阅读说明：本技术 一种黑磷纳米粒子-纳米铜相互掺杂的纳米复合物及其制备方法与应用 (Black phosphorus nanoparticle-nano copper mutually-doped nano composite and preparation method and application thereof ) 是由 张丹丹 施庆珊 刘惠铭 谢小保 王玲玲 刘亚敏 于 2019-09-10 设计创作，主要内容包括：本发明公开了一种黑磷纳米粒子/纳米铜相互掺杂的纳米复合物及其制备方法与应用。该制备方法包括以下步骤：通过超声剥离法制备超小尺寸的黑磷纳米粒子；将黑磷纳米粒子分散到五水硫酸铜或氯化铜和聚乙烯吡咯烷酮混合溶液中,于水浴锅中缓慢逐滴地加入还原剂并磁力搅拌反应2～4h后,离心洗涤制得黑磷纳米粒子/纳米铜相互掺杂的纳米复合物。本发明提供的方法首先通过铜离子和黑磷周边孤对电子的相互作用,使得铜离子均匀地分散到黑磷纳米粒子周围,然后在还原剂的作用下铜离子被还原原位生长为纳米铜,并在聚乙烯吡咯烷酮的保护下制得该纳米复合物。该纳米复合物中的纳米铜与高电子活性的黑磷纳米粒子结合,可实现协同增强的抗菌作用。(the invention discloses a black phosphorus nanoparticle/nano copper mutually doped nano composite and a preparation method and application thereof. The preparation method comprises the following steps: preparing ultra-small black phosphorus nanoparticles by an ultrasonic stripping method; dispersing the black phosphorus nanoparticles into copper sulfate pentahydrate or a mixed solution of copper chloride and polyvinylpyrrolidone, slowly dropwise adding a reducing agent into a water bath kettle, magnetically stirring for reaction for 2-4 h, and centrifugally washing to obtain the black phosphorus nanoparticle/nano copper mutually-doped nano composite. The method provided by the invention comprises the steps of firstly enabling copper ions to be uniformly dispersed around black phosphorus nanoparticles through the interaction of the copper ions and the arc pair electrons around the black phosphorus, then reducing the copper ions under the action of a reducing agent to grow into nano copper in situ, and preparing the nano composite under the protection of polyvinylpyrrolidone. The nano copper in the nano composite is combined with the black phosphorus nano particles with high electronic activity, so that the synergistically enhanced antibacterial effect can be realized.)

1. a preparation method of a black phosphorus nanoparticle/nano copper mutually doped nano composite is characterized in that the black phosphorus nanoparticle and the nano copper are mutually doped to prepare the nano composite.

2. the method of claim 1, comprising the steps of:

and uniformly mixing a copper sulfate pentahydrate solution or a copper chloride solution with polyvinylpyrrolidone, adding black phosphorus nanoparticles, uniformly mixing, putting the mixed solution into a water bath kettle at the temperature of 40-60 ℃, adding a sodium borohydride or hydrazine hydrate solution for reaction, centrifugally collecting precipitates, washing and drying to obtain the nano composite with the black phosphorus nanoparticles and the nano copper doped with each other.

3. The method of claim 2, comprising the steps of:

(1) Preparing black phosphorus nanoparticles:

S1: dispersing the black phosphorus crystals into an organic solvent, performing water bath ultrasonic treatment for 2-6 hours under the condition that the power is 80-100W, and then performing probe pulse ultrasonic treatment for 4-8 hours to obtain a mixed solution;

S2: centrifuging the mixed solution obtained in the step S1 at 4000-6000 rpm for 20-40 min, removing the precipitate, taking supernatant, centrifuging the supernatant at 10000-14000 rpm for 20-40 min, collecting the precipitate, washing the precipitate with deionized water, and freeze-drying to obtain black phosphorus nanoparticles;

(2) Preparing a black phosphorus nanoparticle/nano copper mutually doped nano composite:

and (2) dissolving copper sulfate pentahydrate or copper chloride and polyvinylpyrrolidone in deionized water simultaneously to obtain a solution A, adding the black phosphorus nanoparticles prepared in the step (1) into the solution A, carrying out ultrasonic mixing in a water bath at 40-60 ℃, then adding a sodium borohydride solution, carrying out constant-temperature stirring reaction for 2-4 h, centrifuging, collecting precipitates, washing the precipitates with deionized water, and freeze-drying to obtain the black phosphorus nanoparticle/nano copper mutually doped nano composite.

4. The method as claimed in claim 3, wherein the organic solvent is N-methylpyrrolidone.

5. the method for preparing the black phosphorus nanoparticle/nanocopper-doped nanocomposite according to claim 3, wherein the power of the probe pulse ultrasound in the step (1) is 300-600W, the pulse frequency is 2s on and 4s off, and when the probe pulse ultrasound is performed, the black phosphorus crystal dispersion liquid is placed in ice water, and ice is continuously added in the ultrasound process.

6. The method for preparing the black phosphorus nanoparticle/nanocopper-doped nanocomposite as claimed in claim 2 or 3, wherein the mass ratio of the polyvinylpyrrolidone to the copper sulfate pentahydrate or the copper chloride in the step (2) is 1:2 to 1: 5.

7. The method for preparing a black phosphorus nanoparticle/nanocopper-doped nanocomposite as claimed in claim 2 or 3, wherein the black phosphorus nanoparticle in the step (2) is added in an amount of 0.002 times the total weight of copper sulfate pentahydrate or copper chloride and polyvinylpyrrolidone.

8. The method for preparing black phosphorus nanoparticle/nanocopper intermingled nanocomposite as claimed in claim 2 or 3, wherein the concentration of the sodium borohydride solution in the step (2) is 0.5mol/L, and the addition amount thereof is one percent of the volume of the solution A.

9. A black phosphorus nanoparticle/nanocopper intermingled nanocomposite, characterized in that the nanocomposite is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the black phosphorus nanoparticle/nanocopper intermingled nanocomposite according to claim 9 for the preparation of bacteriostatic or bactericidal agents.

Technical Field

the invention relates to the technical field of nano materials, in particular to a black phosphorus nanoparticle/nano copper mutually doped nano composite and a preparation method and application thereof.

Background

The two-dimensional layered nano material has attracted particular attention due to its unique properties since its birth, and particularly, graphene and various composites using graphene as a substrate have wide application prospects, including sensing, tumor treatment, biological imaging, catalysis and other fields. In recent years, a new nano material, namely Black Phosphorus (BP), is considered to be a two-dimensional material with development potential higher than graphene, and the material is not in a regular planar structure, but each P atom is connected with three other P atoms to form a folded sheet, so that lone pair electrons of the material are exposed outside, the material has a high-activity property and can be used for charge transfer, the specific surface area is greatly increased, and the material has excellent biocompatibility, and degradation products are nontoxic substances such as phosphate and phosphate. Therefore, BP has a great research value in the aspects of biomedicine, diagnostic imaging and the like, and research results show a continuous rising trend, but research on the aspect of antibiosis is slightly weak, so that applying black phosphorus to antibacterial treatment still needs a continuous effort.

Silver or gold elements are most commonly used as the broad-spectrum antibacterial agents among inorganic antibacterial agents, but both silver ions and gold ions cause excessive accumulation of heavy metals in the body to damage health, and the use of silver or gold ions is not advocated at present. However, copper element does not have such a concern, and copper occupies an important position in trace elements of the human body and can be smoothly discharged along with metabolism. And the cost of gold and silver is relatively high, and in order to save the cost, the copper replaces gold and silver antibacterial products to become a popular trend. It is noted that the antibacterial effect of copper is slightly weak as compared with silver, and thus how to improve and enhance its antibacterial performance is of great importance.

Disclosure of Invention

The invention aims to provide a black phosphorus nanoparticle/nano copper mutually doped nano composite and a preparation method and application thereof. The nano composite has synergistic antibacterial effect between the black phosphorus nano particles and the nano copper, so that the antibacterial efficiency is obviously improved, and the nano composite can be used for preparing a bacteriostatic agent or a bactericide.

the technical scheme adopted by the invention is as follows:

A preparation method of a black phosphorus nanoparticle/nano copper doped nano composite is disclosed, which is a nano composite prepared by mutually doping black phosphorus nanoparticles and nano copper.

Preferably, the blue copperas solution or the copper chloride solution is mixed with the polyvinylpyrrolidone uniformly, then the black phosphorus nanoparticles are added and mixed uniformly, the mixed solution is put into a water bath kettle at the temperature of 40-60 ℃, sodium borohydride or hydrazine hydrate solution is added for reaction, the precipitate is collected by centrifugation, and the nano-composite with the black phosphorus nanoparticles and the nano-copper doped mutually is obtained after washing and drying.

Further preferably, the method comprises the following steps:

(1) Preparing black phosphorus nanoparticles:

S1: dispersing the black phosphorus crystals into an organic solvent, performing water bath ultrasound for 2-6 hours under the condition that the power is 80-100W, and then performing probe pulse ultrasound with the power of 300-600W, the pulse frequency of 2s on and 4s off and the duration of 4-8 hours to obtain a mixed solution;

S2: centrifuging the mixed solution obtained in the step S1 at 4000-6000 rpm for 20-40 min, removing the precipitate, taking supernatant, centrifuging the supernatant at 10000-14000 rpm for 20-40 min, collecting the precipitate, washing the precipitate with deionized water, and freeze-drying to obtain black phosphorus nanoparticles;

(2) preparing a black phosphorus nanoparticle/nano copper mutually doped nano composite:

And (2) simultaneously dissolving copper sulfate pentahydrate or copper chloride and polyvinylpyrrolidone in deionized water to obtain a solution A, adding the black phosphorus nanoparticles prepared in the step (1) into the solution A, carrying out ultrasonic mixing in a water bath at 40-60 ℃, then slowly dropwise adding a sodium borohydride solution, carrying out stirring reaction at a constant temperature for 2-4 h, centrifugally collecting precipitates, washing the precipitates with deionized water, and freeze-drying to obtain the black phosphorus nanoparticle/nano copper mutually doped nano composite.

preferably, the organic solvent in the step (1) is N-methylpyrrolidone.

Preferably, the particle size of the black phosphorus nanoparticles prepared in the step (1) is 5-20 nm.

Preferably, when the probe pulse ultrasound is performed in the step (1), the black phosphorus crystal dispersion liquid is placed in ice water, and during the ultrasound process, the ice is continuously added to prevent the dispersion liquid from being overheated, so as to promote the excessive oxidation of the black phosphorus.

Preferably, the mass ratio of the polyvinylpyrrolidone to the copper sulfate pentahydrate or the copper chloride in the step (2) is 1: 2-1: 5.

preferably, the addition amount of the black phosphorus nanoparticles in the step (2) is 0.002 times of the total weight of the copper sulfate pentahydrate or the copper chloride and the polyvinylpyrrolidone.

Preferably, the concentration of the sodium borohydride solution in the step (2) is 0.5mol/L, the solvent is deionized water, and the addition amount is one percent of the volume of the solution A.

in the step (2), the uniformly dispersed copper ions grow into nano-copper in situ around the black phosphorus nanoparticles under the action of a reducing agent sodium borohydride, and under the protection of polyvinylpyrrolidone, a nano-composite in which the black phosphorus nanoparticles and the nano-copper are doped with each other is formed.

In order to prepare black phosphorus nanoparticles as small as possible, in step (1), black phosphorus crystals are added into an organic solvent N-methyl pyrrolidone in a mode of assisting stripping of the black phosphorus crystals by water bath ultrasound and probe ultrasound together, and probe pulse ultrasound is carried out for 4-8 hours after 2-6 hours of water bath ultrasound, wherein the water bath ultrasound power is 80-100W, the probe ultrasound power is 300-600W, and the pulse frequency is 2s for on and 4s for off. And during later probe supersound, will put black phosphorus crystal dispersion liquid in ice water, the supersound in-process is paid attention to and is continuously added ice, prevents that the dispersion liquid from overheated, promotes black phosphorus excessive oxidation. And finally, carrying out low-speed centrifugation at the rotating speed of 4000-6000 rpm to remove large sediment particles, and carrying out high-speed centrifugation on the supernatant at the rotating speed of 10000-14000 rpm to collect sediment so as to obtain the ultra-small black phosphorus nanoparticles.

The specific operation in the step (2) is that polyvinylpyrrolidone and copper sulfate pentahydrate or copper chloride are added into deionized water according to the mass ratio of 1: 2-1: 5 and are uniformly mixed, and the purpose of polyvinylpyrrolidone is to protect nano copper and prevent nano copper from being rapidly oxidized. And then adding black phosphorus nanoparticles, performing ultrasonic mixing uniformly, enabling copper ions to be uniformly dispersed around the black phosphorus nanoparticles through the interaction of the metal cation copper ions and lone pair electrons around the black phosphorus, then putting the black phosphorus nanoparticles into a water bath, slowly and dropwise adding a sodium borohydride solution, and performing magnetic stirring reaction for 2-4 hours. For the generation of the nano copper, only the reducibility of the black phosphorus is relied on, the strength is relatively weak, and a proper amount of sodium borohydride solution is added, and the strong reducibility of the sodium borohydride solution is beneficial to the rapid growth of the nano copper. Under the action of reducing agent sodium borohydride, copper ions distributed around the black phosphorus are quickly reduced and grow into nano copper in situ, and are protected by polyvinylpyrrolidone, so that the nano composite with black phosphorus nanoparticles and nano copper doped with each other is prepared.

The invention also claims the black phosphorus nano particle/nano copper mutually doped nano composite prepared by the preparation method.

According to the technical scheme, the ultra-small black phosphorus nanoparticles and the nano copper are doped and compounded with each other, so that the antibacterial efficiency can be greatly improved through a synergistic effect, and on one hand, the nano copper can destroy a bacterial structure by generating active oxygen to achieve the aim of sterilization; on the other hand, in the nano composite, the black phosphorus nanoparticles are small in size, relatively active in physicochemical property and good in surrounding electron mobility, the yield of active oxygen can be improved through an electron transfer effect, and the sterilization effect of the two synergistic effects is more obvious. The black phosphorus nanoparticle/nano copper mutually doped nano composite can be used for preparing bacteriostatic agents or bactericides.

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

The preparation method provided by the invention is simple to operate, mild in condition and low in cost; the prepared nano composite effectively combines black phosphorus nano particles and nano copper, and can play a synergistic antibacterial role; the nano-composite degradation products can be discharged out of the body through metabolism, the biological safety is very high, and the application prospect is very wide.

Drawings

FIG. 1 is a schematic flow chart of the present invention for preparing a black phosphorus nanoparticle/nano copper doped nano composite.

FIG. 2 is a transmission electron microscope scanning image of the black phosphorus nanoparticles (left side view) and the black phosphorus nanoparticles/nano-copper doped nano-composites (right side view) prepared by the present invention.

Fig. 3 is a statistical chart of the antibacterial effect of the black phosphorus nanoparticle/nano copper co-doped nano composite and the nano copper prepared by the invention by a flow cytometer, BP/Cu: black phosphorus nanoparticle/nano copper mutual doping nano composite, Cu: nano copper, BP: black phosphorus nanoparticles, PBS: PBS solution.

Detailed Description

The following examples are further illustrative of the present invention and are not intended to be limiting thereof.

The following examples illustrate the process for preparing black phosphorus nanoparticle/nanocopper intermingled nanocomposites in the figure 1.