CN114885960A - Nano-titanium dioxide-loaded metal organic antibacterial material and preparation method and application thereof - Google Patents

Nano-titanium dioxide-loaded metal organic antibacterial material and preparation method and application thereof Download PDF

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Publication number
CN114885960A
CN114885960A CN202210534069.7A CN202210534069A CN114885960A CN 114885960 A CN114885960 A CN 114885960A CN 202210534069 A CN202210534069 A CN 202210534069A CN 114885960 A CN114885960 A CN 114885960A
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antibacterial material
preparation
titanium dioxide
stirring
metal organic
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熊剑波
左俊
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East China Institute of Technology
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East China Institute of Technology
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691Coordination polymers, e.g. metal-organic frameworks [MOF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J35/39
    • B01J35/40
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/845Cobalt
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a nano titanium dioxide-loaded metal organic antibacterial material and a preparation method thereof, relating to the field of material chemistry, wherein the method comprises the following steps: dissolving ZIF-9 in an ethanol solvent, carrying out ultrasonic treatment, adding tetrabutyl titanate and ammonia water under stirring to obtain a reaction solution, carrying out magnetic stirring on the reaction solution under an anhydrous condition, transferring the solution into a reaction kettle after stirring, heating, and centrifuging, washing and drying the product in sequence after heating to obtain the antibacterial material. The material of the invention has certain bacteriostasis to colibacillus and bacillus.

Description

Nano-titanium dioxide-loaded metal organic antibacterial material and preparation method and application thereof
Technical Field
The invention relates to the field of material chemistry, in particular to a nano titanium dioxide-loaded metal organic antibacterial material and a preparation method and application thereof.
Background
With the progress of society and the improvement of living standard, people pay more and more attention to the healthy living environment, the awareness of antibiosis and mildew prevention is continuously strengthened, and the antibacterial material becomes a hotspot of the current social research. Moreover, bacterial and fungal infection is a difficult problem to human beings, and due to abuse of antibiotics, bacteria and fungi in the environment generate certain drug resistance, so that the research of a material with a certain sterilization effect is particularly important.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a nano titanium dioxide-loaded metal organic antibacterial material, and a preparation method and application thereof.
The technical solution of the invention is as follows:
dissolving ZIF-9 in an ethanol solvent, performing ultrasonic treatment, adding tetrabutyl titanate and ammonia water under stirring to obtain a reaction solution, performing magnetic stirring on the reaction solution under an anhydrous condition, transferring the solution into a reaction kettle after stirring, heating, centrifuging, washing and drying products in sequence after heating is finished, thus obtaining the antibacterial material.
In a preferred embodiment of the present invention, the tetrabutyl titanate is added in a mass ratio of 0.1-0.6:1 to ZIF-9.
As a preferable embodiment of the present invention, the heating temperature is 100-150 ℃.
In a preferred embodiment of the present invention, the drying temperature is 50 to 90 ℃.
As a preferable scheme of the invention, the preparation method of ZIF-9 is as follows: weighing 1.04-5.25g of cobalt nitrate crystal and 0.85-4.25g of benzimidazole, putting the cobalt nitrate crystal and the benzimidazole into a reaction kettle, adding 50-80ml of DMF, then carrying out magnetic stirring, putting the mixture into an oven for drying after the stirring is finished to obtain a purple crystal, washing the purple crystal with DMF, then washing with dichloromethane, and putting the mixture into the oven for drying after the washing is finished to obtain the catalyst.
The invention also discloses a nano titanium dioxide-loaded metal organic antibacterial material prepared by any one of the preparation methods.
The invention also discloses application of the antibacterial material in inhibiting escherichia coli and/or bacillus.
The invention has the beneficial effects that: the antibacterial material of the invention is prepared by loading titanium dioxide on a ZIF-9 material, wherein the ZIF-9 material is a porous frame structure formed by continuously connecting organic ligands and metal ions and has a structureControllable structure and modifiable active functional group. Meanwhile, the internal porous structure of the ZIF-9 material provides a larger contact area and active metal active sites, and the adsorption and loading performance is enhanced. Therefore, the antibacterial material combined with the ZIF-9 material has adjustable pore channels and high adsorption and load performance, and more adsorbed TiO is improved 2 The possibility that the bacillus subtilis has a certain inhibition effect on the growth of escherichia coli and bacillus is also found.
Drawings
FIG. 1 is a thermogravimetric analysis of the samples of examples 1-3;
FIG. 2 is a powder diffraction pattern of the samples of examples 1-4;
FIG. 3 is a graph showing the antibacterial activity of the samples of examples 1 to 4 against E.coli;
FIG. 4 is a graph showing the antibacterial activity of the samples of examples 1 to 4 against Bacillus;
in the figure, 1-example 1; 2-example 2; 3-example 3; 4-example 4.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Dissolving ZIF-9 in an ethanol solvent, performing ultrasonic treatment for 20 minutes, and adding the mixture, which is mixed with the ZIF-9 in a mass ratio of 0.01: 1:2.4 tetrabutyl titanate and ammonia water, and carrying out magnetic stirring for 12 hours under anhydrous conditions. After stirring, the solution was transferred to a 100ml reactor and heated at 150 ℃ for 12 hours. After heating, the product was centrifuged 3 times, washed twice with distilled water, and dried at 60 ℃ for 12 hours.
The preparation method of ZIF-9 comprises the following steps: 1.05g of cobalt nitrate crystals and 0.855g of benzimidazole were weighed into a 100ml reaction vessel, and 60ml of DMF was added, followed by magnetic stirring for 30 minutes. And after stirring, putting the mixture into a 135 ℃ oven for heating for 48h, washing the obtained purple crystal twice with DMF (dimethyl formamide), then washing twice with dichloromethane, and after washing, putting the mixture into a 60 ℃ oven for drying for 12h to obtain a product, and drying the product for 12h at 60 ℃.
Example 2
Dissolving ZIF-9 in an ethanol solvent, performing ultrasonic treatment for 20 minutes, adding tetrabutyl titanate and ammonia water which are mixed with the ZIF-9 in a mass ratio of 0.03:1 under stirring, and performing magnetic stirring for 12 hours under an anhydrous condition. After stirring, the solution was transferred to a 100ml reactor and heated at 150 ℃ for 12 hours. After heating, the product was centrifuged 3 times, washed twice with distilled water, and dried at 60 ℃ for 12 hours.
The preparation method of ZIF-9 comprises the following steps: 1.05g of cobalt nitrate crystals and 0.85g of benzimidazole were weighed into a 100ml reaction vessel, and 60ml of DMF was added, followed by magnetic stirring for 30 minutes. And after stirring, putting the mixture into a 135 ℃ oven to be heated for 48h, washing the obtained purple crystal twice with DMF (dimethyl formamide), then washing twice with dichloromethane, and after washing, putting the mixture into a 60 ℃ oven to be dried for 12h to obtain a product, and drying the product for 12h at the temperature of 60 ℃.
Example 3
Dissolving ZIF-9 in an ethanol solvent, performing ultrasonic treatment for 20 minutes, and adding the mixture, which is mixed with the ZIF-9 in a mass ratio of 0.1: 1:2.4 tetrabutyl titanate and ammonia water, and carrying out magnetic stirring for 12 hours under anhydrous conditions. After stirring, the solution was transferred to a 100ml reactor and heated at 150 ℃ for 12 hours. After heating, the product was centrifuged 3 times, washed twice with distilled water, and dried at 60 ℃ for 12 hours.
The preparation method of ZIF-9 comprises the following steps: 1.05g of cobalt nitrate crystals and 0.85g of benzimidazole were weighed into a 100ml reaction vessel, and 60ml of DMF was added, followed by magnetic stirring for 30 minutes. And after stirring, putting the mixture into a 135 ℃ oven to be heated for 48h, washing the obtained purple crystal twice with DMF (dimethyl formamide), then washing twice with dichloromethane, and after washing, putting the mixture into a 60 ℃ oven to be dried for 12h to obtain a product, and drying the product for 12h at the temperature of 60 ℃.
Example 4
Dissolving ZIF-9 in an ethanol solvent, performing ultrasonic treatment for 20 minutes, adding tetrabutyl titanate and ammonia water which are mixed with the ZIF-9 in a mass ratio of 0.6:1:2.4 under stirring, and performing magnetic stirring for 12 hours under an anhydrous condition. After stirring, the solution was transferred to a 100ml reactor and heated at 150 ℃ for 12 hours. After heating, the product was centrifuged 3 times, washed twice with distilled water, and dried at 60 ℃ for 12 hours.
The preparation method of ZIF-9 comprises the following steps: 1.05g of cobalt nitrate crystals and 0.85g of benzimidazole were weighed into a 100ml reaction vessel, and 60ml of DMF was added, followed by magnetic stirring for 30 minutes. And after stirring, putting the mixture into a 135 ℃ oven to be heated for 48h, washing the obtained purple crystal twice with DMF (dimethyl formamide), then washing twice with dichloromethane, and after washing, putting the mixture into a 60 ℃ oven to be dried for 12h to obtain a product, and drying the product for 12h at the temperature of 60 ℃.
Comparative example 1
1.05g of cobalt nitrate crystals and 0.85g of benzimidazole were weighed into a 100ml reaction vessel, and 60ml of DMF was added, followed by magnetic stirring for 30 minutes. And after stirring, putting the mixture into a 135 ℃ oven to be heated for 48h, washing the obtained purple crystal twice with DMF (dimethyl formamide), then washing twice with dichloromethane, and after washing, putting the mixture into a 60 ℃ oven to be dried for 12h to obtain a product, and drying the product for 12h at the temperature of 60 ℃ to obtain the ZIF-9.
The following performance tests were conducted on the above examples and comparative examples, and the test results are shown in FIGS. 1 to 4.
(1) Thermogravimetric analysis test, the test result is shown in figure 1; as can be seen from FIG. 1, the composites of examples 1-3 have good thermal stability, and the content is still as high as 80% at 1000 ℃, which greatly expands the application thereof under high temperature conditions.
(2) The samples of examples 1-4 and comparative example 1 were subjected to powder diffraction analysis tests, the results of which are shown in FIG. 2; as can be seen from FIG. 2, the powder diffraction characteristics of ZIF-9 are consistent with the crystallographic characteristics of the R3 hexagonal symmetric space group crystal system. The samples of examples 1-4 had substantially identical characteristic peaks and contained ZIF-9 and TiO 2 The characteristic peak of (A) shows that four complexes contain ZIF-9 and TiO 2
(3) And (3) antibacterial test: respectively and uniformly coating culture solution containing Escherichia coli and Bacillus (coating amount of 200 μ l, bacteria concentration of 109cfu/ml) on beef extract peptone culture medium in sterile environment of ultra-clean bench, diagonally dividing the culture medium into uniform culture medium after strain is uniformly coated and inoculated4 portions, the samples (10mg) of examples 1 to 4 were applied uniformly to the medium after inoculation. The obtained product is placed in a constant temperature incubator at 20 ℃ for 24 hours, and then taken out to observe the production condition of the colony, and the test results are shown in figure 3 and figure 4. The experimental results show that the sample of example 4 has inhibitory effect on the growth of both Escherichia coli and Bacillus, and the material of example 3 has significant inhibitory effect on the growth of Escherichia coli. The other two materials had no inhibitory effect on the growth of both bacteria. The reason may be that the ZIF-9 material is a porous metal-organic framework material, which has the function of increasing the specific surface area, the content of ZIF-9 is too small, the pore property of the material is deteriorated, the specific surface area is small, and the nano TiO is caused 2 The active sites of (a) are reduced, thereby reducing the antibacterial activity of the composite material. Moreover, the antibacterial material has the advantages of fully combining the porosity of MOFs materials, increasing the surface area of the materials and loading nano TiO 2 Better dispersibility and better bacteriostatic effect than single TiO 2
The above additional technical features can be freely combined and used in superposition by those skilled in the art without conflict. The above description is only a preferred embodiment of the present invention, and the technical solutions that achieve the objects of the present invention by substantially the same means are within the protection scope of the present invention.

Claims (7)

1. A preparation method of a nano titanium dioxide-loaded metal organic antibacterial material is characterized by dissolving ZIF-9 in an ethanol solvent, carrying out ultrasonic treatment, adding tetrabutyl titanate and ammonia water under stirring to obtain a reaction solution, carrying out magnetic stirring on the reaction solution under an anhydrous condition, transferring the solution into a reaction kettle after stirring, heating, and centrifuging, washing and drying products in sequence after heating to obtain the antibacterial material.
2. The preparation method of the nano titanium dioxide-loaded metal organic antibacterial material according to claim 1, wherein the mass ratio of the addition amount of tetrabutyl titanate to ZIF-9 is 0.1-0.6: 1.
3. The method as claimed in claim 1, wherein the heating temperature is 100-150 ℃.
4. The method for preparing the nano titanium dioxide-loaded metal organic antibacterial material according to claim 1, wherein the drying temperature is 50-90 ℃.
5. The preparation method of the nano titanium dioxide-loaded metal organic antibacterial material according to claim 1, wherein the preparation method of the ZIF-9 is as follows: weighing 1.04-5.25g of cobalt nitrate crystal and 0.85-4.25g of benzimidazole, putting the cobalt nitrate crystal and the benzimidazole into a reaction kettle, adding 50-80ml of DMF, then carrying out magnetic stirring, putting the mixture into an oven for drying after the stirring is finished to obtain a purple crystal, washing the purple crystal with DMF, then washing with dichloromethane, and putting the mixture into the oven for drying after the washing is finished to obtain the catalyst.
6. A nano titanium dioxide-loaded metal organic antibacterial material is characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. Use of the antibacterial material according to claim 6 for inhibiting escherichia coli and/or bacillus.
CN202210534069.7A 2022-05-17 2022-05-17 Nano-titanium dioxide-loaded metal organic antibacterial material and preparation method and application thereof Pending CN114885960A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120294921A1 (en) * 2010-01-27 2012-11-22 Xiaozhong Huang Antibacterial agent and method of preparing the same
CN102886279A (en) * 2011-07-20 2013-01-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for coating metal nanoparticles on surface of nano-titania
CN109499620A (en) * 2018-12-10 2019-03-22 怀化学院 TiO2The preparation method of/ZIF-8 composite photo-catalyst
CN112958054A (en) * 2021-02-02 2021-06-15 天津城建大学 TiO 22@ ZIF-67 composite nano material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120294921A1 (en) * 2010-01-27 2012-11-22 Xiaozhong Huang Antibacterial agent and method of preparing the same
CN102886279A (en) * 2011-07-20 2013-01-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for coating metal nanoparticles on surface of nano-titania
CN109499620A (en) * 2018-12-10 2019-03-22 怀化学院 TiO2The preparation method of/ZIF-8 composite photo-catalyst
CN112958054A (en) * 2021-02-02 2021-06-15 天津城建大学 TiO 22@ ZIF-67 composite nano material and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHENSUO YAN,ET AL.: ""Co-ZIF-9/TiO2 nanostructure for superior CO2 photoreduction activity"" *
杨静;扶教龙;徐孝文;: "载银沸石基纳米二氧化钛抗菌性能研究" *
车广波;马裕枫;王莹;李寓函;: "二氧化钛/金属有机骨架复合材料的制备及其应用" *

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Application publication date: 20220812