CN113751070A - Carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst, preparation method and application - Google Patents
Carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst, preparation method and application Download PDFInfo
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- CN113751070A CN113751070A CN202111189447.4A CN202111189447A CN113751070A CN 113751070 A CN113751070 A CN 113751070A CN 202111189447 A CN202111189447 A CN 202111189447A CN 113751070 A CN113751070 A CN 113751070A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/785—Polymers containing nitrogen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/42—Phosphorus; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/44—Elemental carbon, e.g. charcoal, carbon black
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
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- B01J35/39—
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- B01J35/61—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst, which comprises the following steps: preparing pre-reaction solution of urea and potassium hydroxide, partial thermal decomposition, and freeze drying to obtain spongy freeze dried powder. And carrying out thermal polymerization on the freeze-dried powder to obtain the carbon nitride nano gauze, washing and collecting. The carbon nitride nano gauze is pre-reacted with dopamine hydrochloride under the conditions of room temperature and darkness, and then is reacted under the conditions of illumination, oxygen and higher temperature. And finally, depositing silver phosphate in situ through electrostatic adsorption and ion exchange. The g-C3N4 nano-gauze with high catalytic activity is prepared by a freezing-gas pore-making method combined with a controllable potassium ion doping method, and the carbon nitride/polydopamine/silver phosphate hybrid nano-catalyst with a superlattice structure is prepared by controllable supermolecule assembly. The prepared nano-catalyst has excellent biocompatibility and wide application prospect in the aspects of in-situ ROS generation and in-situ oxygen supply in organisms.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic nano materials, and particularly relates to a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst, and a preparation method and application thereof.
Background
Graphite-phase carbon nitride (g-C3N 4) is a highly biocompatible, non-toxic (half-lethal oral dose: 5000mg/kg) visible light active polymer semiconductor. g-C3N4, the bandwidth is about 2.7ev, and the band gap structure can theoretically absorb sunlight with the wavelength less than 460nm to perform water reduction and oxidation, so that Reactive Oxygen Species (ROS) and oxygen are generated. However, due to the problems of small specific surface area, poor electron transfer capability, serious photocarrier recombination and the like of the bulk g-C3N4, the ROS generating activity and the Oxygen Evolution Reaction (OER) activity of the original g-C3N4 are limited.
The research shows that: it reacts with another Ag3PO4After the semiconductor catalyst forms a heterojunction, the charge transmission efficiency is enhanced, the electron-hole reset is inhibited, and the catalytic efficiency is enhanced. Many researchers are targeting Ag3PO4The preparation of g-C3N4 composite catalyst was studied accordingly. This type of invention is primarily directed to improving g-C3N4/Ag by surface modification3PO4The interfaces of the heterojunctions are in contact. Wherein, Xianzhu et al prepared silver phosphate/carbon nitride heterojunction (publication: CN 109012721A); song Li Min et al prepared a silver phosphate/carbon nitride composite membrane (publication No. CN 105214700A); okinawa et al prepared a bismuth tungstate/carbon nitride/silver phosphate heterojunction (publication: CN 109847771A). Although these studies were conducted on g-C3N4/Ag through optimized heterojunction construction3PO4The catalytic activity of the composite catalyst is partially improved, and the application effect of the composite catalyst in the chemical field is improved. However, the existing form of Ag3PO4the/g-C3N 4 hybrid catalyst is not suitable for biomedical applications. This is because (1) current Ag3PO4the/g-C3N 4 semiconductor catalyst has poor dispersibility and stability in water phaseAnd poor biocompatibility. (2) Catalytic activity remains limited, which necessitates high doses for biomedical applications to ensure that an effective dose of ROS and oxygen is generated at the focal tissue site. Not to be neglected, even if the catalyst has low histo-heterogeneity and good biocompatibility, the degradation, metabolism and discharge of the nano materials still bring additional burden to the organism. These disadvantages are to be overcome by effective surface modification, morphology change, active site construction and mass transfer design of the catalyst.
In summary, the existing g-C3N4/Ag3PO4The biomedical application of catalyst materials is difficult.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst, a preparation method and application thereof. The invention finally forms a multi-layer heterojunction structure which is a superlattice structure and is periodically generated by an extremely thin semiconductor single crystal film by regulating and controlling the doping behavior and the oxidation self-polymerization behavior among dopamine molecular layers. The prepared carbon nitride/polydopamine/silver phosphate superlattice nano catalyst material has good biological activity. And can generate ROS under acidic condition and generate oxygen under alkaline condition. Thereby being used for treating infectious wounds.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the following steps:
the method comprises the following steps: putting the urea solution and the potassium hydroxide solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, pre-reacting for 4-8 h at 80-120 ℃, taking out, putting into a freeze dryer, and freeze-drying to obtain sponge urea freeze-dried powder;
secondly, performing thermal polymerization reaction on the spongy urea freeze-dried powder in the step one in a muffle furnace, cooling after the reaction is finished, and washing and drying to obtain carbon nitride nano gauze;
step three, adding the carbon nitride nano gauze in the step two into double distilled water, and performing ultrasonic treatment to obtain a dispersion liquid; adding dopamine hydrochloride into the dispersion liquid, and stirring and reacting for 0.5-1.5 h; then adding an alkaline solution into the reaction material to adjust the pH value of the reaction material to 8.0-10, reacting for 24 hours at the temperature of 60-100 ℃, filtering the product, washing and drying to obtain a carbon nitride/polydopamine superlattice structure;
step four, adding the carbon nitride/polydopamine superlattice structure in the step three into water for ultrasonic dispersion, and then adding AgNO3Stirring and reacting for 5-15 min under the condition of keeping out of the sun, and then adding Na3PO4And stirring and reacting for 5-15 min under the condition of keeping out of the sun, and washing and drying a reaction product after suction filtration to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst.
The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that the mass ratio of urea to potassium hydroxide in the first step is as follows: (420-20160): 1.
The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that in the second step, the reaction temperature of the thermal polymerization reaction is 500-600 ℃, and the reaction time of the thermal polymerization reaction is 2-4 hours.
The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that the mass ratio of the dopamine hydrochloride to the carbon nitride nano gauze in the third step is 1 (1-4).
The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that in the third step, the alkaline solution is a tris solution, a sodium hydroxide solution, a triethylamine aqueous solution or a buffer solution with the pH value of 8-10.
The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that the buffer solution is potassium dihydrogen phosphate-sodium hydroxide buffer solution, boric acid-borax buffer solution, glycine-sodium hydroxide buffer solution or borax-sodium hydroxide buffer solution.
The carbon nitride/polydopamineThe preparation method of the silver phosphate superlattice nano catalyst is characterized by comprising the step four of AgNO3And the mass ratio of the carbon nitride/polydopamine superlattice structure is (0.85-7.65): 1, and AgNO3And Na3PO4Is 1.34: 1.
In addition, the invention also provides the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst prepared by the preparation method.
Further, the invention provides an application of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method in water photolysis to produce oxygen.
Furthermore, the invention provides an application of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst prepared by the preparation method in preparation of a medicament for treating infectious wounds.
Compared with the prior art, the invention has the following advantages:
1. the invention is different from PDA which only coats the surface of the catalyst, in the invention, the 'multilayer heterojunction structure formed by periodically generating an extremely thin semiconductor single crystal film', namely a superlattice structure, is finally formed due to the regulation and control of the doping behavior and the oxidation self-polymerization behavior between dopamine molecular layers. This superlattice structure formed by carbon nitride and polydopamine is first reported.
2. The carbon nitride/polydopamine/silver phosphate superlattice nano catalyst has the advantages of enhanced visible light utilization rate, prolonged carrier life and accelerated carrier separation. On the premise of selecting the high-biocompatibility base material, the hybrid superlattice nano catalyst with high catalytic activity and a proper energy band structure can utilize water with the highest organism content as a substrate, and finally generate ROS in an acidic microenvironment in an organism in a catalytic manner, and oxygen in an alkaline microenvironment. I.e., to effect on-demand therapy corresponding to disease progression (e.g., infectious wound healing progression) (see fig. 1).
3. The carbon nitride nano-gauze prepared by doping gas elements, preparing holes and freeze drying has more points, surface and body defects and large specific surface area, and can provide a large number of photocatalytic active sites.
4. The superlattice structure constructed by inserting the polydopamine molecular layer between the carbon nitride layers can improve the visible light utilization rate and accelerate the electron hole separation rate, thereby achieving the purpose of improving the photocatalytic performance.
5. The carbon nitride/polydopamine/silver phosphate superlattice nano catalyst material has good biological activity. And can generate ROS under acidic condition and generate oxygen under alkaline condition. Thereby being used for treating infectious wounds.
The technical solution of the present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
Drawings
Fig. 1 is a model diagram of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst for microenvironment-regulated ROS antibiosis and in-situ oxygen supply.
Fig. 2 is a process flow of preparing the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst of the present invention.
FIG. 3 shows the SEM and TEM photographs of the products obtained in the steps of example 1.
FIG. 4 shows surface Zeta potential and nitrogen adsorption ratio surface analysis of the product of each step of example 1 of the present invention and pore size distribution of the final product.
FIG. 5 shows the X-ray diffraction pattern and Fourier transform infrared absorption spectrum analysis of the product obtained in each step of example 1 of the present invention.
FIG. 6 shows steady-state, transient fluorescence analysis of the product obtained in the steps of example 1.
FIG. 7 is a transient photocurrent analysis of the product of example 1.
FIG. 8 is a chemical impedance analysis of the product obtained in each step of example 1 of the present invention.
FIG. 9 shows high resolution SEM images of final products obtained in examples 4, 5 and 8 of the present invention.
Fig. 10 is a cell biocompatibility analysis in application example 1 of the present invention.
FIG. 11 shows the photolytic oxygen production activity of example 2 of application of the present invention.
FIG. 12 is a graph showing the efficacy of the treatment of infected wounds of mice according to application example 3 of the present invention.
Detailed Description
Example 1
Referring to the flowchart of fig. 2, the present embodiment includes the following steps:
dissolving 200g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.1g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 2mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 6h at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 2 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 100mg of dopamine hydrochloride into the dispersion, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 1.21mg/mL of tris solution into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 3mmol (0.51g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; then, 1mmol (0.38g) of Na was added3PO4Light-resistant, 800 rpmReacting for 10min under the condition of magnetic stirring per minute; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
FIG. 3 is a high resolution scanning and transmission electron micrograph of the product of each step of example 1, showing the morphology of the product obtained in this example. As can be seen, the obtained g-C3N4 nano gauze has the size of about 200nm and a porous surface structure; the obtained g-C3N4/PDA has a regular superlattice structure; in situ deposition of Ag on the surface of g-C3N4/PDA3PO4The particle size is small and uniform. These micro-phenotypes are the structural basis for the high catalytic activity of the nanocatalysts.
FIG. 4a is a surface zeta potential analysis of the product of each step of example 1. Therefore, the g-C3N4 nano tissue obtained by the invention has the surface potential which is obviously greater than that of the blocky g-C3N4, which reflects that the g-C3N4 nano tissue obtained by the invention has more point, surface and body defects. The g-C3N4/PDA surface potential after further self-assembly with PDA supermolecule becomes more negative, which further enhances the monodispersity and stability of the nano catalyst in water, and is one of the reasons of high subsequent catalytic activity. FIG. 4a is a nitrogen adsorption specific surface area analysis of the products of the respective steps of example 1. The results show that the specific surface area of the g-C3N4 nano tissue prepared by the invention is more than 300cm2And/g, the specific surface area after the supermolecule self-assembly with the PDA is further increased. The large specific surface area means that a large number of photocatalytically active sites can be provided. The characteristics are based on the high catalytic activity of the g-C3N4/PDA/Ag3PO4 heterojunction nano-catalyst prepared on the basis of the g-C3N4/PDA superlattice assembly.
FIG. 5a is a Fourier transform infrared spectrum of the product of each step of example 1 demonstrating the material composition of the product of each step compounding the design of the invention illustrated in FIG. 1. FIG. 5b is an X-ray diffraction analysis of the product obtained in each step of example 1, which shows that the interlayer spacing of carbon nitride after doping dopamine molecules is changed from 0.3nm to 0.33nm, which results in improved mass transfer performance of the catalyst and enhanced permeability to substrate water molecules; it can be seen that the crystal structure of each part of the product of the invention is consistent with the assumption.
FIG. 6 shows the transient and steady state fluorescence changes resulting from the modifications at each step in example 1. Visible preparation of superlattice structure and in-situ deposition of Ag3PO4The steady-state fluorescence of g-C3N4 is reduced after heterojunction preparation, and the fluorescence lifetime is shortened. This shows that the decrease in energy released in the form of radiative transitions for the same light absorption is indirectly reflected in an increased photo-chemical conversion capability of the resulting catalyst in this way of preparation.
FIG. 7 shows the transient photocurrent variation caused by the modification steps in example 1. The result shows that the construction of the superlattice structure and the subsequent construction of the heterojunction can inhibit the recombination of photon-generated carriers, thereby achieving the aim of enhancing the photocatalytic activity.
FIG. 8 is an electrochemical impedance analysis of the modified product of each step in example 1. The results show that the construction of the superlattice structure and the subsequent construction of the heterojunction can accelerate the separation and migration of the photon-generated carriers, thereby further enhancing the photocatalytic activity.
Example 2
The embodiment comprises the following steps:
dissolving 200g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.05g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 0.5mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 6h at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 2 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 100mg of dopamine hydrochloride into the dispersion, and reacting for 0.5h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 1.21mg/mL of tris solution into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 9mmol (1.53g) of AgNO3Reacting for 8min under the condition of magnetic stirring at 800 r/min in a dark place; 3mmol (1.44g) of Na were added thereto3PO4Reacting for 12min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
Example 3
The embodiment comprises the following steps:
dissolving 100g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.05g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 1mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 4 hours at 100 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 2g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 4 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment at 60kHz for 30min to obtain a uniform dispersion liquid; adding 50mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 0.04mg/mL sodium hydroxide solution into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 60 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 1mmol (0.17g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; further, 0.33mmol (0.127g) of Na was added3PO4Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
Example 4
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.15g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 2mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 8 hours at 80 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 600 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 3 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 150mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding triethylamine water solution with volume concentration of 0.1% into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 100 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 9mmol (1.53g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; 3mmol (1.14g) of Na were added thereto3PO4Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
FIG. 9a is a high resolution SEM of the final product of example 4. The obtained nano catalyst g-C3N4/PDA/Ag3PO4The size is about 400nm, the grain size of the in-situ generated Ag3PO4 is about 20nm, the monodispersity is better, and the surface of the g-C3N4/PDA is completely covered.
Example 5
The embodiment comprises the following steps:
dissolving 200g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.05g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 0.5mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 6h at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 580 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 2.5 h; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 200mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1.5 hours under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding a potassium dihydrogen phosphate-sodium hydroxide buffer solution into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 3mmol (0.51g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; then, 1mmol (0.38g) of Na was added3PO4Reacting for 8min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
FIG. 9b is a high resolution SEM of the final product of example 5. The obtained nano catalyst g-C3N4/PDA/Ag3PO4About 800nm in size, in-situ generated Ag3PO4The particle size is about 10nm, the monodispersity is better, and the surface of the product is covered more completely with g-C3N 4/PDA.
Example 6
The embodiment comprises the following steps:
dissolving 200g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.1g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 1mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 8 hours at 80 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 3 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 80mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 1.21mg/mL of tris solution into the reaction material, and adjusting the pH value of the reaction material to 8; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 3mmol (0.51g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; then, 1mmol (0.38g) of Na was added3PO4Reacting for 5min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
Example 7
The embodiment comprises the following steps:
dissolving 100g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.15g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 1.5mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 4 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 4g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 2.5 h; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 100mg of dopamine hydrochloride into the dispersion, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 0.04mg/mL sodium hydroxide solution into the reaction material, and adjusting the pH value of the reaction material to 9; reacting for 24 hours at 90 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 3mmol (0.51g) of AgNO3Reacting for 5min under the condition of magnetic stirring at 800 r/min in a dark place; then, 1mmol (0.38g) of Na was added3PO4Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
Example 8
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.05g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 0.5mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 8 hours at 100 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 3 hours; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 200mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 0.04mg/mL sodium hydroxide solution into the reaction material, and adjusting the pH value of the reaction material to 8.5; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 1mmol (0.17g) of AgNO3Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; further, 0.33mmol (0.127g) of Na was added3PO4Reacting for 10min under the condition of magnetic stirring at 800 r/min in a dark place; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
FIG. 9c is a high resolution SEM of the final product of example 8. The obtained nanocatalysisAgent g-C3N4/PDA/Ag3PO4About 600nm in size, in-situ generated Ag3PO4The particle size is about 5nm, the monodispersity is better, and the surface of the product is partially covered by g-C3N 4/PDA.
Example 9
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, fixing the volume to 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain a uniform urea stock solution; dissolving 0.05g of KOH in 75mL of double distilled water, and performing ultrasonic treatment at 30kHz for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 0.5mL of KOH stock solution, putting into a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, and reacting for 6h at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing at-20 ℃ for 12h, transferring to-80 ℃ for 24h, and freeze-drying in a freeze dryer to obtain sponge urea freeze-dried powder;
step two, taking 2g of the spongy urea freeze-dried powder obtained in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible, and wrapping the ceramic crucible with double-layer tinfoil; preheating a muffle furnace to 600 ℃, then putting a ceramic crucible filled with sponge urea freeze-dried powder into the preheated muffle furnace, and carrying out thermal polymerization for 2.5 h; taking out, cooling, washing for 3 times by double distilled water, drying and collecting to obtain the carbon nitride nano gauze g-C3N 4;
step three, weighing 200mg of g-C3N4 obtained in the step two, adding the g-C3N4 into 320mL of double distilled water, and carrying out ultrasonic treatment on 60kHz for 30 minutes to obtain a uniform dispersion liquid; adding 50mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h under the condition of magnetic stirring at room temperature of 300 revolutions per minute; then adding 0.04mg/mL sodium hydroxide solution into the reaction material, and adjusting the pH value of the reaction material to 10; reacting for 24 hours at 80 ℃ under the condition of opening or introducing oxygen; carrying out suction filtration and separation on the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing for 3 times by using double distilled water, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, taking 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three, adding 150mL of water for ultrasonic dispersion, and then adding 9mmol (1.53g) of AgNO3Reacting for 15min under the condition of magnetic stirring at 800 r/min in a dark place; 3mmol (1.14g) of Na were added thereto3PO4Light-shielding, 800 rpmReacting for 15min under the condition of magnetic stirring; filtering and separating the reaction product by using a sand core funnel with the diameter of 0.2 mu m, washing the reaction product for 3 times by using double distilled water, drying and collecting the reaction product to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag3PO4。
Application example 1
g-C3N4/PDA/Ag prepared in example 13PO4The superlattice nano-catalyst is co-cultured with animal somatic cells. The specific operation and experimental results are as follows:
first, L929 (mouse fibroblast) cells were seeded into 96-well plates and incubated until adherent. Then, the medium containing the sample at 300. mu.g/mL was used in place of the original medium, and the cells were co-cultured in a cell culture incubator for 72 hours. Next, the mixed medium was removed and gently rinsed with PBS. Finally, LIVE/DEADTM cell viability/cytotoxicity kits were used for detection and laser confocal fiberoptic imaging.
As shown in fig. 10, green cells are live cells and red cells are dead cells. It can be seen that the products of the steps of the present invention have good biocompatibility, which is obtained by mixing the g-C3N4/PDA/Ag3PO4The superlattice nano catalyst is used as an application foundation in the field of biomedicine.
Application example 2
The g-C3N4/PDA/Ag obtained in example 13PO4The superlattice nano-catalyst is applied to visible light water photolysis to generate oxygen under alkaline conditions. And compared with the oxygen production efficiency of the product of each step of example 1. The specific operation and experimental results are as follows:
150mg of g-C3N4/PDA/Ag3PO4Adding the superlattice nano catalyst solid powder into 100mL of 1M KOH aqueous solution, and then adding 1g of AgNO3Performing ultrasonic treatment for 15min, adding into a reaction bottle, placing the reaction bottle in an atmosphere controller, removing air in the bottle through nitrogen, vacuumizing for 0.5h, placing in a multi-channel photocatalytic reaction device, irradiating for 4h by xenon light, monitoring generated gas on line by using a gas chromatograph, wherein the detector is a TCD thermal conductivity detector, and the carrier gas is high-purity nitrogen or argon.
As shown in FIG. 11, the g-C3N4/PDA/Ag3PO4The superlattice nano catalyst has the oxygen production activity of 500 mu mol/g/h, and the oxygen production activity is obviously reduced after 4 times of circulation, which shows that the superlattice nano catalyst has good visible light stability.
Application example 3
The g-C3N4/PDA/Ag obtained in example 13PO4The superlattice nano-catalyst is applied to treatment of mouse skin infectious wounds. The specific operation and experimental results are as follows:
female Balb/c mice (about 18g) at 4 weeks of age were anesthetized and unhaired prior to modeling. First, a full-thickness wound model was created using a skin biopsy punch with a diameter of 8 mm. Then, the mixture will contain 2X 108CFU/mL E.coli and 1X 108A mixed bacterial suspension of CFU/mL Staphylococcus aureus was inoculated onto the wound. Finally, the mice were divided into 4 groups (8 mice per group); (1) negative control: no treatment is carried out; (2) positive control: mupirocin ointment (300mg, 2 wt%) was administered (3) to the simulated sunlight treatment group; (4) g-C3N4/PDA/Ag3PO4Group administered (300mg, 1 wt%); (5) simulated sunlight combined g-C3N4/PDA/Ag3PO4And (4) treatment groups. The left and right treatment plans are once a day; the group involved in simulated solar treatment comprises the following simulated solar treatment schemes: 100mW/cm2Is irradiated with a Xe lamp with a filter (AM 1.5G) for 1 hour at an optical density of (1).
As shown in FIG. 12, the simulated sunlight combined g-C3N4/PDA/Ag under the condition of wound diameter of 8mm3PO4The treatment group completed epithelial regeneration on day 10, while the negative and positive control groups did not complete healing on day 15. The outstanding curative effect is that the microenvironment in the inflammatory phase of the infectious wound is acidic, and the treatment requires antibiosis; once in the remodeling stage, the wound microenvironment becomes basic, and one of the corresponding therapeutic requirements is in situ oxygen supply to accelerate cell proliferation and differentiation. Use of simulated sunlight in combination with g-C3N4/PDA/Ag3PO4The advantages of treating hair are: (1) using ROS-generating g-C3N4/PDA/Ag3PO4The photocatalyst replaces antibiotics for antibiosis, so that the accumulation of drug resistance and the generation of drug-resistant bacteria can be effectively avoided; (2) using in situ catalytic water splittingg-C3N4/PDA/Ag for oxygen decomposition3PO4The photocatalyst replaces remote oxygen supply depending on blood circulation, and can avoid the defect of uncontrollable space-time distribution caused by high reactivity of oxygen and components in a body. In conclusion, on the premise of good biocompatibility and high visible light catalytic activity, the g-C3N4/PDA/Ag prepared by the invention3PO4The superlattice nano-catalyst can utilize water with the highest organism content as a substrate to realize that ROS is generated in situ under an acidic microenvironment in an inflammatory period of infected wounds to play an antibacterial role; excellent efficacy of in situ oxygen production in alkaline microenvironment during remodeling to accelerate the re-epithelialization process.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the following steps:
the method comprises the following steps: putting the urea solution and the potassium hydroxide solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, pre-reacting for 4-8 h at 80-120 ℃, taking out, putting into a freeze dryer, and freeze-drying to obtain sponge urea freeze-dried powder;
secondly, performing thermal polymerization reaction on the spongy urea freeze-dried powder in the step one in a muffle furnace, cooling after the reaction is finished, and washing and drying to obtain carbon nitride nano gauze;
step three, adding the carbon nitride nano gauze in the step two into double distilled water, and performing ultrasonic treatment to obtain a dispersion liquid; adding dopamine hydrochloride into the dispersion liquid, and stirring and reacting for 0.5-1.5 h; then adding an alkaline solution into the reaction material to adjust the pH value of the reaction material to 8.0-10, reacting for 24 hours at the temperature of 60-100 ℃, filtering the product, washing and drying to obtain a carbon nitride/polydopamine superlattice structure;
step four, the carbon nitride/polydopamine superlattice in the step three is subjected toAdding the structure into water for ultrasonic dispersion, and then adding AgNO3Stirring and reacting for 5-15 min under the condition of keeping out of the sun, and then adding Na3PO4And stirring and reacting for 5-15 min under the condition of keeping out of the sun, and washing and drying a reaction product after suction filtration to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst.
2. The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein the mass ratio of urea to potassium hydroxide in the first step is as follows: (420-20160): 1.
3. The method for preparing carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein the reaction temperature of the thermal polymerization reaction in the second step is 500-600 ℃, and the reaction time of the thermal polymerization reaction is 2-4 h.
4. The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein the mass ratio of the dopamine hydrochloride to the carbon nitride nano gauze in the third step is 1 (1-4).
5. The method for preparing the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein the alkaline solution in the third step is a tris solution, a sodium hydroxide solution, a triethylamine aqueous solution or a buffer solution with a pH value of 8-10.
6. The method for preparing carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 5, characterized in that the buffer solution is potassium dihydrogen phosphate-sodium hydroxide buffer solution, boric acid-borax buffer solution, glycine-sodium hydroxide buffer solution or borax-sodium hydroxide buffer solution.
7. A nitriding according to claim 1The preparation method of the carbon/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the step four of AgNO3And the mass ratio of the carbon nitride/polydopamine superlattice structure is (0.85-7.65): 1, and AgNO3And Na3PO4Is 1.34: 1.
8. The carbon nitride/polydopamine/silver phosphate superlattice nano catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method according to any one of claims 1 to 7 in water photolysis for generating oxygen.
10. Use of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method according to any one of claims 1 to 7 in preparation of a medicament for treating infectious wounds.
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