CN111069623A - Green preparation method for metal nano material - Google Patents
Green preparation method for metal nano material Download PDFInfo
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- CN111069623A CN111069623A CN201911326245.2A CN201911326245A CN111069623A CN 111069623 A CN111069623 A CN 111069623A CN 201911326245 A CN201911326245 A CN 201911326245A CN 111069623 A CN111069623 A CN 111069623A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention relates to the technical field of nano material preparation, and discloses a green preparation method for a metal nano material, which comprises the following steps: 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution; dissolving a silver salt and a protective agent in a water-soluble solvent; adding strong sodium oxide to adjust the pH value of the solution; adding pectin solution, heating and magnetically stirring at rotation speed of 1200r/min and temperature of 70 deg.C for 15 min; adding AgNO3The solution is continuously stirred at the rotating speed of 800r/min for 60 min. The invention adopts reproducible and degradable biological macromolecule citrus pectin as a reducing agent and a stabilizing agent to replace the reducing agent and the stabilizing agent in the traditional preparation process, so as to determine the green synthesis process of the silver nanoparticles by optimizing the preparation conditions.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a green preparation method for a metal nano material.
Background
In recent years, nanotechnology has become a hot research topic in various industries, and nanocomposites are mainly composed of polymers and metal particles. In recent years, nanotechnology has become a focus of research in various industries, and nanocomposites are mainly composed of polymersAnd metal particles. Among the numerous metal nanoparticles, Ag Nanonics (AgNPs)S) Due to its diversity and broad-spectrum antibacterial activity, it has been widely used in the fields of sensors, catalysts, biomedicine, water and atmosphere purification, food fresh-keeping detection, etc. Conventional preparation of AgNPSThe chemical reduction method has the advantages of low cost, convenient operation and the like, and has the main defects of toxic solvents, harmful byproducts and high consumption.
Pectin has the characteristics of low toxicity, good biocompatibility, biodegradability, easiness in forming colloid and the like, and is an excellent biological macromolecular material for preparing metal nanoparticles, however, pectin has the characteristics of low toxicity, good biocompatibility, biodegradability, easiness in forming colloid and the like at the present stage, and is an excellent biological macromolecular material for preparing metal nanoparticles, and the preparation research on pectin metal nanoparticles at the present stage is just started, so that the defects of poor environmental protection of a preparation method, high consumption of chemical reagents, high energy cost and the like exist.
Disclosure of Invention
Technical problem to be solved
The invention provides a green preparation method for a metal nano material, and aims to solve the problems that the preparation method is not environment-friendly enough, chemical reagents are consumed more, energy cost is high and the like in the current stage of preparation research on pectin metal nano particles.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a green preparation method for metal nano materials comprises the following specific preparation steps:
s1, silver salt 6.5g, protective agent 2-4g/L, pectin solution 3g/L and AgNO31mL of solution;
s2, dissolving silver salt and a protective agent in a water-soluble solvent;
s3, adding strong sodium oxide to adjust the pH value of the solution;
s4, adding pectin solution, heating and magnetically stirring at the rotation speed of 1200r/min and the temperature of 70 ℃ for 15 min;
s5, adding AgNO3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
Preferably, the PH range in step S3 is 7-8.
Preferably, the protective agent is PVP and sodium hexametaphosphate.
Preferably, the AgNO3The concentration of (B) is 0.3mol to 0.7 mol.
Preferably, the preparation steps of the pectin solution are as follows:
1, oven drying pericarpium Citri Tangerinae at 65 deg.C, dewatering, cooling, pulverizing, sieving, boiling, and bleaching in warm water to white and odorless;
a2, mixing the HCL solution and the orange peel powder according to the proportion of 20:1, adding the mixture into water with the water temperature of 85 ℃, stirring for 90min, and then filtering the liquid;
a3, placing the substance obtained by filtering the substance a2 into a centrifuge for centrifugation at the rotation speed of 4000r/min for 15min, and then filtering after adding ethanol with the volume fraction of 95% for precipitation for 1 h;
a4, washing the product of a3 after filtration by ethanol with the volume fraction of 90 percent, and then drying in an oven at the temperature of 45 ℃ for 40 min.
Preferably, the boiling step in the a1 is used for removing enzymes in orange peel, and the time is 5-10 min.
Preferably, the screening step in the a1 is carried out by using a screening element with the mesh size of below 40 meshes.
(III) advantageous effects
Compared with the prior art, the environment-friendly preparation method for the metal nano material provided by the embodiment of the invention adopts renewable and degradable biological macromolecule citrus pectin as a reducing agent and a stabilizing agent to replace the reducing agent and the stabilizing agent in the traditional preparation process, so that the environment-friendly synthesis process of the silver nano particles is ensured through optimizing the preparation conditions, the cost is lower compared with that of the preparation method, the operation is more convenient, and the consumption of chemical raw materials and energy sources in the traditional preparation process is reduced.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
This document provides an overview of various implementations or examples of the technology described in this disclosure, and is not a comprehensive disclosure of the full scope or all features of the disclosed technology.
Drawings
FIG. 1 is a schematic diagram showing the change of stirring temperature to the amount of nano-silver produced when pectin solution is added in the present invention;
FIG. 2 is a structural diagram of the change of the concentration of pectin solution to the yield of nano-silver in the present invention;
FIG. 3 is a TEM image of preparing nano-silver with 6g/L pectin according to the present invention;
FIG. 4 is a particle distribution histogram of nano-silver prepared from 6g/L pectin according to the present invention;
FIG. 5 is a TEM image of 3g/L pectin prepared nano-silver according to the present invention;
FIG. 6 is a particle distribution histogram of nano-silver prepared from 3g/L pectin according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a green preparation method for a metal nano material, which comprises the following steps:
the first step, 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min at the temperature of 70 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
The protective agent is PVP and sodium hexametaphosphate.
Further, the preparation steps of the pectin solution in the invention are as follows:
1. oven drying pericarpium Citri Tangerinae at 65 deg.C, dehydrating, cooling, pulverizing, sieving with 40 mesh sieve, boiling for 5-10min, and bleaching in warm water to white and odorless;
2. mixing the HCL solution and the orange peel powder according to a ratio of 20:1, adding into water with the water temperature of 85 ℃, stirring for 90min, and then filtering the liquid;
3. putting the substances obtained by filtration in the second step into a centrifuge for centrifugation at the rotating speed of 4000r/min for 15min, and then adding ethanol with the volume fraction of 95% for precipitation for 1h and then filtering;
4. and (3) washing the product filtered in the third step by using ethanol with the volume fraction of 90%, and then drying the product in an oven at the temperature of 45 ℃ for 40 min.
Example 1
3g/L pectin solution prepared by the method, and changing the temperature of the pectin solution in the fourth step of the preparation method when stirring, and performing spectral scanning after the preparation:
comparative experiment 1
A green preparation method for metal nano materials comprises the following specific steps:
the first step, 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotation speed of 1200r/min and the temperature of 60 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
Comparative experiment 2
A green preparation method for metal nano materials comprises the following specific steps:
the first step, 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min at the temperature of 70 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
A green preparation method for metal nano materials comprises the following specific steps:
the first step, 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min and the temperature of 80 ℃ for 15 min;
the fifth step,Adding AgNO with the concentration of 0.3mol to 0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
As can be seen from FIG. 1, when the reaction temperature was 70 ℃, a strong peak appeared around 410nm, which indicates that a large amount of silver nanoparticles were formed; when the temperature is raised to 80 ℃, the generated nano particles start to aggregate and precipitate, so the temperature of 70 ℃ used for stirring the pectin solution in the preparation method provided by the invention is the optimal temperature.
Example 2
Dissolving pectin with 20g/L NaOH to prepare 50mL of pectin solutions with concentrations of 1, 3 and 6g/L, reacting at 70 ℃ for 1min to generate nano-silver, diluting the solution after reaction by 300 times, and performing spectral scanning at 300-600nm by an ultraviolet-visible spectrophotometer:
comparative experiment 1
A green preparation method for metal nano materials comprises the following specific steps:
the first step, silver salt 6.5g, protective agent 2-4g/L, pectin solution 1g/L and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min at the temperature of 70 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
Comparative experiment 2
A green preparation method for metal nano materials comprises the following specific steps:
the first step, 6.5g of silver salt, 2-4g/L of protective agent, 3g/L of pectin solution and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min at the temperature of 70 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
A green preparation method for metal nano materials comprises the following specific steps:
first step, silver salt 6.5g, protective agent 2-4g/L, pectin solution 6g/L and AgNO31mL of solution;
secondly, dissolving silver salt and a protective agent in a water-soluble solvent;
thirdly, adding strong sodium oxide to adjust the pH value of the solution, wherein the pH value range is 7-8;
fourthly, adding pectin solution, heating and magnetically stirring at the rotating speed of 1200r/min at the temperature of 70 ℃ for 15 min;
fifthly, adding AgNO with the concentration of 0.3mol-0.7mol3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
As can be seen from FIG. 2, the solution has a distinct absorption peak near 410nm, which proves that nano-silver is generated, and when the mass concentration of pectin is 3g/L, the absorption peak is the highest, i.e. 3g/L is the optimum pectin concentration required for generating nano-silver; when the pectin concentration is more than 3g/L, a large amount of galacturonic acid is produced, resulting in no redox reaction with AgNO 3.
Example 3
The nano-silver samples prepared in the comparative tests 2 and 3 in the example 2 were collected, the nano-silver samples were observed and compared in the form of nano-silver obtained under different preparation conditions by a transmission electron microscope, and the particle size was statistically analyzed, and the detection results were as follows:
as shown in FIG. 3 and FIG. 4, under the optimal reaction conditions, the prepared silver nanoparticles with pectin concentration of 6g/L are spherical, and the particle size of the observed nanoparticles is mainly distributed between 30 and 75 nm.
As shown in FIG. 5 and FIG. 6, under the optimal reaction conditions, the prepared nano silver particles with pectin concentration of 3g/L are spherical, the dispersibility and the separation degree are good, the particle size reaction time is 1min, and the citrus pectin is mainly distributed between 5nm and 15 nm.
According to the comparative test, the fact that the concentration of 3g/L pectin generates nano silver with smaller particle size compared with the concentration of 6g/L pectin is probably because silver ions are limited in pectin macromolecules by anionic groups and are adsorbed on a loose alkali hydrolysis pectin matrix, the pectin concentration is increased, the trend of the synthesized nano particles to be larger disappears, the synthesized nano particles begin to be aggregated into large particles and cause the reduction of the maximum light absorption value, and the spherical nano silver with smaller particle size has better antibacterial performance than the spherical nano silver with larger particle size, so that the optimal process condition for preparing the nano silver provided by the invention is that 3g/L pectin is hydrolyzed by alkali, and 1mL of AgNO with the concentration of 0.3mol-0.7mol is dripped3Solution and temperature at 70 ℃.
In conclusion, renewable and degradable biological macromolecule citrus pectin is used as a reducing agent and a stabilizing agent to replace the reducing agent and the stabilizing agent in the traditional preparation process, so that the green synthesis process of the silver nanoparticles is ensured through the optimization of preparation conditions, and compared with the preparation method, the cost is lower, and the operation is more convenient.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A green preparation method for metal nano materials is characterized by comprising the following specific preparation steps of:
s1, silver salt 6.5g, protective agent 2-4g/L, pectin solution 3g/L and AgNO31mL of solution;
s2, dissolving silver salt and a protective agent in a water-soluble solvent;
s3, adding strong sodium oxide to adjust the pH value of the solution;
s4, adding pectin solution, heating and magnetically stirring at the rotation speed of 1200r/min and the temperature of 70 ℃ for 15 min;
s5, adding AgNO3And continuously stirring the solution at the rotating speed of 800r/min for 60min, and taking out the silver nanoparticles with brown external substances.
2. The green production method for metal nano-materials according to claim 1, wherein the pH value in the step S3 is 7-8.
3. A green preparation method for metal nano-materials according to claim 1, characterized in that the protective agents are PVP and sodium hexametaphosphate.
4. The green preparation method for metal nano-material according to claim 1, characterized in thatIn that the AgNO3The concentration of (B) is 0.3mol to 0.7 mol.
5. The green preparation method for the metal nano-material according to claim 1, wherein the pectin solution is prepared by the following steps:
1, oven drying pericarpium Citri Tangerinae at 65 deg.C, dewatering, cooling, pulverizing, sieving, boiling, and bleaching in warm water to white and odorless;
a2, mixing the HCL solution and the orange peel powder according to the proportion of 20:1, adding the mixture into water with the water temperature of 85 ℃, stirring for 90min, and then filtering the liquid;
a3, placing the substance obtained by filtering the substance a2 into a centrifuge for centrifugation at the rotation speed of 4000r/min for 15min, and then filtering after adding ethanol with the volume fraction of 95% for precipitation for 1 h;
a4, washing the product of a3 after filtration by ethanol with the volume fraction of 90 percent, and then drying in an oven at the temperature of 45 ℃ for 40 min.
6. A green preparation method for metal nano-materials according to claim 5, wherein the boiling step in a1 is used for removing enzyme from orange peel for 5-10 min.
7. The green production method for metal nano-materials according to claim 5, wherein the a1 is screened with a screening element of 40 mesh or less.
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| US11766720B2 (en) * | 2021-10-07 | 2023-09-26 | King Fahd University Of Petroleum And Minerals | Method of making silver nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11766720B2 (en) * | 2021-10-07 | 2023-09-26 | King Fahd University Of Petroleum And Minerals | Method of making silver nanoparticles |
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