CN111978595B - Environment-friendly silver-loaded antibacterial agent based on plant waste powder and preparation method thereof - Google Patents
Environment-friendly silver-loaded antibacterial agent based on plant waste powder and preparation method thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010908 plant waste Substances 0.000 title claims abstract description 78
- 239000000843 powder Substances 0.000 title claims abstract description 75
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 63
- 239000004332 silver Substances 0.000 title claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 8
- 229940071536 silver acetate Drugs 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 6
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- ZJDGKLAPAYNDQU-UHFFFAOYSA-J [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O ZJDGKLAPAYNDQU-UHFFFAOYSA-J 0.000 description 2
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- HBHGBLBFPSHCGR-UHFFFAOYSA-L [Ag+].P([O-])([O-])=O.[Zr+4] Chemical compound [Ag+].P([O-])([O-])=O.[Zr+4] HBHGBLBFPSHCGR-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
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- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an environment-friendly silver-loaded antibacterial agent based on plant waste powder and a preparation method thereof. The method is obtained by adding plant waste powder, silver salt and silane coupling agent in a certain proportion, uniformly mixing, and controlling the reaction temperature and time. According to the invention, the silver ions are uniformly adsorbed under the action of the porous structure by utilizing the rich reducing groups and porous structures of the plant waste, the nano silver is subjected to in-situ reduction growth under the action of the reducing groups, and meanwhile, the nano silver is uniformly anchored in the plant tissue and on the surface of the plant tissue by virtue of the porous structure, so that the preparation of the silver-loaded antibacterial agent is realized in one step in the drying process of the plant waste powder. The invention solves the problems of high cost, easy agglomeration, easy dissolution of silver ions, weak interaction force with a high polymer material and the like of nano-silver, takes plant waste powder as a substrate, is environment-friendly and easy to obtain, has low cost, accords with the sustainable development concept, has simple preparation process, and avoids additional use of special equipment and reagents, especially reducing agents.
Description
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to an antibacterial agent and a preparation method thereof, and especially relates to an environment-friendly silver-loaded antibacterial agent based on plant waste powder and a preparation method thereof.
Background
With the improvement of health and safety awareness and demand of people, materials with antibacterial function are receiving more and more attention. Imparting antimicrobial properties to the material may improve its durability and extend its useful life to some extent. In addition, the high-efficiency antibacterial property can also meet the functional requirements of health and harmlessness, and the application field of the material is widened. Therefore, the development of antibacterial agents is an emerging industry. The antibacterial agents are various in variety and can be divided into two categories, namely inorganic antibacterial agents and organic antibacterial agents according to different chemical components. Although the organic antibacterial agent has a remarkable antibacterial effect in a short time, it has disadvantages of poor durability, high toxicity, easy volatilization and easy decomposition, and the like, so that it is limited in material processing. In contrast, inorganic antibacterial agents have outstanding long-term action and good heat resistance, and can be widely used for preparing polymer composite materials with antibacterial functions.
The nano silver antibacterial agent is a representative of inorganic antibacterial agents, has the advantages of low toxicity, high efficiency, broad spectrum, durability, no drug resistance and the like, and has advantages in the market and the antibacterial field. However, the nano silver antibacterial agent has high surface energy and is easily aggregated to form large-size particles, thereby reducing the dispersibility and antibacterial efficiency. In addition, the nano silver antibacterial agent is easy to dissolve silver ions, and the release of the nano silver antibacterial agent can shorten the antibacterial effective period. In addition, the use of a large amount of nano-silver antibacterial agent increases the cost and causes the enrichment of silver in the ecological environment. In order to solve the above problems, studies have been made to anchor nano-silver uniformly on a certain substrate, thereby producing a silver-loaded antibacterial agent with better efficiency. For example, patent document CN105532731B discloses a method for preparing a slow-release zirconium phosphonate silver-loaded antibacterial agent, which specifically comprises using zirconium phosphonate as a substrate, performing radiation crosslinking modification on the zirconium phosphonate with chitosan, and then performing vortex loading on silver ions to obtain a target antibacterial agent, but the method is complex in process, time-consuming, and limited in scale. Patent document CN106172386A discloses a method for preparing silver-loaded shell powder antibacterial agent, which specifically comprises mixing natural shell powder with sodium citrate solution and silver salt solution, and reducing with reducing agent sodium borohydride solution to obtain silver-loaded shell powder. Although the method takes natural and easily-obtained and environment-friendly animal shells as a substrate, a reducing agent is additionally used, and the preparation of the shell powder needs anaerobic calcination and has a complex process. Patent document CN111202091A discloses a method for preparing silver-loaded mesoporous silica antibacterial material, which specifically comprises preparing mesoporous silica by using tannic acid as a non-surfactant template, and reducing silver ions to generate nano silver. Although the method has mild conditions and does not use toxic reagents, the method relates to the preparation of mesoporous silica substrate and is complex. Patent document CN107312315B discloses a method for preparing a lignin/silver composite antibacterial agent, in which silver is loaded on lignin, and the defects of poor stability, short duration of efficacy and high cost of silver-based antibacterial agents are overcome, but lignin needs to be separated and extracted from plants or papermaking waste liquid, and a concentrated acid, a concentrated alkali or an organic solvent is needed in the process, so that the risk of environmental pollution is increased, and the method needs to perform carboxylation modification on lignin, and involves a large amount of processes for adjusting the pH value, so that the process is complicated. Patent document CN109997871A discloses a one-step method of nano silver loaded hydrothermal carbon spheres and a preparation method thereof, which comprises the specific steps of removing impurities from the collected biomass complete components, washing and drying, preparing into fine particles under the action of mechanical external force of a crusher and a ball mill, then dissolving the biomass complete components in a sodium hydroxide/urea system at low temperature, after dissolving, dripping a prepared silver ammonia solution, uniformly mixing, pouring the uniformly mixed solution into a high-temperature high-pressure reaction kettle together for hydrothermal reaction, and after the reaction is completed, centrifuging, washing, ultrasonic, centrifuging, and freeze-drying to obtain the nano silver loaded hydrothermal carbon spheres. Although the method solves the problems of easy agglomeration and instability of nano-silver, the biomass waste and the reducing groups contained in the biomass waste are fully utilized, the related process is complex, sodium hydroxide/urea is required to be used for dissolving the biomass, the operations such as centrifugation, washing, ultrasound and the like are required, the reaction is required to be carried out at high temperature and high pressure, and the reaction condition requires that the temperature is higher than 210 ℃.
Disclosure of Invention
Aiming at the problems of high cost, easy agglomeration, easy dissolution of silver ions and the like of the existing nano-silver antibacterial agent, and simultaneously overcoming the defects of weak acting force of nano-silver and a substrate, complex process and reagent (especially needing to additionally use a reducing agent), complex substrate preparation, high environmental pollution risk and the like in the existing preparation technology of the silver-loaded antibacterial agent, the invention provides the silver-loaded antibacterial agent based on plant waste powder and the preparation method thereof. The plant waste substrate used in the method contains rich plant conducting tissues, has a porous structure and a large specific surface area, and is beneficial to growth and uniform loading of nano-scale functional particles. Meanwhile, the porous structure is beneficial to slowing down the release of the nanoparticles. In terms of chemical composition, cellulose, hemicellulose, lignin and widely-existing plant polyphenol in plant wastes are rich in groups with high reducibility such as alcoholic hydroxyl, phenolic hydroxyl, sulfydryl and the like, so that sites can be provided for in-situ growth and anchoring of nano silver, and additional use of a reducing agent is avoided.
The method takes natural and easily-obtained and environment-friendly plant waste powder as a substrate, takes the rich reductive groups and porous structures into consideration, designs that silver ions are uniformly adsorbed under the action of the porous structures, and nanometer silver is reduced and grown in situ under the action of the reductive groups and can be uniformly anchored in plant tissues and on the surfaces of the plant tissues by virtue of the porous structures. In the process, the in-situ growth and anchoring of the nano silver and the surface treatment of the obtained antibacterial agent are simultaneously realized in the drying process of the plant waste powder. The method solves the problems of high cost, easy agglomeration, easy dissolution of silver ions and the like of the nano-silver, the selected substrate is environment-friendly and easy to obtain, the cost is low, the waste utilization accords with the sustainable development concept, the preparation process does not need special equipment, is simple and green, and the additional use of a reducing agent in the existing silver-loaded antibacterial agent preparation technology is avoided.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a silver-loaded antibacterial agent based on plant waste powder, which comprises the following steps:
crushing plant wastes, and grinding the plant wastes into powder to obtain plant waste powder;
dissolving 5-40 parts of silver salt in water, sequentially adding 50-90 parts of plant waste powder and 1-12 parts of silane coupling agent, uniformly stirring, adsorbing in a dark place, and drying to obtain the silver-loaded antibacterial agent based on the plant waste powder.
Preferably, the plant waste comprises one or a mixture of several of crop straws, waste wood and plant shells.
Preferably, the silver salt comprises one of silver nitrate, silver acetate or a mixture thereof.
Preferably, the molecular structure of the silane coupling agent has one end capable of interacting with a group in the plant waste and the other end capable of interacting with the nanoparticle.
Preferably, the silane coupling agent comprises one or a mixture of more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (ethyloxy) silane, and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the adsorption time in the dark is 10-200 min.
Preferably, the drying time is 10-36h, and the temperature is 60-120 ℃.
Preferably, the particle size of the plant waste powder is in the range of 40-600 mesh.
The invention also provides a silver-loaded antibacterial agent based on the plant waste powder, which comprises the following components in parts by weight:
5-40 parts of silver salt; 50-90 parts of plant waste powder; 1-12 parts of a silane coupling agent.
Preferably, the plant waste comprises one or a mixture of several of crop straws, waste wood and plant shells;
the silver salt comprises one or a mixture of silver nitrate and silver acetate;
one end of the molecular structure of the silane coupling agent can act with a group in the plant waste, and the other end of the molecular structure of the silane coupling agent can act with the nano-particles;
the silane coupling agent comprises one or a mixture of more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (ethyl) oxysilane and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
The silver-loaded antibacterial agent based on the plant waste powder solves the problems of high nano-silver cost, easy agglomeration, easy silver ion dissolution and the like, and does not additionally use a reducing agent.
Compared with the prior art, the invention has the following beneficial effects:
1. in the aspect of preparation process, the nano-silver is directly loaded in one step in the drying process of the plant waste powder, and the method has the advantages of simple process, environmental protection, low cost and large-scale production. The existing method needs to use complicated equipment and even toxic reagents.
2. In the aspect of substrate selection, the plant waste powder is used as a carrier, the raw materials are easily available, the variety is rich, the natural and harmless effects are realized, the cost is low, the green and environment-friendly effects are realized, and the waste utilization conforms to the sustainable development concept. Most of the carriers used in the existing method need to be synthesized and prepared independently, so that the process is complex, and the risk of environmental pollution is increased.
3. In the aspect of conception, the invention not only utilizes the rich reducing groups and porous structures of the plant wastes to realize the in-situ growth, uniform loading and slow release of the nano-silver, but also integrates the loading of the nano-silver, the drying of the antibacterial agent and the surface treatment into a whole, simplifies the process flow, and can be applied to high polymer materials after the surface treatment of the silane coupling agent. The existing method can realize uniform dispersion of the nano silver, but the growth of the existing method needs an additional reducing agent, and the process is complex.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron micrograph of the antibacterial agent obtained in example 1 and comparative example 1; wherein FIG. 1(a) shows the antibacterial agent obtained in comparative example 1; FIG. 1(b) shows the antibacterial agent obtained in example 1;
FIG. 2 is an EDS spectrum of the antibacterial agent obtained in example 1;
fig. 3 is an XRD pattern of the antibacterial agent obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
The plant waste (bamboo wood) is crushed and ground into powder, and 200-mesh plant waste powder is obtained. Dissolving 27 parts by weight of silver nitrate in water, sequentially adding 63 parts by weight of plant waste powder (bamboo wood powder) and 10 parts by weight of gamma-aminopropyltriethoxysilane, uniformly stirring, adsorbing for 100min in a dark place, and then drying in an oven at 90 ℃ for 24h to obtain the silver-loaded antibacterial agent based on the plant waste powder, wherein the scanning electron microscope picture of the silver-loaded antibacterial agent is shown in figure 1b, the EDS picture of the silver-loaded antibacterial agent is shown in figure 2, and the XRD picture of the silver-loaded antibacterial agent is shown in figure 3. The results show that: the nano silver is uniformly dispersed on the plant waste powder, the average grain diameter of the nano silver is about 14.0nm, the interface between the nano silver and the substrate is fuzzy, and the acting force of the nano silver and the substrate is strong. The antibacterial rates of the prepared silver-loaded antibacterial agent on escherichia coli and staphylococcus aureus are respectively 98% and 96% (the antibacterial performance test standard is GB/T21510-2008).
Example 2
Pulverizing plant waste (coconut shell), and grinding into powder to obtain 100 mesh plant waste powder. According to the weight portion, 5 portions of silver acetate are dissolved in water, 90 portions of plant waste powder (coconut shell powder) and 5 portions of gamma-glycidyl ether oxypropyl trimethoxy silane are sequentially added, the mixture is uniformly stirred and then adsorbed for 10min in a dark place, and then the mixture is placed in a 60 ℃ oven to be dried for 36h, so that the silver-loaded antibacterial agent based on the plant waste powder is obtained, and the scanning electron microscope image, the EDS (electronic Desorption) spectrum and the XRD (X-ray diffraction) spectrum of the silver-loaded antibacterial agent are similar to those of example 1.
Tests show that the nano silver is uniformly dispersed on the plant waste powder, and the average grain diameter of the nano silver is about 16.8 nm. The antibacterial rate of the prepared silver-loaded antibacterial agent to escherichia coli and staphylococcus aureus is 97% and 94% respectively (the antibacterial performance test standard is GB/T21510-2008).
Example 3
The plant waste (wheat straw) is crushed and ground into powder to obtain 40-mesh plant waste powder. Dissolving 37 parts of silver nitrate and 3 parts of silver acetate in water by weight, sequentially adding 59 parts of plant waste powder (straw powder) and 1 part of gamma-methacryloxypropyltrimethoxysilane, uniformly stirring, adsorbing for 200min in a dark place, and then drying in an oven at 120 ℃ for 10h to obtain the silver-loaded antibacterial agent based on the plant waste powder, wherein a Scanning Electron Microscope (SEM) picture, an EDS (electronic diffraction system) picture and an XRD (X-ray diffraction) picture of the silver-loaded antibacterial agent are similar to those in example 1.
Tests show that the nano silver is uniformly dispersed on the plant waste powder, and the average grain diameter of the nano silver is about 18.3 nm. The antibacterial rate of the obtained antibacterial agent to escherichia coli and staphylococcus aureus is 100% (the antibacterial performance test standard is GB/T21510-2008).
Example 4
The plant waste (poplar) is crushed and ground into powder to obtain 600-mesh plant waste powder. Dissolving 38 parts by weight of silver nitrate in water, sequentially adding 50 parts by weight of plant waste powder (poplar powder) and 12 parts by weight of vinyl triethoxysilane, uniformly stirring, adsorbing for 60min in a dark place, and then placing in an oven at 100 ℃ for drying for 18h to obtain the silver-loaded antibacterial agent based on the plant waste powder, wherein the scanning electron microscope image, the EDS spectrum and the XRD spectrum of the silver-loaded antibacterial agent are similar to those of example 1.
Tests show that the nano silver is uniformly dispersed on the plant waste powder, and the average grain diameter of the nano silver is about 17.6 nm. The antibacterial rate of the obtained antibacterial agent to escherichia coli and staphylococcus aureus is 100% (the antibacterial performance test standard is GB/T21510-2008).
Comparative example 1
The plant waste (bamboo wood) is crushed and ground into powder, and 200-mesh plant waste powder is obtained. Dissolving 30 parts by weight of silver nitrate in water, adding 70 parts by weight of plant waste powder (bamboo wood powder), uniformly stirring, adsorbing for 100min in a dark place, and then placing in an oven at 90 ℃ for drying for 24h to obtain the silver-loaded antibacterial agent based on the plant waste powder, wherein a scanning electron microscope image of the silver-loaded antibacterial agent is shown in figure 1 (a). Compared with example 1, the raw material proportion and the preparation method of the comparative example are the same, and the difference is only that: this comparative example did not have a silane coupling agent added. The results show that the nano silver is not uniformly dispersed on the plant waste powder and the interfacial force of the nano silver and the substrate is weak, thus resulting in a deterioration of the antibacterial effect of the obtained antibacterial agent. The antibacterial rate of the obtained antibacterial agent to escherichia coli and staphylococcus aureus is 86% and 88% respectively (the antibacterial performance test standard is GB/T21510-.
Comparative example 2
This comparative example was prepared in substantially the same manner as example 2, except that: the silver acetate and the plant waste powder (coconut husk powder) added in the comparative example are respectively in parts by weight: 1 part and 94 parts.
The result shows that the nano silver is uniformly dispersed on the plant waste powder, but the antibacterial rate of the obtained antibacterial agent to escherichia coli and staphylococcus aureus is only 68% and 61% (the antibacterial performance test standard is GB/T21510-.
Comparative example 3
This comparative example was prepared in substantially the same manner as example 4, except that: the silver nitrate and the plant waste powder (poplar powder) added in the comparative example are respectively in parts by weight: 44 parts and 44 parts.
The result showed that the average particle size of nano silver grown on the plant waste powder was about 46.2 nm. The antibacterial rate of the obtained antibacterial agent to escherichia coli and staphylococcus aureus is only 83% and 78% (the antibacterial performance test standard is GB/T21510-2008).
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (8)
1. A preparation method of a silver-loaded antibacterial agent based on plant waste powder is characterized by comprising the following steps:
crushing plant wastes, and grinding the plant wastes into powder to obtain plant waste powder;
dissolving 5-40 parts of silver salt in water, sequentially adding 50-90 parts of plant waste powder and 1-12 parts of silane coupling agent, uniformly stirring, adsorbing in a dark place, and drying to obtain the silver-loaded antibacterial agent based on the plant waste powder;
the light-resistant adsorption time is 10-200 min;
the drying time is 10-36h, and the temperature is 60-120 ℃.
2. The method of preparing a silver-loaded antimicrobial agent based on plant waste powder of claim 1, wherein: the plant waste comprises one or a mixture of several of crop straws, waste wood and plant shells.
3. The method of preparing a silver-loaded antimicrobial agent based on plant waste powder of claim 1, wherein: the silver salt comprises one of silver nitrate and silver acetate or a mixture of the silver nitrate and the silver acetate.
4. The method of preparing a silver-loaded antimicrobial agent based on plant waste powder of claim 1, wherein: one end of the molecular structure of the silane coupling agent can act with groups in plant wastes, and the other end of the molecular structure of the silane coupling agent can act with nano-silver.
5. The method of preparing a silver-loaded antimicrobial agent based on plant waste powder according to claim 1 or 4, wherein: the silane coupling agent comprises one or a mixture of more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
6. The method of preparing a silver-loaded antimicrobial agent based on plant waste powder of claim 1, wherein: the particle size range of the plant waste powder is 40-600 meshes.
7. The silver-loaded antibacterial agent prepared by the preparation method of the silver-loaded antibacterial agent based on plant waste powder as claimed in claim 1, which is characterized by comprising the following components in parts by weight:
5-40 parts of silver salt; 50-90 parts of plant waste powder; 1-12 parts of a silane coupling agent.
8. The silver-loaded antimicrobial agent based on plant waste powder of claim 7, wherein the plant waste comprises one or a mixture of crop straw, wood waste, plant husk;
the silver salt comprises one or a mixture of silver nitrate and silver acetate;
one end of the molecular structure of the silane coupling agent can act with a group in the plant waste, and the other end of the molecular structure of the silane coupling agent can act with the nano-silver;
the silane coupling agent comprises one or a mixture of more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
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Effective date of registration: 20231120 Address after: Room 510, Building B, Science and Technology Innovation Park, No. 398 Mahuan Road, Lihai Street, Yuecheng District, Shaoxing City, Zhejiang Province, 312366 Patentee after: Saiweide (Zhejiang) Medical Equipment Co.,Ltd. Address before: 050000 105, building C, Beijing Tianjin Hebei Collaborative Innovation Demonstration Park, No. 769 Taihang street, high tech Zone, Shijiazhuang City, Hebei Province Patentee before: Shijiazhuang Yuanding New Material Co.,Ltd. Patentee before: SHANGHAI JIAO TONG University |