CN113751070B - 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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- CN113751070B CN113751070B CN202111189447.4A CN202111189447A CN113751070B CN 113751070 B CN113751070 B CN 113751070B CN 202111189447 A CN202111189447 A CN 202111189447A CN 113751070 B CN113751070 B CN 113751070B
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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 liquid of urea and potassium hydroxide, carrying out partial thermal decomposition, and freeze-drying to obtain spongy freeze-dried powder. And (5) performing thermal polymerization on the freeze-dried powder to obtain the carbon nitride nano tissue, washing and collecting. The carbon nitride nanometer tissue reacts with dopamine hydrochloride under the conditions of room temperature and darkness, and then reacts under the conditions of illumination, oxygenation and higher temperature. Finally, silver phosphate is deposited in situ through electrostatic adsorption and ion exchange. The high-catalytic-activity g-C3N4 nano tissue is prepared by combining a freezing-gas pore-forming method and 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-situ ROS generation and in-situ oxygen supply in organisms.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalysis nano materials, and particularly relates to a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst, a preparation method and application thereof.
Background
Graphite phase carbon nitride (Graphitic carbon nitride, g-C3N 4) is a visible light active polymer semiconductor with high biocompatibility and no toxicity (oral half-life: 5000 mg/kg). g-C3N4, the bandwidth is about 2.7ev, and the band gap structure can absorb sunlight with the wavelength less than 460nm to reduce and oxidize water theoretically, so that Reactive Oxygen Species (ROS) and oxygen are generated. However, due to the small specific surface area of the bulk g-C3N4, poor electron transfer capability, serious photo-generated carrier recombination and other problems, the ROS generation activity and Oxygen Evolution Reaction (OER) activity of the original g-C3N4 are limited.
Studies have shown that: it is combined with another Ag 3 PO 4 Semiconductor catalyst heterojunction formationAfter that, the charge transport efficiency is enhanced, the electron-hole reset is suppressed, and the catalytic efficiency is enhanced. Many researchers are directed to Ag 3 PO 4 The preparation of the g-C3N4 composite catalyst is correspondingly studied. This type of invention is mainly directed to improving g-C3N4/Ag by surface modification 3 PO 4 Interface contact of the heterojunction. Among them, xia Mingzhu et al prepared a silver phosphate/carbon nitride heterojunction (publication number: CN109012721 a); song Limin et al prepared a silver phosphate/carbon nitride composite film (publication No. CN 105214700A); he Jinyun et al prepared a tungstic acid/carbon nitride/silver phosphate heterojunction (publication No. CN 109847771A). Although these studies construct the pair g-C3N4/Ag through optimized heterojunction 3 PO 4 The catalytic activity of the composite catalyst is partially improved, and the application effect of the composite catalyst in the chemical industry field is improved. However, the existing form Ag 3 PO 4 the/g-C3N 4 composite catalyst is not suitable for biomedical applications. This is because (1) current Ag 3 PO 4 the/g-C3N 4 semiconductor catalyst has poor dispersibility and stability in water phase and poor biocompatibility. (2) Catalytic activity is limited, which necessitates high doses for biomedical applications to ensure efficient metering of ROS and oxygen production at focal tissue sites. It is not negligible that even though these catalysts have low tissue heterogeneity, they have good biocompatibility, and the degradation, metabolism, and excretion of these nanomaterials still place additional burden on the body. These drawbacks are to be overcome by effective catalyst surface modification, morphology modification, active site architecture and mass transfer design.
In summary, the existing g-C3N4/Ag 3 PO 4 Biomedical applications of catalyst materials are 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. According to the invention, through regulating and controlling the doping behavior and the oxidation self-aggregation behavior between the dopamine molecules, a multi-layer heterojunction structure formed by periodically generating an extremely thin semiconductor single crystal film, namely a superlattice structure, is finally formed. The prepared carbon nitride/polydopamine/silver phosphate superlattice nano catalyst material has good biological activity. And is capable of generating ROS under acidic conditions and oxygen under alkaline conditions. Thereby being used for the treatment of infectious wounds.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the following steps of:
step one: placing urea solution and potassium hydroxide solution together in a polytetrafluoroethylene-lined high-pressure reaction kettle, pre-reacting for 4-8 hours at 80-120 ℃, taking out, and placing in a freeze dryer for freeze drying to obtain spongy urea freeze-dried powder;
step two, carrying out thermal polymerization reaction on the spongy urea freeze-dried powder in the step one in a muffle furnace, and cooling, washing and drying after the reaction is finished to obtain carbon nitride nano-tissue;
step three, adding the carbon nitride nano tissue obtained in the step two into double distilled water, and performing ultrasonic treatment to obtain dispersion liquid; adding dopamine hydrochloride into the dispersion liquid, and stirring and reacting for 0.5-1.5 h; then adding alkaline solution into the reaction materials to adjust the pH value of the reaction materials to 8.0-10, reacting for 24 hours at 60-100 ℃, and filtering, washing and drying the product to obtain the 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 AgNO 3 Stirring and reacting for 5-15 min under the dark condition, and then adding Na 3 PO 4 Stirring and reacting for 5-15 min under the dark condition, filtering the reaction product, washing and drying 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 by comprising the following steps of: (420-20160): 1.
the preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized in that 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.
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 the alkaline solution in the third step is a tris (hydroxymethyl) aminomethane solution, a sodium hydroxide solution, a triethylamine aqueous solution or a buffer solution with a 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 preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the following steps of 3 And the mass ratio of the carbon nitride to the polydopamine superlattice structure is (0.85-7.65) to 1, agNO 3 And Na (Na) 3 PO 4 The mass ratio of (2) is 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 application of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method in preparing oxygen by photolysis water.
Furthermore, the invention provides an application of the carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method in preparing medicines for treating infectious wounds.
Compared with the prior art, the invention has the following advantages:
1. the invention is different from the PDA that only coats the surface of the catalyst, in the invention, the multi-layer heterojunction structure formed by periodically generating an extremely thin semiconductor single crystal film, namely the superlattice structure is finally formed due to the regulation and control of the doping behavior and the oxidation self-aggregation behavior between the dopamine molecules. This superlattice structure formed from carbon nitride and polydopamine was first reported.
2. The carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst has the advantages of enhanced visible light availability, prolonged carrier service life and accelerated carrier separation. On the premise of selecting a high-biocompatibility base material, the hybridization superlattice nano catalyst with high catalytic activity and proper energy band structure can utilize water with highest organism content as a substrate, and finally catalyze and generate ROS in an acidic microenvironment in an organism, and generate oxygen in an alkaline microenvironment. I.e. to achieve on-demand therapy (as in figure 1) corresponding to the disease process (e.g. infected wound healing process).
3. According to the invention, through doping of gas elements, pore-forming and freeze drying, the obtained carbon nitride nano tissue has more points, surfaces and bulk 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 availability and accelerate the electron hole separation rate, thereby achieving the purpose of improving the photocatalysis performance.
5. The carbon nitride/polydopamine/silver phosphate superlattice nano catalyst material has good biological activity. And is capable of generating ROS under acidic conditions and oxygen under alkaline conditions. Thereby being used for the treatment of infectious wounds.
The technical scheme of the invention is further described in detail below with reference to the detailed description and the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of the carbon nitride/polydopamine/silver phosphate superlattice nanocatalyst of the invention for micro-environment regulated ROS antibacterial and in situ oxygen supply.
Fig. 2 is a process flow of preparing the carbon nitride/polydopamine/silver phosphate superlattice nanocatalyst of the invention.
FIG. 3 is a scanning electron microscope and transmission electron microscope photograph of the product of each step of example 1 of the present invention.
FIG. 4 shows the Zeta potential and nitrogen adsorption specific surface analysis of the product and the pore size distribution of the final product at each step of example 1 of the present invention.
FIG. 5 shows an X-ray diffraction pattern and Fourier transform infrared absorbance spectra of the products of each step of example 1 of the invention.
FIG. 6 shows steady-state, transient fluorescence analysis of the product obtained in the steps of example 1 of the present invention.
FIG. 7 is a transient photocurrent analysis of the product obtained in the steps of example 1 of the present invention.
FIG. 8 shows the chemical impedance analysis of the product obtained in the steps of example 1 of the present invention.
FIG. 9 shows a high resolution scanning electron microscope of the final products obtained in examples 4, 5 and 8.
FIG. 10 shows a cell biocompatibility analysis of application example 1 of the present invention.
FIG. 11 shows the oxygen production activity by photolysis water according to application example 2 of the present invention.
FIG. 12 is a graph showing the effect of the present invention on wound infection in mice according to application example 3.
Detailed Description
Example 1
Referring to the flowchart 2, the present embodiment includes the steps of:
step one, 200g of urea is dissolved in double distilled water and the volume is fixed to reach 625mL,30kHz ultrasonic treatment is carried out for 8min, so that uniform urea stock solution is obtained; dissolving 0.1g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 6 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 2 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; adding 100mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h at room temperature under the magnetic stirring condition of 300 revolutions per minute; then adding 1.21mg/mL of a tris (hydroxymethyl) aminomethane 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 3mmol (0.51 g) of AgNO is added 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; 1mmol (0.38 g) of Na was added 3 PO 4 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
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. The obtained g-C3N4 nano tissue has a size of about 200nm and a porous surface structure; the obtained g-C3N4/PDA has a regular superlattice structure; ag deposited on g-C3N4/PDA surface in situ 3 PO 4 The particle size is small and uniform. These microscopic phenotypes are the structural basis for the high catalytic activity of the nanocatalyst.
FIG. 4a shows the zeta potential analysis of the product of each step of example 1. It can be seen that the g-C3N4 nano-tissue obtained by the invention has a surface potential significantly greater than that of bulk g-C3N4, which reflects that the g-C3N4 nano-tissue obtained by the invention has more defects of points, surfaces and bodies. The g-C3N4/PDA surface potential after further self-assembly with PDA supermolecule becomes more negative, which makes the nano catalyst monodisperse in waterAnd further enhanced stability, is one of the reasons for its subsequent high catalytic activity. FIG. 4c is a nitrogen adsorption specific surface area analysis of the product of each step of example 1. The result shows that the nitrogen adsorption volume of the g-C3N4 nano tissue prepared by the invention is more than 300cm 3 Per g, BET specific surface area of 138.25m 2 And/g, the specific surface area after self-assembly with PDA supramolecules is further increased. This large specific surface area property means that a large number of photocatalytically active sites can be provided. These characteristics are the basis of the high catalytic activity of the g-C3N4/PDA/Ag3PO4 heterojunction nano-catalyst prepared based on 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 composition of matter of the product of each step in combination with the inventive design shown in FIG. 1. FIG. 5b is an X-ray diffraction analysis of the product obtained by carrying out the steps of example 1, showing that the interlayer spacing of carbon nitride after doping with dopamine molecules is changed from 0.3nm to 0.33nm, which improves the mass transfer performance of the catalyst and enhances the permeability to substrate water molecules; it can also be seen that the crystal structure of the products of the various fractions in the present invention is envisaged.
FIG. 6 shows the transient and steady state fluorescence changes resulting from the modifications of the steps in example 1. It can be seen that superlattice structure is prepared and Ag is deposited in situ 3 PO 4 After the heterojunction is prepared, the steady-state fluorescence of g-C3N4 is reduced, and the fluorescence lifetime is shortened. This illustrates the reduced energy released in the form of radiative transitions at the same light absorption, which indirectly reflects the enhanced photo-chemical conversion capability of the catalyst obtained in this manner of preparation.
Fig. 7 shows the change in transient photocurrent caused by each step of modification 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 purpose 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 photogenerated carriers, thereby further enhancing the photocatalytic activity.
Example 2
The embodiment comprises the following steps:
step one, 200g of urea is dissolved in double distilled water and the volume is fixed to reach 625mL,30kHz ultrasonic treatment is carried out for 8min, so that uniform urea stock solution is obtained; dissolving 0.05g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 6 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 2 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; adding 100mg of dopamine hydrochloride into the dispersion liquid, and reacting for 0.5h under the magnetic stirring condition of 300 r/min at room temperature; then adding 1.21mg/mL of a tris (hydroxymethyl) aminomethane 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 9mmol (1.53 g) of AgNO is added 3 The reaction is carried out for 8min under the magnetic stirring condition of light shielding and 800 rpm; 3mmol (1.44 g) of Na was added 3 PO 4 The reaction is carried out for 12min under the conditions of light shielding and 800 revolutions per minute magnetic stirring; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
Example 3
The embodiment comprises the following steps:
step one, dissolving 100g of urea in double distilled water, and performing constant volume to reach 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain uniform urea stock solution; dissolving 0.05g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 4 hours at 100 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, 2g of the spongy urea freeze-dried powder in the step one is taken and placed in a ceramic crucible, covered and wrapped by double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 4 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30min to obtain uniform dispersion; adding 50mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h at room temperature under the magnetic stirring condition 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 1mmol (0.17 g) of AgNO is added 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; then 0.33mmol (0.127 g) Na was added 3 PO 4 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride/polydopamine/silver phosphate superlattice nano catalystChemical agent g-C3N4/PDA/Ag 3 PO 4 。
Example 4
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, and performing constant volume to reach 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain uniform urea stock solution; dissolving 0.15g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 8 hours at 80 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 600 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 3 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; 150mg of dopamine hydrochloride is added into the dispersion liquid, and the mixture reacts for 1 hour under the magnetic stirring condition of 300 revolutions per minute at room temperature; 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 9mmol (1.53 g) of AgNO is added 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; 3mmol (1.14 g) of Na was added 3 PO 4 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; the reaction product was separated by suction filtration through a 0.2 μm sand funnel, washed 3 times with double distilled water, dried and collectedObtaining the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
FIG. 9a is a high resolution scanning electron micrograph of the end product of example 4. The obtained nano catalyst g-C3N4/PDA/Ag 3 PO 4 The size is about 400nm, the in-situ generated Ag3PO4 has the particle size of about 20nm, better monodispersity and comprehensive surface coverage of g-C3N 4/PDA.
Example 5
The embodiment comprises the following steps:
step one, 200g of urea is dissolved in double distilled water and the volume is fixed to reach 625mL,30kHz ultrasonic treatment is carried out for 8min, so that uniform urea stock solution is obtained; 00.05g KOH is dissolved in 75mL double distilled water, and 30kHz ultrasonic treatment is carried out for 2min to form uniform potassium hydroxide stock solution; taking 21mL of urea stock solution, adding 0.5mL of KOH stock solution, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 6 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 580 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 2.5 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; 200mg of dopamine hydrochloride is added into the dispersion liquid, and the reaction is carried out for 1.5 hours under the magnetic stirring condition of 300 revolutions per minute at room temperature; then adding 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine supercrystal obtained in the step three is takenLattice structure, added to 150mL of water for ultrasonic dispersion, then added with 3mmol (0.51 g) of AgNO 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; 1mmol (0.38 g) of Na was added 3 PO 4 The reaction is carried out for 8min under the magnetic stirring condition of light shielding and 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
FIG. 9b is a high resolution scanning electron micrograph of the end product of example 5. The obtained nano catalyst g-C3N4/PDA/Ag 3 PO 4 About 800nm in size, in situ formed Ag 3 PO 4 The particle size is about 10nm, the monodispersity is good, and the surface coverage of the g-C3N4/PDA is more comprehensive.
Example 6
The embodiment comprises the following steps:
step one, 200g of urea is dissolved in double distilled water and the volume is fixed to reach 625mL,30kHz ultrasonic treatment is carried out for 8min, so that uniform urea stock solution is obtained; dissolving 0.1g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 8 hours at 80 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 3 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; adding 80mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h at room temperature under the magnetic stirring condition of 300 r/min; then adding 1.21mg/mL of a tris (hydroxymethyl) aminomethane solution into the reaction material, and adjusting the pH value of the reaction material to 8; reacting for 24 hours at 80 ℃ under the conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 3mmol (0.51 g) of AgNO is added 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; 1mmol (0.38 g) of Na was added 3 PO 4 The reaction is carried out for 5min under the conditions of light shielding and magnetic stirring at 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
Example 7
The embodiment comprises the following steps:
step one, dissolving 100g of urea in double distilled water, and performing constant volume to reach 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain uniform urea stock solution; dissolving 0.15g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 4 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, 4g of the spongy urea freeze-dried powder in the step one is taken and placed in a ceramic crucible, covered and wrapped by double-layer tinfoil; preheating a muffle furnace to 550 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 2.5 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; adding 100mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h at room temperature under the magnetic stirring condition 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 3mmol (0.51 g) of AgNO is added 3 The reaction is carried out for 5min under the conditions of light shielding and magnetic stirring at 800 rpm; 1mmol (0.38 g) of Na was added 3 PO 4 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
Example 8
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, and performing constant volume to reach 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain uniform urea stock solution; dissolving 0.05g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 8 hours at 100 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, taking 3g of the spongy urea freeze-dried powder in the step one, placing the spongy urea freeze-dried powder in a ceramic crucible, covering the ceramic crucible and wrapping the ceramic crucible by double-layer tinfoil; preheating a muffle furnace to 500 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 3 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; 200mg of dopamine hydrochloride is added into the dispersion liquid, and the reaction is carried out for 1h under the magnetic stirring condition of 300 r/min at room temperature; 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 1mmol (0.17 g) of AgNO is added 3 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; then 0.33mmol (0.127 g) Na was added 3 PO 4 The reaction is carried out for 10min under the magnetic stirring condition of light shielding and 800 rpm; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
FIG. 9c is a high resolution scanning electron micrograph of the end product of example 8. The obtained nano catalyst g-C3N4/PDA/Ag 3 PO 4 About 600nm in size, in situ formed Ag 3 PO 4 The particle size is about 5nm, the monodispersity is better, and the surface part of the g-C3N4/PDA is covered.
Example 9
The embodiment comprises the following steps:
dissolving 50g of urea in double distilled water, and performing constant volume to reach 625mL, and performing ultrasonic treatment at 30kHz for 8min to obtain uniform urea stock solution; dissolving 0.05g KOH in 75mL 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, and filling the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50mL volume, and reacting for 6 hours at 120 ℃; taking out the polytetrafluoroethylene lining, pre-freezing for 12 hours at the temperature of minus 20 ℃, transferring to the temperature of minus 80 ℃ for pre-freezing for 24 hours, and then freeze-drying in a freeze dryer to obtain spongy urea freeze-dried powder;
step two, 2g of the spongy urea freeze-dried powder in the step one is taken and placed in a ceramic crucible, covered and wrapped by double-layer tinfoil; preheating a muffle furnace to 600 ℃, then putting a ceramic crucible filled with spongy urea freeze-dried powder into the preheated muffle furnace, and performing thermal polymerization reaction for 2.5 hours; taking out, cooling, washing with double distilled water for 3 times, drying and collecting to obtain carbon nitride nano-tissue g-C3N4;
weighing 200mg of g-C3N4 obtained in the second step, adding the g-C3N4 into 320mL of double distilled water, and performing ultrasonic treatment at 60kHz for 30 minutes to obtain uniform dispersion; adding 50mg of dopamine hydrochloride into the dispersion liquid, and reacting for 1h at room temperature under the magnetic stirring condition 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 conditions of opening or oxygen introduction; filtering and separating the reaction product by using a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain a carbon nitride/polydopamine superlattice structure;
step four, 200mg of the carbon nitride/polydopamine superlattice structure obtained in the step three is taken, 150mL of water is added for ultrasonic dispersion, and then 9mmol (1.53 g) of AgNO is added 3 Light is prevented, and the reaction is carried out for 15min under the magnetic stirring condition of 800 revolutions per minute; 3mmol (1.14 g) of Na was added 3 PO 4 Light is prevented, and the reaction is carried out for 15min under the magnetic stirring condition of 800 revolutions per minute; filtering and separating the reaction product by a 0.2 mu m sand core funnel, washing with double distilled water for 3 times, drying and collecting to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst g-C3N4/PDA/Ag 3 PO 4 。
Application example 1
The g-C3N4/PDA/Ag prepared in example 1 3 PO 4 The superlattice nanocatalyst is co-cultured with the animal body cells. The specific operation and experimental results are as follows:
first, L929 (mouse fibroblasts) cells were seeded into 96-well plates and incubated until adherent. Then, the original medium was replaced with a medium containing 300. Mu.g/mL of the sample, and the cells were co-cultured in a cell culture tank for 72 hours. Next, the mixed media was removed and gently rinsed with PBS. Finally, LIVE/DEAD is used TM Cell viability/cytotoxicity kits were tested and imaged using a confocal laser fiberscope.
As shown in FIG. 10, green cells are living cells and red cells are dead cells. The invention can be seenThe products of each step have good biocompatibility, which is to make the g-C3N4/PDA/Ag 3 PO 4 The superlattice nano-catalyst is used as an application foundation in the biomedical field.
Application example 2
The g-C3N4/PDA/Ag obtained in example 1 3 PO 4 The superlattice nano catalyst is applied to visible light degradation of water to produce 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 g-C3N4/PDA/Ag 3 PO 4 The superlattice nano catalyst solid powder is added into 100mL of 1M KOH aqueous solution, and then 1g of AgNO is added 3 Ultrasonic treatment for 15min, adding into a reaction bottle, placing the reaction bottle in an atmosphere controller, exhausting air in the bottle through nitrogen, vacuumizing for 0.5h, placing in a multi-channel photocatalytic reaction device, irradiating with xenon light for 4h, monitoring generated gas on line by using a gas chromatograph, wherein a detector is a TCD thermal conductivity detector, and carrier gas is high-purity nitrogen or argon.
As shown in FIG. 11, the g-C3N4/PDA/Ag 3 PO 4 The superlattice nano catalyst has oxygen generating activity of 500 mu mol/g/h, and oxygen generating active substances are 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 1 3 PO 4 The superlattice nano-catalyst is applied to the treatment of the skin infectious wound of the mice. The specific operation and experimental results are as follows:
female Balb/c mice (about 18 g) of 4 weeks old were anesthetized and dehaired prior to modeling. First, a full-thickness wound model was established using a skin biopsy punch 8mm in diameter. Then, it will contain 2X 10 8 CFU/mL E.coli and 1X 10 8 A mixed bacterial suspension of CFU/mL staphylococcus aureus was inoculated on the wound. Finally, the mice were divided into 4 groups (8 mice per group); (1) negative control: no treatment is performed; (2) positive control: mupirocin ointment (300 mg,2 wt%) was administered (3) to simulate the sun treatment group; (4) g-C3N4/PDA/Ag 3 PO 4 Dosing group (300 mg,1 wt%); (5) Simulated sunlight combined g-C3N4/PDA/Ag 3 PO 4 Treatment groups. Left and right treatment regimens once daily; the group involved simulated solar therapy was: 100mW/cm 2 Is irradiated with a Xe lamp with a filter (AM 1.5G) for 1 hour.
As shown in FIG. 12, the simulated sunlight was combined with g-C3N4/PDA/Ag at a wound diameter of 8mm 3 PO 4 The treatment group completed epithelial regeneration on day 10, while the negative control group and the positive control group did not complete healing on day 15. The outstanding curative effect is that the microenvironment of the inflammatory phase of the infectious wound is acidic, and the treatment requires antibiosis; once in the remodelling stage, the wound microenvironment turns alkaline, and one of the corresponding therapeutic requirements is in situ oxygen supply, accelerating cell proliferation and differentiation. Combining g-C3N4/PDA/Ag using simulated sunlight 3 PO 4 The advantages of treating hair are: (1) Use of ROS-producing g-C3N4/PDA/Ag 3 PO 4 The photocatalyst replaces antibiotics to perform antibiosis, so that accumulation of drug resistance and generation of drug-resistant bacteria can be effectively avoided; (2) g-C3N4/PDA/Ag for oxygen production using in situ catalytic water splitting 3 PO 4 The photocatalyst replaces remote oxygen supply depending on blood circulation, and the defect that the space-time distribution is uncontrollable due to high reactivity of oxygen and components in the body can be avoided. In a word, on the premise of good biocompatibility and high visible light catalytic activity, the g-C3N4/PDA/Ag prepared by the invention 3 PO 4 The superlattice nano catalyst can utilize water with highest organism content as a substrate to realize in-situ generation of ROS under an acidic microenvironment in an inflammatory phase of an infected wound to play an antibacterial effect; the in-situ oxygen generation in alkaline microenvironment in the remodelling period has the excellent effect of accelerating the re-epithelialization process.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst is characterized by comprising the following steps of:
step one: placing urea solution and potassium hydroxide solution together in a polytetrafluoroethylene-lined high-pressure reaction kettle, pre-reacting for 4-8 hours at 80-120 ℃, taking out, and placing in a freeze dryer for freeze drying to obtain spongy urea freeze-dried powder; the mass ratio of urea to potassium hydroxide is as follows: (420-20160) 1;
step two, carrying out thermal polymerization reaction on the spongy urea freeze-dried powder in the step one in a muffle furnace, and cooling, washing and drying after the reaction is finished to obtain carbon nitride nano-tissue; the reaction temperature of the thermal polymerization reaction is 500-600 ℃, and the reaction time of the thermal polymerization reaction is 2-4 h;
step three, adding the carbon nitride nano tissue obtained in the step two into double distilled water, and performing ultrasonic treatment to obtain dispersion liquid; adding dopamine hydrochloride into the dispersion liquid, and stirring and reacting for 0.5-1.5 h; then adding alkaline solution into the reaction materials to adjust the pH value of the reaction materials to 8.0-10, reacting for 24 hours at 60-100 ℃, and filtering, washing and drying the product to obtain the carbon nitride/polydopamine superlattice structure; the mass ratio of the dopamine hydrochloride to the carbon nitride nano-tissue is 1 (1-4);
step four, adding the carbon nitride/polydopamine superlattice structure in the step three into water for ultrasonic dispersion, and then adding AgNO 3 Stirring and reacting for 5-15 min under the dark condition, and then adding Na 3 PO 4 Stirring and reacting for 5-15 min under the dark condition, filtering the reaction product, washing and drying to obtain the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst.
2. The method for preparing a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein in the third step, the alkaline solution is a tris (hydroxymethyl) aminomethane solution, a sodium hydroxide solution, a triethylamine aqueous solution or a buffer solution with a pH value of 8-10.
3. The method for preparing the carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 2, wherein the buffer solution is a potassium dihydrogen phosphate-sodium hydroxide buffer solution, a boric acid-borax buffer solution, a glycine-sodium hydroxide buffer solution or a borax-sodium hydroxide buffer solution.
4. The method for preparing a carbon nitride/polydopamine/silver phosphate superlattice nano catalyst according to claim 1, wherein in the fourth step, agNO 3 And the mass ratio of the carbon nitride to the polydopamine superlattice structure is (0.85-7.65) 1, agNO 3 And Na (Na) 3 PO 4 The mass ratio of (2) is 1.34:1.
5. A carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method according to any one of claims 1 to 4.
6. Use of a carbon nitride/polydopamine/silver phosphate superlattice nano-catalyst prepared by the preparation method according to any one of claims 1 to 4 in photolysis of water to produce oxygen.
7. Use of a carbon nitride/polydopamine/silver phosphate superlattice nanocatalyst prepared by the method of any one of claims 1 to 4 for the preparation of a medicament for the treatment of infectious wounds.
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