrane and a preparation method thereof. Linear water flow channels are formed among the graphene ultrafiltration membrane diaphragm layers, so that the retention rate of the graphene membrane is increased, organic pollutants can be effectively retained, and higher water flux can be obtained. But the preparation process is too complex, the production cost is higher, and the antibacterial performance is limited.

Patent CN107715699A relates to a preparation method of a polyetherimide photocatalytic ultrafiltration membrane with a titanium dioxide nanowire loaded on the surface. The titanium dioxide nanowires are grown on the surface of the PEI membrane through a low-temperature crystallization technology, so that the hydrophilicity of the membrane is improved, the high rejection rate is kept, the flux of the membrane is improved, and the membrane can be applied to the fields of photocatalytic pollution treatment and the like. However, the membrane has larger pore diameter, a plurality of small particle substances can not be intercepted, and the membrane has no sterilization performance, is easy to cause biological pollution and reduces the service life.

KR20040074362 relates to a method for preparing antibacterial ultrafiltration and microfiltration hollow fiber membrane by phase inversion method. It features that inorganic or organic antiseptic is added into the filming liquid to kill various microbes. Although the antibacterial ultrafiltration membrane and the microfiltration membrane have good antibacterial effect, most of the organic antibacterial agents can be dissolved in a solvent in a membrane casting solution and have low solubility in water, so that the organic antibacterial agents can be concentrated on the surface of the membrane due to the phase transfer effect when in contact with the membrane during solidification, and the antibacterial agents are easily washed away by water to gradually lose antibacterial effect due to no chemical effect between the antibacterial agents and high molecules, so that the lasting antibacterial effect cannot be achieved.

Disclosure of Invention

The invention aims to solve the technical problems and provides a preparation method of an antibacterial copper hydroxide nanowire film, which has the advantages of simple production process, low cost, recyclable materials, lasting effect, controllable membrane aperture size and membrane thickness and membrane aperture series, a low cost, antibacterial capability, good hydrophilicity and good mechanical strength, and a secondary utilization method of the antibacterial copper hydroxide nanowire film, which is simple to operate.

The first purpose of the invention is to provide a preparation method of an antibacterial copper hydroxide nanowire film, which is realized by the following steps:

step one, 2-3g of CuSO₄·5H₂O was added to 100-120ml of distilled water and stirred until completely dissolved.

Step two, under the constant reaction temperature a (a is more than or equal to 20 ℃ and less than or equal to 50 ℃), quickly adding ammonia water (50-70ml, 0.2-0.3mol/L) solution into the CuSO₄Stirring the solution until the reaction is completed, and taking the generated cuprammonium solution as generated Cu (OH)₂A precursor of the nanowire;

step three, continuously dripping NaOH (20-30ml, 1.0-1.2mol/L) solution into the cuprammonia solution prepared in the step two at the constant reaction temperature a at the speed of 2-5ml/min, stirring the solution after the dripping of NaOH is finished, and completely reacting to prepare the overlong Cu (OH)₂A nanowire suspension;

step four, the Cu (OH) prepared in the step three₂Removing water from the nanowire suspension, washing to remove impurity ions, and completely drying to obtain Cu (OH)₂A nanowire film.

Another object of the present invention is to obtain a copper hydroxide nanowire film prepared by the above method.

Another objective of the present invention is to provide a secondary utilization method of the copper hydroxide nanowire film, which is implemented by the following steps:

step one, using the used Cu (OH)₂The nanowire film was placed in a beaker with distilled water, placed in an ultrasonic washer for sonication, Cu (OH)₂The nanowire film can be dispersed again under the action of ultrasound to form Cu (OH)₂A nanowire suspension;

step two, the Cu (OH) prepared in the step one₂Removing water from the nanowire suspension, washing, and drying to obtain reusable Cu (OH)₂The nanowire film realizes the secondary utilization of the film material.

Compared with the prior art, the invention has the beneficial effects that:

the film forming method is simple and convenient, and the production process is simple, controllable and environment-friendly;

secondly, the pore size and the thickness of the copper hydroxide nanowire membrane can be regulated and controlled by regulating the reaction temperature, so that the pore size serialization of the membrane is realized;

the production cost of the membrane material is low, and the membrane material is convenient to popularize and apply;

fourthly, the prepared copper hydroxide nanowire film is of a multi-layer assembled film structure, the thickness of each layer is 300-500nm, and layer-by-layer filtration can be realized;

the prepared copper hydroxide nanowire film has lasting sterilization and bacteriostasis performance, and secondary pollution of purified water is prevented;

sixthly, the prepared copper hydroxide nanowire film has strong sterilization performance on staphylococcus aureus and escherichia coli, and the sterilization rate can reach more than 95%;

the prepared copper hydroxide nanowire films with different apertures can selectively separate methylene blue or methyl blue, so that the treatment of the printing and dyeing sewage is realized

The prepared copper hydroxide nanowire film has high integrity and can not have the defects of cracks, pinholes and the like in the preparation process

⑨ the copper hydroxide nanowire film has strong hydrophilicity, and the water flux is 50-200Lh under the water pressure of 0.1MPa^-1m^-2The mechanical strength is high, and the hydraulic pump can still work normally under the water pressure of 60 MPa;

performing ultrasonic treatment on the copper hydroxide nanowire membrane with failure in the R (chloride) in distilled water to obtain slurry, and preparing a new copper hydroxide nanowire membrane by using a spraying method, a coating method or vacuum filtration to realize secondary utilization of the membrane material.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creating any labor.

FIG. 1(a) shows Cu (OH)₂A coordination assembly mechanism diagram of the nanowire;

FIG. 1(b) shows a multilayer Cu (OH)₂A mechanism diagram of nanowire film formation;

FIG. 1(c) shows Cu (OH)₂Preparing a nanowire film;

FIG. 2(a) shows Cu (OH)₂Macroscopic pictures of nanowire films;

FIG. 2(b) shows Cu (OH)₂Macroscopic pictures of nanowire films;

FIG. 2(c) shows Cu (OH) prepared as described in example 5₂Macroscopic pictures of inorganic ceramic filter elements;

FIG. 3(a) is Cu (OH) prepared at 25 ℃ as described in example 1₂Scanning electron microscope picture of 5 μm resolution on the surface of the nanowire film;

FIG. 3(b) is Cu (OH) prepared at 25 ℃ as described in example 1₂Scanning electron microscope picture of 500nm resolution ratio of the surface of the nanowire film;

FIG. 3(c) is Cu (OH) prepared at 30 ℃ as described in example 2₂Scanning electron microscope picture of 5 μm resolution on the surface of the nanowire film;

FIG. 3(d) is Cu (OH) prepared at 30 ℃ as described in example 2₂Scanning electron microscope picture of 500nm resolution ratio of the surface of the nanowire film;

FIG. 3(e) Cu (OH) prepared at 35 ℃ as described in example 3₂Scanning electron microscope picture of 5 μm resolution on the surface of the nanowire film;

FIG. 3(f) is Cu (OH) prepared at 35 ℃ as described in example 3₂Scanning electron microscope picture of 500nm resolution ratio of the surface of the nanowire film;

FIG. 4(a) is Cu (OH) prepared at 25 ℃ as described in example 1₂Scanning electron microscope picture of 5 μm resolution of nanowire film cross section;

FIG. 4(b) Cu (OH) prepared at 30 ℃ as described in example 2₂Scanning electron microscope picture of 3 μm resolution of nanowire film cross section;

FIG. 4(c) is Cu (OH) prepared at 35 ℃ as described in example 3₂Scanning electron microscope picture of 2 μm resolution of nanowire film cross section;

FIG. 4(d) Cu (OH) prepared at 35 ℃ as described in example 3₂Scanning electron microscope picture of 3 μm resolution of nanowire film cross section;

FIG. 5 shows Cu (OH) produced at different temperatures as described in examples 1-3₂X-ray diffraction patterns of the nanowire films.

FIG. 6(a) Cu (OH) prepared for 25 ℃ as described in example 1₂Scanning the atomic force microscope appearance of the nanowire;

FIG. 6(b) Cu (OH) prepared at 25 ℃ as described in example 1₂Atomic force microscopy force profile spectra of nanowires;

FIG. 6(c) is Cu (OH) prepared at 30 ℃ as described in example 2₂Scanning the atomic force microscope appearance of the nanowire;

FIG. 6(d) Cu (OH) prepared at 30 ℃ as described in example 2₂Atomic force microscopy force profile spectra of nanowires;

FIG. 6(e) Cu (OH) prepared at 35 ℃ as described in example 3₂Scanning the atomic force microscope appearance of the nanowire;

FIG. 6(f) Cu (OH) prepared at 35 ℃ as described in example 3₂Atomic force microscopy force profile spectra of nanowires;

FIG. 7 shows Cu (OH)₂A comparison graph of the bactericidal performance of the nanowire membrane on staphylococcus aureus;

FIG. 8 shows Cu (OH)₂A comparison graph of the bactericidal performance of the nanowire membrane on escherichia coli;

FIG. 9 shows Cu (OH) produced at different temperatures as described in examples 1-3₂Ultraviolet-visible spectra of the nanowire film before and after filtering of the methyl blue;

FIG. 10 shows Cu (OH) produced at different temperatures as described in examples 1-3₂Ultraviolet-visible spectra of the nanowire film before and after the filtering of methylene blue;

FIG. 11(a) is an ultrasonic recombinant Cu (OH) described in example 4₂Scanning electron microscope pictures of 5 μm resolution of the nanowire films;

FIG. 11(b) is the ultrasonic recombination of Cu (OH) described in example 4₂Scanning electron microscope pictures of 1 μm resolution of the nanowire films;

FIG. 12(a) is Cu (OH) produced by the spray coating method described in example 6₂Scanning electron microscope pictures of 3 μm resolution of the nanowire films;

FIG. 12(b) shows Cu (OH) prepared by the spray coating method described in example 6₂Scanning electron microscopy of 500nm resolution of nanowire films.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following detailed description and accompanying drawings. The exemplary embodiments and descriptions of the present invention are provided to explain the present invention, but not to limit the present invention.