CN111226985B - Ni/Ni3S2Nano antibacterial agent and preparation method thereof - Google Patents
Ni/Ni3S2Nano antibacterial agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to Ni/Ni3S2A nano antibacterial agent and a preparation method thereof. Uniformly mixing nickel nitrate, sodium hydroxide, oleic acid, deionized water and ethanol, and preparing a Ni/NiO composite material through microwave reaction and roasting; the prepared Ni/NiO is subjected to microwave vulcanization treatment again to obtain Ni/Ni3S2A composite material. Ni/Ni prepared by the invention3S2The nanoparticles have good antibacterial property to Escherichia coli, and can be used as antibacterial agent for Escherichia coli. The preparation method is simple, low in cost and has potential application prospect.
Description
Technical Field
The invention relates to high-efficiency Ni/Ni3S2A nano antibacterial agent and a preparation method thereof, belonging to the technical field of nano antibacterial materials.
Background
In recent years, transition metal sulfides such as Ni3S2、MoS2、Co8S9Etc. open the forefront of potential electrode materials because they have different stoichiometric compositions, crystal structures, valence states, and morphologies. Compared with corresponding oxides, the transition metal sulfide has richer oxidation-reduction reactions, higher conductivity and more satisfactory mechanical and thermal stability. Of these transition metal sulfides, nickel sulfides have many different phases, such as NiS, Ni3S2、Ni3S4、Ni7S6And Ni9S8It has been widely studied for its excellent redox reversibility, safety, low cost and good mechanical stability. In particular Ni3S2Has the advantages of high theoretical specific capacitance, low cost, simple preparation and the like, and is concerned. Ni3S2Having a continuous Ni-Ni bond network throughout its structure with inherent metallic properties, the resulting high conductivity greatly facilitates the transport of ions and electrons, and thus Ni3S2Are often used to make electrode materials.
The research finds that when Ni3S2And metal M (M ═ Ni, Co, Au) to form M/Ni3S2The composite material can show unique electrochemical property and catalytic property, thereby arousing great research enthusiasm of scientific researchers.
Patent CN 106531477a discloses a preparation method of a nickel/cobalt doped trinickel disulfide energy storage electrode material. Mixing a nickel nanowire film serving as a base material with a thioacetamide solution, carrying out hydrothermal reaction at 130-200 ℃ for 1-24 h, and cleaning to obtain a nickel/nickel disulfide nanowire; carrying out hydrothermal reaction on the nickel/nickel disulfide nanowires, a cobalt salt solution and a mixed solution of ethylenediamine and ethylene glycol at 120-220 ℃ for 0.5-12 h, and washing with deionized water and ethanol to obtain the nickel/cobalt doped nickel disulfide electrode material. The electrode material has large volume ratio capacitance value and good rate performance.
Patent CN 110026566A discloses Au @ Ni of single crystal shell layer3S2Nanoparticles with a core-shell structure and a preparation method thereof. The method comprises the following specific steps: taking a mixed solution of oleylamine and nickel acetylacetonate as a raw material, adding a chloroauric acid toluene solution, and reacting at the temperature of 95-110 ℃ for at least 10min under the condition of argon protective gas to obtain an oleylamine solution of nickel acetylacetonate containing Au nanoparticles; adding 1-dodecanethiol into the mixed solution, reacting at 170-180 ℃ for at least 2h, centrifuging, and ultrasonically cleaning to obtain Au @ Ni3S2Nanoparticles of core-shell structure. The nano particles are face-centered cubic phase Au core and rhombohedral phase Ni3S2A shell layer, wherein, Au @ Ni3S2The diameter of the core-shell structure nano-particles is 15-30 nm, the diameter of the Au core is 5-10 nm, and the hydrogen evolution catalytic performance is excellent.
Juan Jian et al foam nickel (Sn-Ni)3S2Preparation of tin (Sn) -doped Ni on NF) by simple hydrothermal process3S2Nanosheets. The method comprises the following specific steps: a1 cm X9 cm piece of NF (nickel foam) was placed in 50mL of a reaction solution (1.0mmol of H)2NCSNH2,0.15mmol Na2SnO3·3H2O,50mL deionized water) was placed in a stainless steel autoclave at 220 cIs kept in the oven for 5 hours. When the autoclave is naturally cooled to about 25 ℃, a black foam nickel-based product is obtained, deionized water and ethanol are used for washing in sequence, and the black foam nickel-based product is dried for 12 hours at the temperature of 60 ℃, so that the tremella Sn-Ni is synthesized3S2and/NF. Sn-Ni prepared by the method3S2the/NF is an excellent water decomposition electrocatalyst. See ACS appl. mater. interfaces 2018,10, 40568-.
At present, M/Ni3S2The composite material is mainly used as an electrode material and a catalyst. Due to Ni3S2Has the advantages of environmental protection, low price, abundant reserves and the like, so that the development of M/Ni3S2The antimicrobial use of composite materials remains an important research topic for chemists.
Since nickel ions are easy to combine with amino acids in bacterial proteins to cause cytoplasm shrinkage, which leads to loss of replication function and bacterial apoptosis, a simple method for preparing Ni/Ni was sought3S2The composite material and the discussion of the bacteriostatic property thereof are fields to be developed at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Ni/Ni for an antibacterial agent3S2Composite materials and methods for making the same. The invention adopts Ni/Ni synthesized by twice microwave method3S2The nano-particles have good bacteriostatic property on the surface of escherichia coli. Can be used as antibacterial agent for Escherichia coli.
The technical scheme of the invention is as follows:
Ni/Ni3S2The nano antibacterial agent is Ni/Ni with rough surface3S2The average particle size of the nanoparticles is 30-45 nm.
According to the invention, the diameter of the inhibition zone of the antibacterial agent to escherichia coli is preferably 18-22 mm.
According to the invention, the above-mentioned Ni/Ni3S2The preparation method of the nano antibacterial agent comprises the following steps:
(1) taking oleic acid as a dispersing agent, adding nickel nitrate, sodium hydroxide, deionized water and ethanol, uniformly mixing, and carrying out microwave reaction; washing and drying the precipitate, and roasting at 450-550 ℃ for 2-3 h to obtain Ni/NiO nano particles;
(2) adding the Ni/NiO particles into sodium sulfide and deionized water, uniformly mixing, and carrying out microwave reaction; washing and drying the precipitate to obtain Ni/Ni3S2A nano antibacterial agent.
According to the invention, the Ni/NiO in the step (1) is nano-particles, and the average particle size is 20-40 nm. More preferably, the average particle diameter of the Ni/NiO nanoparticles is 30 nm.
According to the invention, the nickel nitrate in the step (1) is nickel nitrate hexahydrate.
According to the invention, the molar ratio of the volume of the oleic acid to the volume of the nickel nitrate in the step (1) is 6-8 mL: 1mmol of the active component; the molar ratio of the nickel nitrate to the sodium hydroxide is 1: 2.5-3.5; the molar ratio of the volume of the added deionized water to the volume of the nickel nitrate is 40-50 mL: 1mmol of the active component; the molar ratio of the volume of the added ethanol to the volume of the nickel nitrate is 6-8 mL: 1 mmol. Further preferably, the molar ratio of the volume of oleic acid to the volume of nickel nitrate is 7 mL: 1mmol of the active component; the molar ratio of nickel nitrate to sodium hydroxide is 1: 3; adding deionized water, wherein the molar ratio of the volume of the added deionized water to the nickel nitrate is 45 mL: 1mmol of the active component; the molar ratio of the volume of the added ethanol to the nickel nitrate is 7 mL: 1 mmol.
Preferably, the microwave reaction in the step (1) is carried out for 1-2 hours; more preferably, the power of the microwave reaction is 500W, and the reaction time is 1.5 h.
Preferably, the precipitate in the step (1) is washed with 95% ethanol for 5-7 times; further preferably, the precipitate is washed 6 times with 95% ethanol.
According to the invention, the drying condition in the step (1) is preferably drying for 24 hours at 80-90 ℃; more preferably, the drying condition is drying at 85 ℃ for 24 h.
According to the invention, the roasting condition in the step (1) is preferably roasting for 2-3 h in a muffle furnace at 450-550 ℃; more preferably, the roasting condition is roasting in a muffle furnace at 500 ℃ for 2.5 hours.
According to the invention, the sodium sulfide in the step (2) is preferably sodium sulfide nonahydrate.
Preferably, in the step (2), the mass ratio of the Ni/NiO to the sodium sulfide is 1: 3-4, and the mass ratio of the volume of the added deionized water to the mass ratio of the Ni/NiO is 40-50 mL: 0.1-0.2 g; more preferably, the mass ratio of the Ni/NiO to the sodium sulfide is 1: 3.5; the mass ratio of the volume of the added deionized water to the Ni/NiO is 45 mL: 0.1 to 0.2 g.
According to the invention, the mode of uniformly mixing in the step (2) is ultrasonic dispersion, and the ultrasonic dispersion time is 1-2 h; further preferably, the ultrasonic dispersion time is 1.5 h.
Preferably, the microwave reaction in the step (2) is carried out for 2-3 h; more preferably, the power of the microwave reaction is 500W, and the reaction time is 2.5 h.
Preferably, the precipitate in the step (2) is washed 3-5 times by using 95% ethanol; further preferably, the washing is performed 4 times with 95% ethanol.
According to the invention, the drying condition in the step (2) is preferably drying for 24 hours at 80-90 ℃; more preferably, the drying condition is drying at 85 ℃ for 24 h.
According to the invention, the Ni/Ni ratio in step (2) is preferably selected3S2The nano antibacterial agent is Ni/Ni3S2Nanoparticles having an average particle diameter of 30 to 45 nm; more preferably, the average particle diameter is 35 nm.
According to the invention, the Ni/Ni3S2The preparation method of the nano antibacterial agent, a preferred embodiment, comprises the following steps:
(1) weighing 6-8mL of oleic acid in a beaker, sequentially adding nickel nitrate, sodium hydroxide, deionized water and ethanol in batches, fully stirring uniformly, transferring to a microwave instrument, and reacting for 1-2 h; the molar ratio of the volume of the oleic acid to the volume of the nickel nitrate is 6-8 mL: 1mmol, wherein the molar ratio of nickel nitrate to sodium hydroxide is 1: 2.5-3.5, and the molar ratio of the volume of deionized water to the volume of nickel nitrate is 40-50 mL: 1mmol, the molar ratio of the volume of the added ethanol to the volume of the nickel nitrate is 6-8 mL: 1mmol of the active component;
washing the obtained precipitate with 95% ethanol for 5-7 times, drying at 80-90 ℃ for 24h, and roasting in a muffle furnace at 450-550 ℃ for 2-3 h to obtain Ni/NiO powder; obtaining Ni/NiO nano particles;
(2) weighing the Ni/NiO nano powder prepared in the step (1) and sodium sulfide, wherein the volume of added deionized water is 40-50 mL, the mass ratio of Ni/NiO to sodium sulfide is 1: 3-4, and the mass ratio of the volume of added deionized water to Ni/NiO is 40-50 mL: 0.1-0.2 g; stirring for 15min, then carrying out ultrasonic dispersion for 1-2 h, and transferring the mixed solution into a microwave instrument for reaction for 2-3 h; washing the precipitate obtained by filtering with 95% ethanol for 3-5 times, and drying at 80-90 ℃ for 24h to obtain Ni/Ni3S2Obtaining powder, namely Ni/Ni3S2An antibacterial agent.
Ni/Ni prepared by the invention3S2Is a nano-particle with rough surface, has an average particle size of 35nm, has good antibacterial property on escherichia coli, and can be used as an antibacterial agent for escherichia coli.
In particular, the microwave instrument selected in the present invention is fully called as microwave catalytic synthesis/extraction instrument (product of Beijing auspicin science and technology development Co., Ltd.), and has a power of 500W. The microwave method has the characteristics of high heating speed, sensitive reaction, uniform heating system and the like.
Specifically, the following description is provided: escherichia coli, which is a gram-negative bacterium having a rod-like shape and flagella around the body and capable of moving. When the resistance of human or animal body is reduced or Escherichia coli invades other parts of human body, peritonitis, septicemia, cholecystitis, cystitis and diarrhea can be caused. Coli live in the human and animal intestinal tract and not in water, if found in water, indicating that the water is contaminated with feces. In hygiene, Escherichia coli is often used as an index for checking whether a water source is contaminated with feces. Coli has a rapid growth, is easy to culture, and has a mutation that can be easily detected, and thus, it is an important biological experimental material and one of the commonly used bacteria for testing antibacterial properties of antibacterial agents.
The antibacterial property of the product is evaluated by adopting a bacteriostatic ring method. Generally, if the diameter of the zone of inhibition is greater than 7mm, then the inhibition is determined to be effective. Meanwhile, the growth of E.coli before and after addition of the antibacterial agent was observed with an OLYMPUS BX51 microscope (Olympus BX51) to evaluate the antibacterial activity. After the antibacterial agent is added, the number of escherichia coli is obviously reduced, and the growth state is obviously changed, which indicates that the antibacterial agent has better performance.
Ni/Ni prepared by the invention3S2The diameter of the antibacterial zone of the nano particles to escherichia coli is 18-22 mm, which shows that the antibacterial property of the product is good, and the nano particles can be used as a nano antibacterial agent.
The invention has the technical characteristics and excellent effects that:
the invention is synthesized in two parts: (1) synthesizing Ni/NiO nano particles by a microwave method; (2) carrying out rapid microwave vulcanization treatment on the prepared Ni/NiO nano-particles to obtain Ni/Ni3S2A composite material. The invention adopts the Ni/NiO powder prepared by the microwave method, and the micro-morphology is Ni/NiO nano-particles with smooth surfaces; the Ni/NiO powder is vulcanized by adopting a microwave method again to prepare Ni/Ni3S2Powder with rough surface Ni/Ni in microscopic appearance3S2And (3) nanoparticles. The Ni/Ni with special morphological characteristics3S2Nanoparticles are one of the important influencing factors for better antibacterial property. Ni/Ni prepared by the invention3S2The rough surface of the nano particles increases the surface area of the composite material and increases the opportunity of close contact with bacteria; metallic nickel and Ni3S2The large amount of nickel ions and sulfur ions in the antibacterial agent make the antibacterial agent easier to combine with amino acids and other substances in proteins, influence the replication function of bacterial cells, lead the bacterial cells to be finally apoptotic, and show higher antibacterial activity.
Ni/Ni prepared by the method of the invention3S2The composite material has the following advantages:
1. the nano Ni/NiO composite material is prepared by a microwave method. Wherein Ni and NiO are both cubic crystalline phases, and the diffraction peaks thereof respectively correspond to standard cards (PDF #65-0380) and (PDF # 47-1049).
2. Sulfurizing by microwave method to obtain Ni/Ni3S2In the composite material, Ni is still in a cubic crystal phase (PDF #65-0380), and Ni3S2The diffraction peaks correspond to standard cards (PDF #44-1418) for the orthorhombic phase. The product has high purity and good crystallinity.
3. The microscopic morphology of the Ni/NiO composite material is smooth-surfaced nano particles; Ni/Ni produced after vulcanization3S2The micro-morphology of the composite material is nano-particles with rough surfaces, and the average particle size is slightly increased.
4、Ni/Ni3S2In the composite material, the particle size is in a nanometer level, so that sulfur and nickel ions in the composite material are more easily bonded with amino acids and other substances in bacterial protein, and the protein is inactivated and dies; in addition, the rough surface is also added with Ni/Ni3S2The active site of the nano-particles contacted with bacteria has better antibacterial activity.
5. The microwave preparation method is rapid and simple, low in cost, high in product purity, good in antibacterial effect and worthy of popularization and application.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the nanopowder prepared in example 1. The ordinate is relative diffraction intensity, and the abscissa is 2 θ diffraction angle. Wherein (a) is the XRD pattern of Ni/NiO; (b) is Ni/Ni3S2XRD pattern of (a).
FIG. 2 is a scanning electron micrograph of the Ni/NiO nanopowder prepared in example 1.
FIG. 3 shows Ni/Ni prepared in example 13S2Scanning electron microscope photograph of the nano powder.
FIG. 4 shows Ni/Ni prepared in example 13S2Low power transmission electron microscope photo of nano powder.
FIG. 5 shows Ni/Ni prepared in example 13S2High power transmission electron microscope photo of nano powder.
FIG. 6 shows Ni/Ni prepared in example 13S2Energy dispersive X-ray spectroscopy (EDS) of the nanopowder.
FIG. 7 is a photograph of the zone of inhibition of Ni/NiO nanopowder prepared in example 1.
FIG. 8 shows Ni/Ni prepared in example 13S2The photograph of the bacteriostatic circle of the nano powder.
FIG. 9 shows Ni/Ni prepared in example 13S2Photomicrographs of the nanopowder. The left picture shows that Ni/Ni is not added3S2Microscopic photograph of growth of colibacillus of nano powder; the right picture shows the addition of Ni/Ni3S2Microscopic photograph of growth of Escherichia coli after nanopowder.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
Example 1A Ni/Ni3S2The preparation method of the nano antibacterial agent comprises the following steps:
(1) weighing 7mL of oleic acid in a beaker, sequentially adding 0.2908g (10mmol) of nickel nitrate hexahydrate, 0.1200g (30mmol) of sodium hydroxide (the molar ratio of the nickel nitrate to the sodium hydroxide is 1:3), 45mL of deionized water and 7mL of ethanol, fully and uniformly stirring, transferring to a microwave instrument, reacting for 1.5h, washing the obtained precipitate with 95% ethanol for 6 times, drying at 85 ℃ for 24h, and roasting at 500 ℃ in a muffle furnace for 2.5h to obtain Ni/NiO powder; the obtained Ni/NiO nano-particles are smooth in surface and have the average particle size of 30 nm. As shown in fig. 2.
(2) 0.1074g of Ni/NiO powder prepared in the step (1) and 0.3759g of sodium sulfide nonahydrate (the mass ratio of Ni/NiO to sodium sulfide nonahydrate is 1:3.5) are weighed, 45mL of deionized water is added, stirring is carried out for 15min, ultrasonic dispersion is carried out for 1.5h, and the mixed solution is transferred to a microwave instrument for reaction for 2.5 h; washing the precipitate with 95% ethanol for 4 times, and drying at 85 deg.C for 24 hr to obtain Ni/Ni3S2Powder with the micro-morphology characteristic of Ni/Ni with rough surface3S2Nanoparticles, average particle size 35 nm. The obtained product is Ni/Ni3S2A nano antibacterial agent. As shown in fig. 3.
Ni/Ni prepared by the invention3S2The test steps of the antibacterial zone of the nanoparticles to escherichia coli are as follows: Ni/Ni prepared by the invention is mixed with 0.9 percent of normal saline3S2Antimicrobial samples were prepared as 10mg/mL suspensions. Weighing about 15mL LB solid culture medium which is sterilized, melted and cooled to 45 ℃, cooling and solidifyingSucking 0.25mL of Escherichia coli suspension on a culture medium, uniformly coating, placing an Oxford cup, and quickly transferring 0.35mL of sample suspension in the Oxford cup. Culturing in a constant temperature box at 37 ℃ for 24h, observing the bacterial growth situation around the sample, and measuring the inhibition zone by using a vernier caliper. All instruments are sterilized under ultraviolet lamp for 20 min.
Wherein LB solid medium: 10.0 g of peptone, 8.5 g of agar powder, 5.0 g of beef extract and 5.0 g of sodium chloride were accurately weighed, dissolved in 1000mL of deionized water, and heated and dissolved with continuous stirring. Boiling for 5min, adjusting pH to 7.0-7.2, subpackaging in 20mL small test tubes with 15mL each, sterilizing at high temperature for 20min in a steam sterilizer, cooling, and refrigerating in a refrigerator at 4 ℃ for later use.
Ni/Ni prepared by the invention3S2The diameter of the inhibition zone of the composite material is 22mm, and the diameter of the larger inhibition zone shows that the Ni/Ni prepared by the invention3S2The nano-particles have stronger antibacterial property to escherichia coli. As shown in fig. 8.
For comparison of antibacterial effect, the diameter of the inhibition zone of the Ni/NiO nano-particles with smooth surfaces prepared by the invention is measured to be 12 mm. The Ni/NiO nano-particles prepared by the invention also have certain antibacterial effect on escherichia coli, but the antibacterial property is lower than that of Ni/Ni with rough surface3S2And (3) nanoparticles. As shown in fig. 7.
Meanwhile, the invention adopts an Olympus BX51 research microscope to observe that Escherichia coli is added with or without Ni/Ni under the same experimental conditions3S2Growth before and after the antimicrobial agent. Observation shows that before the antibacterial agent is added, the growth form of the escherichia coli is uniform rod-shaped, the distribution is dense, and the quantity is large; while adding Ni/Ni3S2After the antibacterial agent is used, the shape change of escherichia coli is large, the rod shape is not obvious enough, the distribution is sparse, and the quantity is obviously reduced. The observation result fully shows that the Ni/Ni with rough surface prepared by the invention3S2The nano-particles have stronger performance of inhibiting the growth of escherichia coli and can be used as an excellent antibacterial agent for the escherichia coli. The observation result of the research type microscope of the Olympus BX51 is consistent with the test result of the inhibition zone. Such asAs shown in fig. 9.
Ni/Ni prepared by the invention3S2The rough surface of the nano particles increases the surface area of the composite material and increases the opportunity of close contact with bacteria; metallic nickel and Ni3S2The large amount of nickel ions and sulfur ions in the antibacterial agent make the antibacterial agent easier to combine with amino acids and other substances in proteins, influence the replication function of bacterial cells, lead the bacterial cells to be finally apoptotic, and show higher antibacterial activity.
Example 2 Ni/Ni prepared as described in example 13S2The nano antibacterial agent has the advantages that the experimental steps are unchanged, 0.2908g of nickel nitrate hexahydrate weighed in the experimental step (1) is unchanged in mass, 0.1074g of Ni/NiO powder prepared in the step (1) weighed in the experimental step (2) is unchanged in mass, and other physical quantities are changed. The difference is that:
in the step (1), the volume of oleic acid is 6 mL; the molar ratio of nickel nitrate to sodium hydroxide is 1: 2.5; adding 40mL of deionized water and 6mL of ethanol; reacting for 1h in a microwave instrument; washing the obtained precipitate with 95% ethanol for 5 times, drying at 85 deg.C for 24 hr, and calcining in 450 deg.C muffle furnace for 3 hr to obtain Ni/NiO powder. The micro-morphology is Ni/NiO nano-particles with smooth surfaces and slight agglomeration, and the average grain diameter is 30-40 nm.
In the step (2), the mass ratio of Ni/NiO to sodium sulfide nonahydrate is 1: 3; adding 40mL of deionized water; ultrasonic dispersion is carried out for 1 h; reacting for 2 hours in a microwave instrument; washing the precipitate with 95% ethanol for 3 times, and drying at 80 deg.C for 24 hr to obtain Ni/Ni3S2And (3) powder. The micro-morphology is Ni/Ni with rough surface and slight agglomeration3S2The average particle size of the nanoparticles is 40-45 nm.
Ni/Ni prepared by the invention3S2The diameter of the inhibition zone of the composite material is 18mm, which shows that the Ni/Ni prepared by the invention3S2The nano-particles have better antibacterial property to escherichia coli, and the antibacterial property of the nano-particles is superior to that of Ni/NiO nano-particles.
Example 3 Ni/Ni prepared as described in example 13S2The nano antibacterial agent has the same experimental steps, and is called in the experimental step (1)The mass of the nickel nitrate hexahydrate is 0.2908g, the mass of the Ni/NiO powder prepared in the step (1) weighed in the experimental step (2) is 0.1074g, and other physical quantities are changed. The difference is that:
in the step (1), the volume of oleic acid is 8 mL; the molar ratio of nickel nitrate to sodium hydroxide is 1: 3.5; adding 50mL of deionized water and 8mL of ethanol; reacting for 2 hours in a microwave instrument; washing the obtained precipitate with 95% ethanol for 7 times, drying at 90 ℃ for 24h, and roasting at 550 ℃ in a muffle furnace for 3h to obtain Ni/NiO powder. The micro-morphology is Ni/NiO nano-particles with smooth surfaces and slight agglomeration, and the average grain diameter is 35-40 nm.
In the step (2), the mass ratio of the Ni/NiO to the sodium sulfide nonahydrate is 1: 4; adding 50mL of deionized water; ultrasonic dispersion is carried out for 2 hours; reacting for 3 hours in a microwave instrument; washing the precipitate with 95% ethanol for 5 times, and drying at 85 deg.C for 24 hr to obtain Ni/Ni3S2And (3) powder. The micro-morphology is Ni/Ni with rough surface and slight agglomeration3S2The average particle size of the nanoparticles is 35-45 nm.
Ni/Ni prepared by the invention3S2The diameter of the inhibition zone of the composite material is 20mm, which shows that the Ni/Ni prepared by the invention3S2The nano-particles have better antibacterial property to escherichia coli, and the antibacterial property of the nano-particles is superior to that of Ni/NiO nano-particles.
Example 4 Ni/Ni prepared as described in example 13S2The nano antibacterial agent has the advantages that the experimental steps are unchanged, 0.2908g of nickel nitrate hexahydrate weighed in the experimental step (1) is unchanged in mass, 0.1074g of Ni/NiO powder prepared in the step (1) weighed in the experimental step (2) is unchanged in mass, and other physical quantities are changed. The difference is that:
in the step (1), the volume of oleic acid is 7 mL; the molar ratio of nickel nitrate to sodium hydroxide is 1: 3; adding 40mL of deionized water and 7mL of ethanol; reacting for 1h in a microwave instrument; washing the obtained precipitate with 95% ethanol for 5 times, drying at 80 ℃ for 24h, and roasting at 550 ℃ in a muffle furnace for 2.5h to obtain Ni/NiO powder. The micro-morphology is Ni/NiO nano-particles with smooth surfaces and slight agglomeration, and the average grain diameter is 20-30 nm.
In the step (2), Ni/NiO and nineThe mass ratio of the hydrated sodium sulfide is 1: 3; adding 50mL of deionized water; ultrasonic dispersion is carried out for 1.5 h; reacting for 2 hours in a microwave instrument; washing the precipitate with 95% ethanol for 4 times, and drying at 80 deg.C for 24 hr to obtain Ni/Ni3S2And (3) powder. The micro-morphology is Ni/Ni with rough surface and slight agglomeration3S2The average particle size of the nanoparticles is 25-40 nm.
Ni/Ni prepared by the invention3S2The diameter of the inhibition zone of the composite material is 21mm, which shows that the Ni/Ni prepared by the invention3S2The nano-particles have better antibacterial property to escherichia coli, and the antibacterial property of the nano-particles is superior to that of Ni/NiO nano-particles.
Claims (13)
1. Ni/Ni3S2The preparation method of the nano antibacterial agent is characterized in that the antibacterial agent is Ni/Ni with rough surface3S2The nano-particles have an average particle size of 30-45 nm, and comprise the following steps:
(1) taking oleic acid as a dispersing agent, adding nickel nitrate, sodium hydroxide, deionized water and ethanol, uniformly mixing, and carrying out microwave reaction; washing and drying the precipitate, and roasting at 450-550 ℃ for 2-3 h to obtain Ni/NiO nano particles;
(2) adding the Ni/NiO particles into sodium sulfide and deionized water, uniformly mixing, and carrying out microwave reaction; washing and drying the precipitate to obtain Ni/Ni3S2A nano antibacterial agent.
2. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the diameter of an inhibition zone of the antibacterial agent to escherichia coli is 18-22 mm.
3. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the molar ratio of the volume of the oleic acid to the volume of the nickel nitrate in the step (1) is 6-8 mL: 1mmol, the molar ratio of nickel nitrate to sodium hydroxide = 1: 2.5-3.5, the molar ratio of the volume of deionized water added to the nickel nitrate is 40-50 mL: 1mmol, the molar ratio of the volume of the added ethanol to the volume of the nickel nitrate is 6-8 mL:1mmol。
4. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the microwave reaction in the step (1) is carried out for 1-2 hours.
5. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the microwave reaction power in the step (1) is 500W, and the reaction time is 1.5 h.
6. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the precipitate in the step (1) is washed for 5-7 times by 95% ethanol.
7. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the drying condition in the step (1) is drying for 24 hours at the temperature of 80-90 ℃.
8. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that in the step (2), the mass ratio of Ni/NiO to sodium sulfide = 1: 3-4, and the mass ratio of the volume of the added deionized water to the mass ratio of Ni/NiO is 40-50 mL: 0.1 to 0.2 g.
9. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the mode of uniformly mixing in the step (2) is ultrasonic dispersion, and the ultrasonic dispersion time is 1-2 hours.
10. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the microwave reaction in the step (2) is carried out for 2-3 hours.
11. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the microwave reaction power in the step (2) is 500W, and the reaction time is 2.5 h.
12. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the precipitate in the step (2) is washed for 3-5 times by using 95% ethanol.
13. Ni/Ni according to claim 13S2The preparation method of the nano antibacterial agent is characterized in that the drying condition in the step (2) is drying for 24 hours at the temperature of 80-90 ℃.
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