CN106938194B - Synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles - Google Patents

Synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles Download PDF

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CN106938194B
CN106938194B CN201710156412.8A CN201710156412A CN106938194B CN 106938194 B CN106938194 B CN 106938194B CN 201710156412 A CN201710156412 A CN 201710156412A CN 106938194 B CN106938194 B CN 106938194B
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张麟
孙彦
游粉粉
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Abstract

The invention relates to a synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles. Firstly, synthesizing brominated silicon dioxide nano particles and SiO2-BIEM-PAM nanoparticles; silver nitrate is used as a silver ion donor, sodium borohydride is used as a reducing agent in SiO2-synthesizing silver nanoparticles in an aqueous solution of BIEM-PAM nanoparticles; centrifugal removal of SiO2-BIEM-PAM nanoparticles to obtain solution-state silver nanoparticles. The nano particles are in a monodisperse spherical structure, and the particle size is 1.0-10.0 nm. The obtained silver nanoparticles are applied to catalyzing p-nitrophenol to be reduced into p-aminophenol, and the obtained normalized reaction rate is higher than 0.8L.mg‑1.s‑1The solution silver nanoparticles are proved to have high catalytic performance. After being stored for 2 months at 4 ℃, the catalytic performance of the catalyst is kept higher than 85 percent, and the PDI of the catalyst is 0.8 measured by a Malvern particle size analyzer.

Description

Synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles
Technical Field
The invention relates to synthesis and application of monodisperse high-performance solution-state silver nanoparticles, belonging to the field of precious metal nano system preparation in the technical field of nano material preparation; in particular to a synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles.
Background
Silver nanoparticles have been widely studied and applied to the fields of catalysis, bioprobes, colorimetric detection, molecular recognition, and the like due to their unique physicochemical characteristics. For example, silver nanoparticles can act as a catalyst to catalyze the reduction of p-nitrophenol. The nitro compound is a common byproduct in the synthesis process of pesticides and dyes, and can cause serious environmental pollution. However, the amino compound formed by reducing the amino compound is a very important chemical and medical intermediate. Therefore, the silver nanoparticles can catalyze and reduce toxic substance para-nitrophenol into important chemical and medical intermediate para-aminophenol. Its catalytic performance is directly related to its nanometer size. However, the nano-size also results in high surface energy and aggregation of silver nanoparticles, thereby limiting their applications. Thus, existing methods for the synthesis of silver nanoparticles, such as ultraviolet radiation, microwave radiation, chemical reduction, photochemistry, aerosol synthesis, wet chemistry techniques, and spray coating methods, typically require various supports and protective agents. The research and development of the preparation method of the silver nanoparticles without the protective agent and the support are of great significance.
Disclosure of Invention
The invention aims to provide a synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles. Synthesis of silica- [ 2- (2-bromoisobutoxy) ethyl methacrylate ] -polyacrylamide (hereinafter abbreviated as SiO) by ATRP method2-BIEM-PAM) nanoparticles. Silver nitrate is used as a silver ion donor, sodium borohydride is used as a reducing agent, and the silver ion donor is added into SiO2Synthesizing silver nanoparticles in a BIEM-PAM nanoparticle aqueous solution, and obtaining the solution-state silver nanoparticles through centrifugal separation. The obtained silver nano particles are applied to catalyzing the reduction reaction of p-nitrophenol. Transmission electron microscope, energy spectrum, ultraviolet spectrophotometer measurement, dynamic light scattering experiment and catalysis experiment confirm that the obtained solution state silver nanoparticle has monodispersity, high catalytic performance and good stability.
The technical scheme of the invention is as follows:
a method for preparing monodisperse high-catalytic-performance solution-state silver nanoparticles comprises the following steps:
(1) synthesizing brominated silica nanoparticles;
(2)SiO2-BIEM-PAM nanoparticle synthesis;
(3) silver nitrate is used as a silver ion donor, sodium borohydride is used as a reducing agent in SiO2-synthesizing silver nanoparticles in an aqueous solution of BIEM-PAM nanoparticles;
(4) by centrifugationRemoving SiO in mixed solution2-BIEM-PAM nanoparticles, to obtain solution-state silver nanoparticles.
The method of the step (1) comprises the following steps: sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran and stirring; stirring for 15-30 min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant pressure titration funnel, adjusting a piston of the constant pressure funnel to ensure that the solution in the funnel completely drips within 30-50 min, and sealing; stirring the mixed solution in an ice bath for 2-3 h, and then placing the system in a water bath at 30 ℃ for reaction; taking out the reaction product, centrifuging and washing to obtain the brominated silica nanoparticles.
Preferably, the mass ratio of the ammoniated silicon dioxide to the triethylamine to the tetrahydrofuran is 0.08-0.2: 0.02-0.4: 1; the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is 0.6-1: 1.
The method of the step (2) is as follows: sequentially adding the brominated silica nanoparticles, methanol and water, then adding 2- (2-bromine isobutoxy) ethyl methacrylate into the solution, stirring and carrying out ultrasonic treatment for 2-3 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution, stirring and carrying out ultrasonic treatment for 5-10 min; introducing nitrogen for 30-50 min, adding cuprous bromide, and continuously introducing nitrogen for 30-50 min; sealing and placing in a water bath at 30 ℃ for reaction; centrifugal separation of the product to obtain SiO2-BIEM-PAM nanoparticles.
Preferably, the mass ratio of the brominated silicon dioxide to the water is 0.02-0.15: 1, and the mass ratio of the methanol to the water is 2.1-4.0: 1; the mass ratio of the 2- (2-bromine isobutoxy) ethyl methacrylate to the brominated silica is 0.1-1: 1; the mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is 2-5: 1, and the mass ratio of the cupric bromide to the cuprous bromide is 0.1-1: 1.
The method of the step (3) is as follows: taking prepared SiO2-BIEM-PAM nano-particles are dispersed in the water passing through the membrane to control SiO2The mass ratio of the BIEM-PAM nano particles to the film-passing water is 0.1-1.5: 1; then adding silver nitrate water solution into the system and leading SiO2Stirring the BIEM-PAM nano particles and silver nitrate at room temperature for 3-5 hours, wherein the mass ratio of the BIEM-PAM nano particles to the silver nitrate is 110-300: 1; then stirring the mixtureAdding a sodium borohydride aqueous solution, enabling the mass ratio of the added sodium borohydride to the added silver nitrate to be 1-120: 1, and continuously stirring for 3-5 hours.
Preferably, the concentration of the silver nitrate aqueous solution is 0.1-10 mM; the concentration of the sodium borohydride aqueous solution is 0.01-1M.
The method of the step (4) is as follows: and (4) removing precipitates from the mixture obtained in the step (3) through centrifugation to obtain solution-state silver nanoparticles.
The monodisperse high-catalytic-performance solution-state silver nanoparticles prepared by the method have a monodisperse spherical structure, and the particle size is 1.0-10.0 nm; the method is applied to the reaction for catalyzing the reduction of p-nitrophenol into p-aminophenol, and the obtained normalized reaction rate is higher than 0.8L.mg-1.s-1The high catalytic performance is proved; after being stored for 2 months at 4 ℃, the catalytic performance of the catalyst is kept higher than 85 percent, and the PDI of the catalyst is 0.8 measured by a Malvern particle size analyzer.
The silver nanoparticles of the present invention are suitable for the application of catalyzing the reduction of p-nitrophenol to p-aminophenol.
The silver nano-particles of the invention are applied as catalysts and environmental remediation agents.
The silver nanoparticles of the present invention are suitable for applications in the biomedical field.
The silver nanoparticle synthesis method is suitable for obtaining stable metal nanoparticles by nanoparticle assistance and exploring the application of ultramicro metal nanoparticle synthesis.
The invention has the beneficial effects that: by means of the auxiliary SiO2And (4) synthesizing the-BIEM-PAM nano particles to obtain monodisperse solution-state silver nano particles, wherein the particle size is 1.0-10.0 nm, and a support and a protective agent are not needed. The synthesized solution-state silver nanoparticles are applied to the reaction of catalyzing p-nitrophenol to be reduced into p-aminophenol, show high catalytic performance, and the obtained normalized reaction rate is higher than 0.8L-1.s-1And the method is superior to the data reported in the literature. And the catalytic performance of the catalyst is kept higher than 85% after the catalyst is stored for 2 months at 4 ℃, and the PDI of the catalyst is 0.8 measured by a Malvern particle size analyzer. Thus, the present inventors have synthesized and confirmed monodisperse solution-state silver nanoparticlesIt has high catalytic performance and good stability. The obtained silver nanoparticles are applied to catalyzing p-nitrophenol to be reduced into p-aminophenol, and toxic pollutants can be changed into important chemical and pharmaceutical intermediates.
Drawings
FIG. 1: SiO synthesized by the invention2-a diagram of the mechanism of synthesis of BIEM-PAM nanoparticles. Wherein the spheres refer to silica nanoparticles.
FIG. 2: electron microscopy of silver nanoparticles synthesized in accordance with the present invention.
Detailed Description
The invention will now be described in detail with reference to the drawings, which are provided for illustration and not for limiting the invention in any way.
The technical scheme of the synthesis method and the application of the monodisperse high-catalytic-performance solution-state silver nanoparticles is summarized as follows:
the preparation and synthesis of the silver nanoparticles in solution state of the invention are summarized as follows:
(1) synthesizing brominated silica nanoparticles;
(2)SiO2-BIEM-PAM nanoparticle synthesis;
(3) silver nitrate is used as a silver ion donor, sodium borohydride is used as a reducing agent in SiO2-synthesizing silver nanoparticles in an aqueous solution of BIEM-PAM nanoparticles;
(4) removing SiO in the mixed solution by centrifugation2-BIEM-PAM nanoparticles, to obtain solution-state silver nanoparticles.
Specifically, it is preferable to use the present invention in any method for achieving the object of the present invention, without being limited thereto.
The method of the step (1) comprises the following steps:
taking the ammoniated silicon dioxide nano particles and washing the ammoniated silicon dioxide nano particles for 3-5 times by using tetrahydrofuran; sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran, controlling the mass ratio of the ammoniated silicon dioxide to the tetrahydrofuran to be 0.08-0.2: 1, controlling the mass ratio of the triethylamine to the tetrahydrofuran to be 0.02-0.4: 1, and stirring for 30-50 min; stirring for 15-30 min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant-pressure titration funnel, wherein the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is controlled to be 0.6-1: 1, adjusting a piston of the constant-pressure funnel to ensure that the solution in the funnel completely drips within 30-50 min, and sealing the flask; stirring the mixed solution in an ice bath for 2-3 h, and then placing the system in a water bath at 30 ℃ for reaction for 20-30 h; and after the reaction is finished, taking out the reaction product, performing centrifugal washing, and sequentially washing with tetrahydrofuran for 3-5 times, ethanol for 3-5 times, water for 3-5 times and methanol for 3-5 times to obtain the brominated silicon dioxide nanoparticles.
The method of the step (2) is as follows:
taking a conical flask, sequentially adding brominated silicon dioxide nanoparticles, methanol and water, and controlling the mass ratio of the brominated silicon dioxide to the water to be 0.02-0.15: 1 and the mass ratio of the methanol to the water to be 2.1-4.0: 1. Then adding 2- (2-bromine isobutoxy) ethyl methacrylate, controlling the mass ratio of 2- (2-bromine isobutoxy) ethyl methacrylate to brominated silicon dioxide to be 0.1-1: 1, stirring for 5-10 min, and carrying out ultrasonic treatment for 2-3 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution; stirring for 5-10 min, and carrying out ultrasound for 5-10 min; introducing nitrogen for 30-50 min, adding cuprous bromide, and continuously introducing nitrogen for 30-50 min; then sealing the bottle mouth with a rubber plug, and placing the bottle mouth in a water bath at 30 ℃ for reaction for 5-10 h; centrifugally separating the product, washing the product to be colorless by using 0.01-1.0M disodium ethylene diamine tetraacetate aqueous solution, washing the product for 3-5 times by using absolute ethyl alcohol and washing the product for 3-5 times by using a membrane to obtain SiO2-BIEM-PAM nanoparticles. The mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is controlled to be 2-5: 1, and the mass ratio of the cupric bromide to the cuprous bromide is controlled to be 0.1-1: 1.
The method of the step (3) is as follows:
taking prepared SiO2dispersing-BIEM-PAM nanoparticles in water for passing through membrane, performing ultrasonic treatment for 1-5min, and controlling SiO2The mass ratio of the-BIEM-PAM nano particles to the film-passing water is controlled to be 0.1-1.5: 1. Then adding 0.1-10 mM silver nitrate aqueous solution into the system, and leading SiO2Controlling the mass ratio of the BIEM-PAM nano particles to the silver nitrate at 110-300: 1, and stirring for 3-5 h at room temperature; then is atAdding a 0.01-1M sodium borohydride aqueous solution under the stirring condition, controlling the mass ratio of the added sodium borohydride to the added silver nitrate to be 1-120: 1, and continuously stirring for 3-5 hours.
The method of the step (4) is as follows:
and (4) removing precipitates from the mixture obtained in the step (3) through centrifugation to obtain solution-state silver nanoparticles. The silver nanoparticles were characterized and tested by transmission electron microscopy and catalytic p-nitrophenol reduction.
The monodisperse high-catalytic-performance solution-state silver nanoparticles prepared by the method have a monodisperse spherical structure, and the particle size is 1.0-10.0 nm; the method is applied to the reaction for catalyzing the reduction of p-nitrophenol into p-aminophenol, and the obtained normalized reaction rate is higher than 0.8L.mg-1.s-1The high catalytic performance is proved; after being stored for 2 months at 4 ℃, the catalytic performance of the catalyst is kept higher than 85 percent, and the PDI of the catalyst is 0.8 measured by a Malvern particle size analyzer.
The details and verification are as follows:
example 1: SiO 22Preparation of BIEM-PAM nanoparticles.
Taking the ammoniated silicon dioxide nano particles and washing the ammoniated silicon dioxide nano particles for 3 times by using tetrahydrofuran; sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran, wherein the mass ratio of the silicon dioxide to the tetrahydrofuran is 0.08997:1, the mass ratio of the triethylamine to the tetrahydrofuran is 0.02737:1, and stirring for 30 min; stirring for 15min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant pressure titration funnel, wherein the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is controlled to be 0.6972:1, adjusting a constant pressure funnel piston to ensure that the solution in the funnel is completely dripped within 30min, and sealing the flask; stirring the mixed solution in an ice bath for 2 hours, and then placing the system in a water bath at 30 ℃ for reaction for 20 hours; after the reaction is finished, the reactant is taken out for centrifugal washing, and is washed by tetrahydrofuran for 3 times, ethanol for 3 times, water for 3 times and methanol for 3 times in sequence, so that the brominated silicon dioxide nano-particles are obtained.
Taking a conical flask, adding the brominated silica nanoparticles, methanol and water in sequence, and controlling the mass ratio of the brominated silica to the water to be 0.125:1, and controlling the mass ratio of the methanol to the water to be 2.3754: 1. Then adding 2- (2-bromine isobutoxy) ethyl methacrylate, controlling the quality of 2- (2-bromine isobutoxy) ethyl methacrylate and brominated silicon dioxide at 0.1564:1, stirring for 5min, and performing ultrasonic treatment for 2 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution; stirring for 5min, and performing ultrasonic treatment for 5 min; introducing nitrogen for 30min, adding cuprous bromide, and introducing nitrogen for 30 min; then sealing the bottle mouth with a rubber plug, and placing the bottle mouth in a water bath at 30 ℃ for reaction for 8 hours; centrifuging, washing with 0.1M disodium ethylene diamine tetraacetate water solution to colorless, washing with anhydrous ethanol for 3 times, and washing with membrane for 3 times to obtain SiO2-BIEM-PAM nanoparticles. The mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is controlled to be 2.7:1, and the mass ratio of the cupric bromide to the cuprous bromide is controlled to be 0.1545: 1. The preparation process is shown in figure 1.
Taking prepared SiO2dispersing-BIEM-PAM nanoparticles in water for passing through membrane, performing ultrasonic treatment for 2min, and controlling SiO2The mass ratio of the BIEM-PAM nano particles to the film-passing water is controlled to be 0.5833: 1. Then, 0.7mM silver nitrate aqueous solution was added to the system, and SiO was allowed to stand2Controlling the mass ratio of the BIEM-PAM nano particles to the silver nitrate to be 117.65:1, and stirring for 4 hours at room temperature; then adding 0.1M sodium borohydride aqueous solution under the condition of stirring, controlling the mass ratio of the added sodium borohydride to the added silver nitrate at 95.4:1, and continuously stirring for 3 hours. The resulting mixture was centrifuged (9000rpm, 20min), and the supernatant was taken and the precipitate was removed to obtain stable silver nanoparticles in a solution state.
Example 2: SiO 22Preparation of BIEM-PAM nanoparticles.
Taking the ammoniated silicon dioxide nano particles and washing the ammoniated silicon dioxide nano particles for 4 times by using tetrahydrofuran; sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran, controlling the mass ratio of the ammoniated silicon dioxide to the tetrahydrofuran to be 0.08:1 and the mass ratio of the triethylamine to the tetrahydrofuran to be 0.02:1, and stirring for 40 min; stirring for 20min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant pressure titration funnel, wherein the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is controlled to be 0.6:1, adjusting a constant pressure funnel piston to ensure that the solution in the funnel is completely dripped within 40min, and sealing the flask; the mixed solution is stirred for 2.5h in an ice bath, and then the system is placed in a water bath at the temperature of 30 ℃ for reaction for 25 h; after the reaction is finished, the reactant is taken out for centrifugal washing, and is washed by tetrahydrofuran for 4 times, ethanol for 4 times, water for 4 times and methanol for 4 times in sequence, so that the brominated silicon dioxide nano-particles are obtained.
Taking a conical flask, adding the brominated silica nanoparticles, methanol and water in sequence, and controlling the mass ratio of the brominated silica to the water to be 0.02:1 and the mass ratio of the methanol to the water to be 2.1: 1. Then adding 2- (2-bromine isobutoxy) ethyl methacrylate, 2- (2-bromine isobutoxy) ethyl methacrylate and brominated silicon dioxide into the solution, controlling the mass at 0.1:1, stirring for 8min, and performing ultrasonic treatment for 2.5 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution; stirring for 8min, and performing ultrasonic treatment for 8 min; introducing nitrogen for 40min, adding cuprous bromide, and introducing nitrogen for 40 min; then sealing the bottle mouth with a rubber plug, and placing the bottle mouth in a water bath at 30 ℃ for reaction for 5 hours; centrifuging, washing with 0.01M disodium ethylene diamine tetraacetate water solution to colorless, washing with anhydrous ethanol for 4 times, and washing with membrane for 4 times to obtain SiO2-BIEM-PAM nanoparticles. The mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is controlled to be 2:1, and the mass ratio of the copper bromide to the cuprous bromide is controlled to be 0.1: 1.
Taking prepared SiO2dispersing-BIEM-PAM nanoparticles in water for passing through membrane, performing ultrasonic treatment for 1min, and controlling SiO2The mass ratio of the BIEM-PAM nano particles to the film-passing water is controlled to be 0.1: 1. Then, 0.1mM silver nitrate aqueous solution was added to the system, and SiO was allowed to stand2Controlling the mass ratio of the BIEM-PAM nano particles to the silver nitrate at 110:1, and stirring for 3 hours at room temperature; then adding 0.01M aqueous solution of sodium borohydride under the condition of stirring, controlling the mass ratio of the added sodium borohydride to the added silver nitrate at 1:1, and continuously stirring for 3 hours. The resulting mixture was centrifuged (9000rpm, 20min), and the supernatant was taken and the precipitate was removed to obtain stable silver nanoparticles in a solution state.
Example 3: SiO 22-BIEM-PAM nanoemnsAnd (3) preparing particles.
Taking the ammoniated silicon dioxide nano particles and washing the ammoniated silicon dioxide nano particles for 5 times by using tetrahydrofuran; sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran, controlling the mass ratio of the ammoniated silicon dioxide to the tetrahydrofuran to be 0.2:1 and the mass ratio of the triethylamine to the tetrahydrofuran to be 0.4:1, and stirring for 50 min; stirring for 30min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant pressure titration funnel, wherein the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is controlled to be 1:1, adjusting a piston of the constant pressure funnel to ensure that the solution in the funnel is completely dripped within 50min, and sealing the flask; stirring the mixed solution in an ice bath for 3 hours, and then placing the system in a water bath at 30 ℃ for reaction for 30 hours; after the reaction is finished, the reactant is taken out for centrifugal washing, and is washed by tetrahydrofuran 5 times, ethanol 5 times, water 5 times and methanol 5 times in sequence, so that the brominated silicon dioxide nano-particles are obtained.
Taking a conical flask, adding the brominated silica nanoparticles, methanol and water in sequence, and controlling the mass ratio of the brominated silica to the water to be 0.15:1 and the mass ratio of the methanol to the water to be 4.0: 1. Then adding 2- (2-bromine isobutoxy) ethyl methacrylate, controlling the mass ratio of 2- (2-bromine isobutoxy) ethyl methacrylate to the solution at 1:1, stirring for 10min, and performing ultrasonic treatment for 3 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution; stirring for 10min, and performing ultrasonic treatment for 10 min; introducing nitrogen for 50min, adding cuprous bromide, and introducing nitrogen for 50 min; then sealing the bottle mouth with a rubber plug, and placing the bottle mouth in a water bath at 30 ℃ for reaction for 10 hours; centrifuging, washing with 1.0M disodium ethylene diamine tetraacetate water solution to colorless, washing with anhydrous ethanol for 5 times, and washing with membrane for 5 times to obtain SiO2-BIEM-PAM nanoparticles. The mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is controlled to be 5:1, and the mass ratio of the copper bromide to the cuprous bromide is controlled to be 1: 1.
Taking prepared SiO2dispersing-BIEM-PAM nanoparticles in water for 5min by ultrasonic treatment, and controlling SiO2The mass ratio of the BIEM-PAM nano particles to the film-passing water is controlled to be 1.5: 1. Then adding 10mM silver nitrate aqueous solution to the system and allowingSiO2Controlling the mass ratio of the BIEM-PAM nano particles to the silver nitrate at 300:1, and stirring for 5 hours at room temperature; then adding a 1M sodium borohydride aqueous solution under the condition of stirring, controlling the mass ratio of the added sodium borohydride to the added silver nitrate at 120:1, and continuously stirring for 5 hours. The resulting mixture was centrifuged (9000rpm, 20min), and the supernatant was taken and the precipitate was removed to obtain stable silver nanoparticles in a solution state.
Example 4: characterization of silver nanoparticles.
And (3) dropping a drop of solution-state sample on a copper sheet, naturally drying at room temperature to obtain an electron microscope sample, and detecting by a JEM-2100F electron microscope at 200kV, as shown in figure 2. It can be seen that the silver nanoparticles are small black dots that are uniformly distributed, as shown in fig. 2. The particle size of the silver nanoparticles was determined to be 1.8 ± 0.25nm using the particle size analysis software Nano Measurer 1.2. The photograph of the solution is shown in the inset of FIG. 2, since the solution contains SiO2BIEM-PAM nanoparticles, the solution being milky white.
Example 5: and (5) detecting the catalytic performance.
The reaction system was 45 mL. Firstly, 39.7mL of membrane-passing water and 3mL of 1mM p-nitrophenol solution are added into a 150mL conical flask, and the solution is light yellow; an additional 2mL of 4.5M sodium borohydride solution was added and the solution instantaneously changed from pale yellow to bright yellow. 0.3ml of silver nanoparticle solution was added thereto, and the mixture was magnetically stirred at room temperature (25 ℃ C.). The bright yellow color of the solution gradually became lighter to colorless as the reaction proceeded. The reaction process is sampled at regular time, and the absorption value of p-nitrophenol at the wavelength of 400nm is detected by using UV-Vis spectrum to monitor the reaction process.
In the catalytic reduction reaction, because the concentration of sodium borohydride is far greater than that of p-nitrophenol, the concentration of sodium borohydride is considered to be constant in the reaction, and the reaction rate is irrelevant to the concentration of sodium borohydride. The catalytic reaction can thus be described by first order reaction kinetics with a rate constant passing through ln (A)t/A0)＝-kappt is calculated, where t is the reaction time, A0Is the initial absorbance value of the reactant, AtIs the absorbance value, k, of the reactants at time tappIs the apparent rate constant. Because k isappValue and inverseThe amount of silver nanoparticles used is related to, for ease of comparison, kappThe catalytic performance was evaluated by normalizing the amount of silver nanoparticles to obtain a normalized rate constant k.
ln(At/A0) And (3) drawing and linearly fitting the time t, wherein the obtained correlation coefficient is more than 0.995, which shows that the correlation coefficient and the time t accord with a linear relation, and the catalytic reduction process is proved to accord with first-order reaction kinetics. Calculating the apparent rate constant k of the reaction by fitting the slope values obtained by the straight lineappIs 17.6x 10-3s-1Normalized rate constant k is 0.892L.mg-1.s-1. The rate constant is higher than the data reported in the literature.
In addition, after the synthesized solution-state silver nanoparticles are stored for 2 months at 4 ℃, the PDI of the synthesized solution-state silver nanoparticles is 0.8 measured by a Malvern particle size analyzer, which shows that the obtained solution-state silver nanoparticles can still keep good monodispersity, the catalytic performance of the prepared solution-state silver nanoparticles keeps 88.3% of the initial catalytic activity, and the solution-state silver nanoparticles are proved to have good stability.
In summary, the experimental results show that SiO is passed through2The BIEM-PAM nano-particles assist in successfully synthesizing the solution-state spherical silver nano-particles with monodispersity, high catalytic performance and good stability. The particle size of the silver nano-particles is 1.8 +/-0.25 nm, the silver nano-particles have extremely high catalytic performance in the reduction reaction of catalytic p-nitrophenol, and the silver nano-particles are superior to data reported in literatures.
The invention provides a synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles, and structural morphology and catalytic performance of the solution-state silver nanoparticles are inspected through a transmission electron microscope, an energy spectrum, ultraviolet spectrophotometer measurement, a dynamic light scattering experiment and a catalytic experiment, which are described by embodiments. It will be apparent to those skilled in the art that the present technology can be practiced with modification of, or with appropriate modification and combination of, the methods described herein without departing from the spirit, scope, and concept of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (8)

1. A method for preparing monodisperse high-catalytic-performance solution-state silver nanoparticles is characterized by comprising the following steps:
(1) the synthesis method of the brominated silica nanoparticles comprises the following steps: sequentially adding ammoniated silicon dioxide, triethylamine and tetrahydrofuran and stirring; stirring for 15-30 min under ice bath, adding a mixed solution of 2-bromoisobutyryl bromide and tetrahydrofuran by using a constant pressure funnel, adjusting a piston of the constant pressure funnel to ensure that the solution in the funnel completely drips within 30-50 min, and sealing; stirring the mixed solution in an ice bath for 2-3 h, and then placing the system in a water bath at 30 ℃ for reaction; taking out the reactant, centrifuging and washing to obtain brominated silicon dioxide nanoparticles;
(2)SiO2the synthesis of BIEM-PAM nano particles comprises the following specific steps: sequentially adding brominated silica nanoparticles, methanol and water, then adding 2- (2-bromine isobutoxy) ethyl methacrylate into the solution, stirring and carrying out ultrasound for 2-3 min; then sequentially adding acrylamide, copper bromide and N, N, N' -pentamethyldiethylenetriamine into the solution, stirring and carrying out ultrasonic treatment for 5-10 min; introducing nitrogen for 30-50 min, adding cuprous bromide, and continuously introducing nitrogen for 30-50 min; sealing and placing in a water bath at 30 ℃ for reaction; centrifugal separation of the product to obtain SiO2-BIEM-PAM nanoparticles;
(3) silver nitrate is used as a silver ion donor, sodium borohydride is used as a reducing agent in SiO2-synthesizing silver nanoparticles in an aqueous solution of BIEM-PAM nanoparticles;
(4) removing SiO in the mixed solution by centrifugation2-BIEM-PAM nanoparticles, to obtain solution-state silver nanoparticles.
2. The method as claimed in claim 1, wherein the mass ratio of the aminated silica, triethylamine and tetrahydrofuran is 0.08-0.2: 0.02-0.4: 1; the mass ratio of the 2-bromoisobutyryl bromide to the tetrahydrofuran is 0.6-1: 1.
3. The method according to claim 1, wherein the mass ratio of the brominated silica to the water is 0.02 to 0.15:1, and the mass ratio of the methanol to the water is 2.1 to 4.0: 1; the mass ratio of the 2- (2-bromine isobutoxy) ethyl methacrylate to the brominated silica is 0.1-1: 1; the mass ratio of the acrylamide to the N, N, N' -pentamethyldiethylenetriamine is 2-5: 1, and the mass ratio of the cupric bromide to the cuprous bromide is 0.1-1: 1.
4. The method as claimed in claim 1, wherein the method of step (3) is as follows: taking prepared SiO2-BIEM-PAM nano-particles are dispersed in the water passing through the membrane to control SiO2The mass ratio of the BIEM-PAM nano particles to the film-passing water is 0.1-1.5: 1; then adding silver nitrate water solution into the system and leading SiO2Stirring the BIEM-PAM nano particles and silver nitrate at room temperature for 3-5 hours, wherein the mass ratio of the BIEM-PAM nano particles to the silver nitrate is 110-300: 1; and then adding a sodium borohydride aqueous solution under the stirring condition, keeping the mass ratio of the added sodium borohydride to the added silver nitrate at 1-120: 1, and continuously stirring for 3-5 hours.
5. The method according to claim 4, wherein the concentration of the silver nitrate aqueous solution is 0.1 to 10 mM; the concentration of the sodium borohydride aqueous solution is 0.01-1M.
6. The monodisperse high catalytic performance solution state silver nanoparticle prepared by the method of claim 1, which is characterized in that the nanoparticle has a monodisperse spherical structure, and the particle size is 1.0-10.0 nm; after being stored at 4 ℃ for 2 months, the PDI of the cells was 0.8 as measured by a malvern particle size analyzer.
7. The use of silver nanoparticles prepared by the method of claim 1 for catalyzing the reduction of p-nitrophenol to p-aminophenol.
8. The silver nanoparticles prepared by the method of claim 1 are suitable for biomedical applications, environmental remediation or ultra-micro metal nanoparticle synthesis.
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