CN114916541A - Preparation method of high-durability silver-based antibacterial material - Google Patents

Preparation method of high-durability silver-based antibacterial material Download PDF

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CN114916541A
CN114916541A CN202210684517.1A CN202210684517A CN114916541A CN 114916541 A CN114916541 A CN 114916541A CN 202210684517 A CN202210684517 A CN 202210684517A CN 114916541 A CN114916541 A CN 114916541A
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molecular sieve
antibacterial material
hybridized
naa molecular
silver
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徐会君
杜庆洋
陈龙
孙武珠
李成峰
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Shandong University of Technology
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Shandong University of Technology
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a novel method for preparing a high-durability silver-series antibacterial material by encapsulating sub-nano silver clusters in a Zn hybridized NaA molecular sieve. Weighing Zn hybridized NaA molecular sieve and AgNO according to the molar ratio of 1:10 3 Adding a certain amount of deionized water to form a suspension, stirring, and preparing Ag by liquid-phase ion exchange + -Zn hybridized NaA molecular sieve antibacterial material. Ag to be prepared + Adding deionized water into the Zn-hybridized NaA molecular sieve antibacterial material to prepare 2 wt.% suspension, adding a certain amount of sodium vanadate and ethanol to enable the concentration of the sodium vanadate to be 0.3 wt.% and the concentration of the ethanol to be 2 mol/L, uniformly stirring, irradiating for a certain time, filtering, washing and drying to obtain the Ag (0) -Zn-hybridized NaA molecular sieve antibacterial material. The silver sub-nano particle size in the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material prepared by the invention is 0.1-0.35 nm, and has good antibacterial durability.

Description

Preparation method of high-durability silver-series antibacterial material
Technical Field
The invention relates to the field of functional materials, in particular to a preparation method of a high-durability silver-based antibacterial material.
Background
Bacterial infection is one of the important factors threatening human health and life safety, and bacteria causing common infection are escherichia coli, staphylococcus aureus and the like. Once the bacteria acquire resistance and become more resistant, the therapeutic effect of the drug is weakened, thereby prolonging the treatment time of the disease and ultimately increasing the medical expense. The problem of infectious diseases caused by different pathogenic microorganisms, as well as the resistance of bacteria, is a serious public health problem worldwide today. Therefore, how to kill or inhibit harmful bacteria in the environment has been the focus of research for many years, and the development and application of antibacterial materials are the key.
The antibacterial material can be divided into natural antibacterial material and synthetic antibacterial material, and the synthetic antibacterial material includes organic antibacterial material and inorganic antibacterial material. The inorganic antibacterial material has the characteristics of both the stability of the inorganic material and the high efficiency of antibacterial ingredients, and is developed as the mainstream of the antibacterial material. Silver has strong antibacterial ability, has broad-spectrum inhibition effect on bacteria, has wide medical application, and can kill 16 bacteria such as escherichia coli, staphylococcus aureus and the like. Silver-based antibacterial materials have become a focus of research in inorganic antibacterial materials. Silver-containing antibacterial agents developed at home and abroad are various, such as silver-carrying molecular sieve antibacterial agents, silver-carrying oxide antibacterial agents, silica gel antibacterial agents, alumina and activated carbon antibacterial agents. However, the silver-based antibacterial material has some disadvantages, such as poor stability in aqueous solution and easy loss, and silver ions can also react with anions commonly found in water to form insoluble substances, thereby losing antibacterial activity, so that the durability of the silver-based antibacterial agent is a problem to be solved.
The invention aims to provide a preparation method of a high-durability silver-based antibacterial material.
Disclosure of Invention
The technical scheme adopted by the invention is as follows: zn hybridized NaA molecular sieve is used as a carrier material, and Ag is prepared by a liquid phase ion exchange method + Loaded on a Zn hybridized NaA molecular sieve to prepare the antibacterial material. Adding a certain amount of sodium vanadate into the loaded Ag + Adding a certain amount of ethanol into the Zn-hybridized NaA molecular sieve suspension, uniformly mixing, irradiating for a certain time by light, filtering, washing and drying to obtain the Zn-hybridized NaA molecular sieve antibacterial material loaded with silver nanoclusters. The method mainly comprises the following steps:
(1) according to a molar ratio of 110 weighing Zn hybridized NaA molecular sieve and AgNO 3 Adding deionized water to form suspension, stirring, and preparing Ag by liquid-phase ion exchange + -Zn hybridized NaA molecular sieve antibacterial material;
(2) ag prepared in the step (1) + Adding deionized water into the Zn hybridized NaA molecular sieve antibacterial material to prepare 2 wt.% suspension;
(3) adding a certain amount of sodium vanadate and ethanol into the mixture obtained in the step (2), wherein the concentration of the sodium vanadate is 0.3 wt.%, and the concentration of the ethanol is 2 mol/L;
(4) irradiating the light of (3) for a certain time;
(5) filtering the product obtained in the step (4), and washing with deionized water;
(6) and (5) drying to obtain the Ag (0) -Zn hybrid NaA molecular sieve antibacterial material.
In a preferred embodiment, the light illuminating the suspension may be ultraviolet light or visible light.
In a preferred embodiment, the light irradiation time is 100-200 seconds.
In a preferred embodiment, the Ag (0) -Zn hybrid NaA molecular sieve antibacterial material prepared by the method has the silver sub-nanoparticle size of 0.1-0.35 nm and good antibacterial durability.
The existence of simple substance silver in the prepared Ag (0) -Zn hybridized NaA molecular sieve antibacterial material sample can be identified by using ultraviolet-visible spectrum analysis; the size of the simple substance silver can be observed by adopting a high-resolution transmission electron microscope; the method can be used for measuring Ag in 0.3 wt.% antibacterial material after 10 times of deionized water cyclic soaking by adopting an atomic absorption spectrophotometry + The durability of the antibacterial material is judged by the concentration of (2).
Adding sodium vanadate into Ag + After the Zn hybridized NaA molecular sieve antibacterial material suspension is reacted with water to decompose into sodium metavanadate, the metavanadate catalyzes ethanol to reduce silver ions into silver simple substances under the action of light excitation, the existence of vanadium starts the formation process of silver clusters, the silver simple substances grow continuously to form the silver clusters along with the extension of irradiation time, and the silver clusters grow until the Zn hybridized NaA molecular sieve is filled and become immobile. In the absence of Ag + Ethanol is added into the suspension of the-Zn hybridized NaA molecular sieve antibacterial materialIn the case of (3), reduction of silver ions was not observed even after ultraviolet irradiation for 10 minutes. Irradiation of Ag in the Presence of ethanol + No reduction of silver ions was observed for the-Zn hybrid NaA molecular sieve antibacterial material suspension. Adding sodium vanadate Ag by irradiation in the presence of ethanol + The suspension of-Zn hybrid NaA molecular sieve antibacterial material resulted in a significant change in solution color, and less than 3 minutes of uv irradiation was sufficient to turn the milky suspension green, a typical color modification due to the formation of reduced silver nanoparticles in the solution.
When the suspension is irradiated by ultraviolet rays, new ultraviolet-visible bands appear at 275, 300, 325, 371 and 414 nm, and the intensities of the bands are increased along with the prolonging of the irradiation time and are characterized by the electron transition of the sub-nanometer reduced Ag species. After 30 seconds of treatment, particles with a particle size of more than 0.3 nm appeared in the spectra. Furthermore, the new bands at 432 and 562 nm are due to the formation of silver nanoparticles. The variation of these bands is direct evidence of the formation of sub-nanosilver clusters in Zn-hybridized NaA molecular sieve cages. The silver nanoparticles have a size of 0.1-0.35 nm and the crystal form remains intact by HRTEM observation. The Ag nanoparticles appear as bright white dots in the transmission image, while the black dots correspond to the surrounding molecular sieve framework.
The invention develops a new method for encapsulating sub-nano silver clusters in a Zn hybridized NaA molecular sieve. Nanosilver clusters control their preparation on the atomic scale, which is crucial for tuning their properties, and the development of efficient size-selective metal cluster synthesis methods and their integration into suitable solid supports is constantly being sought. However, to use a restrictive support, the present invention selects Zn hybrid NaA molecular sieves as a support, which is an effective solution to overcome this problem, as clusters tend to irreversibly aggregate into larger nanoparticles. Silver sub-nanoparticles are synthesized in a Zn hybridized NaA molecular sieve cage under the condition of no organic template, and the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material is prepared. The limitation of the zeolite framework cage on the silver sub-nanoparticles makes the silver sub-nanoparticles not easy to contact with external oxygen and water, and avoids oxidation and lossThe Ag (0) -Zn hybridized NaA molecular sieve antibacterial material has good antibacterial durability. 0.3 wt.% of the antibacterial material was soaked in deionized water for 10 cycles and no Ag was detected in the solution + The antibacterial material prepared by the invention is proved to have good durability.
Detailed Description
Example 1
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water is added to form a suspension, and the suspension is stirred for 4 hours at 50 ℃, filtered and washed. 950 g of deionized water and 2.85 g of Na are added 3 VO 4 76 mL of ethanol, irradiated with 200W of UV light for 200 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.35 nm, and Ag is not detected in the solution after the antibacterial material of 0.3 wt.% is circularly soaked in deionized water for 10 times + 。
Example 2
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water was added to form a suspension, which was stirred at 50 ℃ for 4 hours, filtered and washed. 950 g of deionized water and 2.85 g of Na were added 3 VO 4 76 mL of ethanol, irradiated with 200W of UV light for 100 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.16 nm, and Ag is not detected in the solution of 0.3 wt.% of the antibacterial material after 10 times of deionized water cyclic soaking + 。
Example 3
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water was added to form a suspension, which was stirred at 50 ℃ for 4 hours, filtered and washed. 950 g of deionized water and 2.85 g of Na were added 3 VO 4 76 mL of ethanol, irradiated with 200W of UV light for 150 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.28 nm, and 0.3 wt.% of the antibacterial material is not detected in a solution after 10 times of deionized water cyclic soakingGoes out of Ag + 。
Example 4
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water was added to form a suspension, which was stirred at 50 ℃ for 4 hours, filtered and washed. 950 g of deionized water and 2.85 g of Na are added 3 VO 4 76 mL of ethanol, irradiated with 200W of visible light for 200 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.26 nm, and Ag is not detected in the solution of 0.3 wt.% of the antibacterial material after 10 times of deionized water cyclic soaking + 。
Example 5
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water was added to form a suspension, which was stirred at 50 ℃ for 4 hours, filtered and washed. 950 g of deionized water and 2.85 g of Na are added 3 VO 4 76 mL of ethanol, irradiated with 200W of visible light for 100 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.1 nm, and Ag is not detected in the solution after the antibacterial material of 0.3 wt.% is circularly soaked in deionized water for 10 times + 。
Example 6
Weighing 18 g of Zn hybridized NaA molecular sieve and 1.7 g of AgNO 3 350 g of deionized water is added to form a suspension, and the suspension is stirred for 4 hours at 50 ℃, filtered and washed. 950 g of deionized water and 2.85 g of Na were added 3 VO 4 76 mL of ethanol, irradiated with 200W of visible light for 150 seconds. Filtering the obtained product, washing with deionized water, and drying to prepare the Ag (0) -Zn hybridized NaA molecular sieve antibacterial material. The size of silver sub-nano particles in the antibacterial material is 0.21 nm, and Ag is not detected in the solution of 0.3 wt.% of the antibacterial material after 10 times of deionized water cyclic soaking + 。

Claims (1)

1. A novel method for preparing a high-durability silver-based antibacterial material by encapsulating sub-nano silver clusters in a Zn-hybridized NaA molecular sieve is characterized by comprising the following steps: push buttonWeighing Zn hybridized NaA molecular sieve and AgNO according to the molar ratio of 1:10 3 Adding a certain amount of deionized water to form a suspension, stirring, and preparing Ag by liquid phase ion exchange + -Zn hybridized NaA molecular sieve antibacterial material, Ag prepared from it + Adding deionized water into the Zn hybridized NaA molecular sieve antibacterial material to prepare a suspension of 2 wt.%, adding a certain amount of sodium vanadate and ethanol to make the concentration of the sodium vanadate be 0.3 wt.% and the concentration of the ethanol be 2 mol/L, uniformly stirring, irradiating for a certain time, filtering, washing and drying to obtain an Ag (0) -Zn hybridized NaA molecular sieve antibacterial material; the light illuminating the suspension may be ultraviolet light or visible light; the light irradiation time is 100-200 seconds; the size of silver sub-nano particles in the Ag (0) -Zn hybrid NaA molecular sieve antibacterial material prepared by the invention is 0.1-0.35 nm, and Ag is not detected in the solution after the 0.3 wt.% antibacterial material is circularly soaked in deionized water for 10 times + And has good antibacterial durability.
CN202210684517.1A 2022-06-17 2022-06-17 Preparation method of high-durability silver-based antibacterial material Pending CN114916541A (en)

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