CN112156805A - Preparation of silver-doped soft carbon-carbon nitride-TiO by using waste cotton2Method for compounding materials - Google Patents
Preparation of silver-doped soft carbon-carbon nitride-TiO by using waste cotton2Method for compounding materials Download PDFInfo
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- CN112156805A CN112156805A CN202011116636.4A CN202011116636A CN112156805A CN 112156805 A CN112156805 A CN 112156805A CN 202011116636 A CN202011116636 A CN 202011116636A CN 112156805 A CN112156805 A CN 112156805A
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 26
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract
Hair brushThe method for preparing silver-doped soft carbon-carbon nitride-TiO by using waste cotton2The composite material is prepared with waste cotton as material and through calcining in nitrogen atmosphere to form soft carbon, and embedding Ag in the micropores of the soft carbon to prevent the soft carbon from growing and deforming. Adopting quaternary ammonium salt intercalation auxiliary grinding method to make g-C3N4Grinding the granules to form small layers g-C3N4Nano-sheet is treated by ultrasonic oscillation in isopropanol solution of polyvinylpyrrolidone to strip out single-layer g-C3N4Nanosheets. Then the single layer g-C is put in a vibration impact mill3N4Mixing and grinding the nano-sheets and isopropyl titanate, and finally carrying out hydrothermal loading on the nano-sheets and soft carbon doped with silver quantum dots together to improve the photocatalytic performance of the soft carbon, silver and nano-graphite phase carbon nitride and titanium dioxide.
Description
Technical Field
The invention belongs to the technical field of textile engineering, and particularly relates to a method for preparing silver-doped soft carbon-carbon nitride-TiO by using waste cotton fibers2A method of compounding a material.
Background
TiO2The catalyst is the most widely used catalyst at present, is cheap and non-toxic, has low cost, has good photostability and chemical stability, has high absorptivity to ultraviolet rays, can be excited by the ultraviolet rays less than 387nm to generate electron-hole pairs, and has large forbidden bandwidth. Compared with rutile and brookite TiO2Anatase TiO2Has relatively strong oxidation-reduction capability and high photocatalytic activity, and has strong adsorption effect on organic pollutants.
Graphite phase carbon nitride (g-C)3N4) Is a polymer semiconductor material containing no metal component. The photocatalyst has the advantages of low cost, no toxicity, good thermal stability and chemical stability, moderate band gap, visible light response and proper electronic band structure, is an ideal material for preparing the photocatalyst, and has better performance of photocatalytic degradation of pollutants than other metal oxide narrow band gap materials.
In the molecular chain of the cotton cellulose, each glucose ring has three active hydroxyl groups, and the hydroxyl groups are associated with hydrogen bonds in the molecular chain and among the molecular chains. Intermolecular forces exist among molecular chains, but the acting force is far smaller than that of a hydrogen bond, so that the destruction and regeneration of the hydrogen bond have great influence on the modification of the cotton fiber, including physical and chemical properties. The alkali treatment of cotton fiber is the simplest and the most mature modification process in the chemical modification method of cotton fiber. The method mainly comprises the steps of placing cotton fibers in a strong alkaline solution for swelling, obtaining alkali cellulose after treatment, and neutralizing the alkali cellulose by acid, so that the crystallinity of the cotton fibers is reduced. The modified cotton fiber has certain performance improvement in physical performance.
The cotton fiber can be calcined into soft carbon and hard carbon at a certain temperature. Hard carbon is difficult to graphitize, is thermal decomposition of high molecular polymer, and does not meet the experimental requirements of the patent. The soft carbon is of a hollow structure, and the surface of the soft carbon is provided with a plurality of small holes with smaller apertures, so that smaller substances can be well embedded in the small holes without growing up and deforming, and the soft carbon has a large specific surface area and adsorption capacity.
Ag is a cheap material with wide sources, has excellent conductivity and strong electron capture capacity, and can improve the photocatalytic performance and the degradation and adsorption capacity by depositing the Ag on soft carbon.
Research shows that the preparation method can be used for preparing the product with the g-C content by hydrothermal, calcining, microwave heating and other methods3N4And TiO2Between which a Z-type or II-type heterojunction is established, and photogenerated electrons are from g-C3N4The conduction band of (A) is transferred to TiO by Z-type carrier transport2In the valence band, followed by oxidation and reduction processes, respectively, in TiO2Valence band and g-C of3N4The two processes are respectively carried out at different positions of the catalyst, so that the photocatalytic efficiency is greatly improved. However, there is currently concern about the use of waste cotton fibers for the preparation of silver-doped quantum dot carbon/g-C3N4/TiO2The related art of the photocatalytic composite material has not been reported.
Disclosure of Invention
The invention aims to provide a method for preparing silver-doped soft carbon-carbon nitride-TiO by using waste cotton2A method of compounding a material. Firstly, the waste cotton fiber is cleaned, swelled and calcined in nitrogen environment to prepare the soft carbon. Secondly, adopting a quaternary ammonium salt intercalation auxiliary grinding method to mix g-C3N4Grinding the granules to form small layers g-C3N4Nano-sheet is treated by ultrasonic oscillation in isopropanol solution of polyvinylpyrrolidone to strip out single-layer g-C3N4Nanosheets. Finally, grinding-hydrothermal synthesis technology is adopted to obtain g-C3N4Nanosheet and TiO2Carrying out vibration smashing type grinding on the precursor isopropyl titanate mixed solution, and then carrying out hydrothermal reaction together with soft carbon to prepare silver-doped quantum dot carbon/g-C3N4/TiO2A photocatalytic composite material.
The invention adopts the technical scheme that the silver-doped soft carbon-carbon nitride-TiO is prepared by using waste cotton2The method for preparing the composite material comprises the following specific operation steps:
step 1, calcining waste cotton fibers into soft carbon fibers in a nitrogen environment after cleaning and swelling;
step 2, freezing and grinding the soft carbon fiber obtained in the step 1 into powder, and embedding the silver quantum dots into micropores of the soft carbon under the conditions of light shielding and ultrasound to obtain the soft carbon powder doped with the silver quantum dots;
step 3, grinding graphite phase carbon nitride particles into few-layer nanosheets, performing ultrasonic oscillation treatment in isopropanol solution of polyvinylpyrrolidone, and stripping out single-layer g-C3N4Nanosheets;
step 4, the monolayer g-C3N4Addition of nanosheets to TiO2The precursor isopropyl titanate is vibrated, smashed and ground in absolute ethyl alcohol solution at the temperature of minus 30 ℃ to prepare g-C3N4/TiO2Compounding the solution;
step 5, adding the silver quantum dot-doped soft carbon powder into g-C3N4/TiO2Continuously vibrating, smashing and grinding the composite solution, and finally subjecting the mixed solution to high temperature and high pressureCarrying out hydrothermal reaction to prepare the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
In the step 1, the specific processes of cleaning, swelling and calcining the waste cotton fibers in a nitrogen atmosphere to prepare the soft carbon are as follows:
step 1.1: cutting waste cotton fibers into fibers with the length of 2.0-5.0 mm, immersing the fibers into NaOH solution with the molar concentration of 0.3-0.6M, carrying out water bath treatment at 80-120 ℃ for 20-40 min, soaking the fibers in deionized water for 3-5 times, each time for 20-40 min, and carrying out vacuum drying at 80-120 ℃ for 4-8 h;
step 1.2: soaking the washed cotton fibers in 50-60% by mass of an N-methylmorpholine-N-oxide aqueous solution, heating in a water bath at 60-70 ℃ for 20-30 min, soaking in deionized water for 3-5 times, each time for 20-40 min, and vacuum drying at 80-120 ℃ for 4-8 h;
preparing a KOH solution with the molar concentration of 10-14M, then soaking the dried cotton fibers in the KOH solution, and adding the fibers and the solution into a 100ml polytetrafluoroethylene inner container; then placing the inner container in a stainless steel reaction kettle, covering and sealing the stainless steel reaction kettle, heating the stainless steel reaction kettle to 100-140 ℃, and carrying out constant temperature treatment at the speed of 5-10 r/min for 2-5 h; after the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 2-3 times by using deionized water, wherein each time lasts for 10-30 min, and finally soaking the fiber for 1-2 times by using the deionized water, and drying the fiber in a freeze dryer;
step 1.3: putting the fibers treated in the step 1.2 into a coverless quartz boat, transferring the fibers into a tube furnace, and carrying out nitrogen atmosphere environment at 1-5 ℃ for min-1Heating to 500-600 ℃ at a heating rate, and carrying out constant temperature treatment for 2-5 h; and after the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 10-30 min by absolute ethyl alcohol, soaking the quartz boat for 10-30 min, soaking the quartz boat for 3-5 times by deionized water for 10-20 min each time, and vacuum drying the quartz boat for 5-8 h at the temperature of 80-130 ℃ to obtain the soft carbon fiber.
In the step 2, the soft carbon fiber is frozen and ground into powder, and the specific preparation process of the silver quantum dot doped soft carbon comprises the following steps:
step 2.1: adding the soft carbon fiber into a freezing and grinding tank, pre-freezing for 20-40 min at the temperature of-30-35 ℃, and then vibrating, pounding and grinding for 20-40 min for 20-40 times, wherein each time lasts for 60 s; washing out the soft carbon powder by using deionized water, and drying in vacuum at 60-80 ℃;
step 2.2: AgNO with the preparation concentration of 1-5 mmol/L3A solution; adding the soft carbon powder treated in the step 2.1 into AgNO3And in the solution, carrying out dark ultrasonic oscillation for 10-30 min at the frequency of 28-35 KHZ, soaking for 10-30 min, centrifuging for 15-20 min at 9000-11000 r/min, and carrying out vacuum drying at 50-80 ℃ to obtain the soft carbon doped with the silver quantum dots.
In step 3, a monolayer g-C is prepared3N4The specific process of the nano-sheet is as follows:
step 3.1: putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out nitrogen atmosphere environment at 1-3 ℃ for min-1Heating to 500-600 ℃ at a heating rate, and carrying out constant temperature treatment for 2-5 h; after the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4Particles;
step 3.2: g to C3N4Putting the particles into a vibration smashing type grinding machine, adding quaternary ammonium salt into the particles, pre-freezing for 20-40 min at the temperature of minus 30-35 ℃, and then performing vibration smashing and grinding for 20-40 min for 20-40 times, wherein each time lasts for 60 s; obtaining a small layer g-C upon completion of the grinding3N4Nanosheets; the obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 10-30 min to strip out a single layer of g-C3N4Nanosheets.
And 3.2, the mass ratio of the ball material during grinding is 80-100: 1.
In step 4, g-C3N4/TiO2The specific preparation process of the composite solution comprises the following steps:
and 4, step 4: measuring isopropyl titanate, dispersant polyethylene glycol 400 and absolute ethyl alcohol, and placing the mixture into a grinding tank to obtain TiO2Precursor isopropyl titanate anhydrous ethanol solution, and then monolayer g-C3N4Addition of nanosheets to TiO2Pre-freezing the precursor isopropyl titanate in an absolute ethanol solution at the temperature of 35 ℃ below zero to 40 DEG C40min, then vibrating, smashing and grinding for 20-40 min, 20-40 times, 60s each time, and obtaining g-C after finishing vibrating, smashing and grinding3N4/TiO2Compounding the solution;
isopropyl titanate, dispersant polyethylene glycol 400, absolute ethyl alcohol and monolayer g-C3N4The proportion of the nanosheets is 0.3-0.6 mL: 0.5-2.0 mL: 15-18 mL: 0.025 to 0.05 g.
In step 5, doping silver quantum dots with soft carbon/g-C3N4/TiO2The specific preparation process of the composite material comprises the following steps:
step 5.1: adding the soft carbon doped with the silver quantum dots in the step 2 into g-C3N4/TiO2Continuously vibrating, smashing and grinding the composite solution for 20-40 min to obtain a composite solution a;
step 5.2: adding the composite solution a into a polytetrafluoroethylene inner container, covering and sealing the inner container, then loading the inner container into a homogeneous reactor, reacting at a constant temperature of 100-140 ℃ for 2-5 h at a rotating speed of 5-10 r/min, and naturally cooling to room temperature; washing the obtained product with absolute ethyl alcohol and deionized water for 10-20 min respectively, repeating for 3-5 times, and freeze-drying; obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
The beneficial effect of the invention is that,
(1) the invention takes the waste cotton as the raw material to recycle the waste, thereby reducing the waste of resources. After alkali treatment and swelling are carried out on the waste cotton, the waste cotton is calcined into soft carbon under the condition of nitrogen atmosphere. The soft carbon is of a hollow structure, has more surface micropores, large contact area and strong adsorption capacity, and can be used for inlaying Ag in the micropores, thereby being beneficial to preventing the Ag from agglomerating and growing up and fully playing the functionality of the Ag.
(2) The invention adopts a quaternary ammonium salt intercalation auxiliary grinding method to mix g-C3N4Grinding the granules to form small layers g-C3N4Nano-sheet is treated by ultrasonic oscillation in isopropanol solution of polyvinylpyrrolidone to strip out single-layer g-C3N4Nanosheets. Then the single layer g-C is subjected to vibration impact type grinding-hydrothermal synthesis technology3N4Nanosheet and TiO2And carrying out vibration smashing type grinding on the precursor isopropyl titanate mixed solution, and then carrying out hydrothermal reaction together with soft carbon.
(3) The silver-doped quantum dot soft carbon/g-C prepared by the invention3N4/TiO2The composite material has strong photocatalytic activity and long service life, can be repeatedly used, and the waste silver-doped quantum dot soft carbon/g-C3N4/TiO2The composite material can be naturally degraded under natural conditions, and cannot cause pollution to the environment.
Drawings
FIG. 1 shows the soft carbon/g-C doped with silver quantum dots obtained in example 1 of the present invention3N4/TiO2Scanning electron microscope photographs of the composite material;
FIG. 2 shows the soft carbon/g-C doped with silver quantum dots obtained in example 4 of the present invention3N4/TiO2Scanning electron microscope photographs of the composite material;
FIG. 3 shows g-C obtained in example 1 of the present invention3N4Atomic force microscopy images of the nanoplatelets;
FIG. 4 shows the soft carbon/g-C of the silver-doped quantum dots obtained in examples 1 and 4 of the present invention3N4/TiO2An X-ray diffraction pattern of the composite;
FIG. 5 shows the soft carbon/g-C of the silver-doped quantum dots obtained in examples 1 and 4 of the present invention3N4/TiO2A raman map of the composite;
FIG. 6(a) is a diagram of the soft carbon/g-C doped with silver quantum dots obtained in example 1 of the present invention3N4/TiO2N of composite material2Adsorption-desorption isotherm plot;
FIG. 6(b) is the soft carbon/g-C of the silver-doped quantum dot obtained in example 1 of the present invention3N4/TiO2Pore size distribution curve plot of the composite material;
FIG. 7 shows the soft carbon/g-C of the silver-doped quantum dots obtained in comparative example 1 and comparative example 2 of the present invention3N4/TiO2The visible light irradiation of the composite material catalyzes the degradation of methylene blue curve.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention uses waste cotton as raw material, calcines the waste cotton into soft carbon under nitrogen environment, and then embeds Ag in micropores of the soft carbon to prevent the waste cotton from growing and deforming. Adopting quaternary ammonium salt intercalation auxiliary grinding method to make g-C3N4Grinding the granules to form small layers g-C3N4Nano-sheet is treated by ultrasonic oscillation in isopropanol solution of polyvinylpyrrolidone to strip out single-layer g-C3N4Nanosheets. Then the single layer g-C is put in a vibration impact mill3N4Mixing and grinding the nano-sheets and isopropyl titanate, and finally carrying out hydrothermal loading on the nano-sheets and soft carbon doped with silver quantum dots together to improve the photocatalytic performance of the soft carbon, silver and nano-graphite phase carbon nitride and titanium dioxide.
Example 1
According to the bath ratio of 1: 50, weighing 5g of cotton fiber, cutting the cotton fiber into 5mm in length, soaking the cotton fiber in 250mL of NaOH solution with the molar concentration of 0.5M, treating the cotton fiber in water bath at 100 ℃ for 30min, then soaking the cotton fiber in deionized water for 3 times, each time for 30min, and carrying out vacuum drying at 110 ℃ for 5 h. Soaking the washed cotton fiber in 50% N-methylmorpholine-N-oxide (NMMO) water solution, heating in water bath at 60 deg.C for 30min, soaking in deionized water for 3 times, each time for 20min, and vacuum drying at 80 deg.C for 5 h. Then 60mL of KOH solution (12M) is prepared according to the bath ratio of 1:80, then 0.75g of alkali-treated cotton fiber is weighed and soaked in the KOH solution, and the fiber and the solution are added into a 100mL polytetrafluoroethylene inner container. Then the liner is placed in a stainless steel reaction kettle and sealed by a cover, the stainless steel reaction kettle is heated to 130 ℃, and the constant temperature treatment is carried out for 3 hours at the speed of 10 r/min. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 3 times with deionized water, 30min each time, finally soaking the fiber for 1 time with the deionized water, and drying the fiber in a refrigerator. Finally, the swelling cotton fiber is put into a quartz boat without a cover, and then is transferred into a tube furnace, and the temperature is 2 ℃ for min under the nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 30min by absolute ethyl alcohol, then soaking the quartz boat for 30min, and de-ionized waterSoaking for 3 times and 10min each time, and vacuum drying at 110 deg.C for 5 hr to obtain soft carbon fiber. Weighing 1g of soft carbon fiber, adding into a freezing grinding tank, pre-freezing at-30 deg.C for 30min, and vibrating, pounding and grinding for 30min for 30 times (each time for 60 s). The soft carbon powder was washed out with deionized water and dried under vacuum at 60 ℃. The AgNO with the volume of 50mL (removing oxygen in water by nitrogen gas) and the concentration of 1.848mmol/L is prepared3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. Weighing g-C3N4Putting the granules into a vibration smashing type grinding machine, wherein the ball material mass ratio during grinding is 100:1, adding quaternary ammonium salt into the grinding machine, pre-freezing for 30min at the temperature of minus 35 ℃, and then performing vibration smashing grinding for 30min for 60s every time for 30 times. Obtaining a small layer g-C upon completion of the grinding3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 0.6mL of isopropyl titanate, 2.0mL of dispersant polyethylene glycol 400 and 18mL of absolute ethanol solution are measured in a grinding tank, and 0.05g of g-C is added3N4Addition of nanosheets to TiO2And (3) vibrating, smashing and grinding the precursor isopropyl titanate in an absolute ethanol solution for 30 min. Then, 0.1g of silver-doped quantum dot soft carbon is added to continue vibrating and smashing for 30min, and a mixed solution is obtained. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the container, then filling the container into a homogeneous reactor, reacting at the constant temperature of 120 ℃ for 3h at the rotating speed of 10r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water for 15min respectively, repeating for 3 times, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
Example 2
According to the bath ratio of 1: 60, weighing 5g of cotton fiber, cutting the cotton fiber into 4mm in length, soaking the cotton fiber in 300mL of NaOH solution with the molar concentration of 0.6M for 30min at 110 ℃, then soaking the cotton fiber in deionized water for 5 times, each time for 10min, and carrying out vacuum drying for 3h at 120 ℃. Soaking the washed cotton fiber in 60% N-methylmorpholine-N-oxide (NMMO) water solution, heating in 70 deg.C water bath for 20min, soaking in deionized water for 4 times (40 min each time), and vacuum drying at 100 deg.C for 6 h. Then 80mL of KOH solution (12M) is prepared according to the bath ratio of 1:80, then 1g of alkali treated cotton fiber is weighed and soaked in the KOH solution, and the fiber and the solution are added into a 100mL polytetrafluoroethylene inner container. Then the inner container is placed in a stainless steel reaction kettle and covered and sealed, the stainless steel reaction kettle is heated to 110 ℃, and the constant temperature treatment is carried out for 5 hours at the speed of 10 r/min. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 2 times with deionized water, 30min each time, and finally soaking the fiber for 1 time with the deionized water, and drying the fiber in a refrigerator. Placing the swollen cotton fiber into a quartz boat without cover, transferring into a tube furnace, and heating at 3 deg.C for min under nitrogen atmosphere-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. And after the reaction is finished, cooling the quartz boat to room temperature, carrying out ultrasonic oscillation for 30min by using absolute ethyl alcohol, soaking for 30min, soaking for 3 times by using deionized water for 10min each time, and carrying out vacuum drying for 5h at 110 ℃ to obtain the soft carbon fiber. Weighing 1.5g of soft carbon fiber, adding into a freezing and grinding tank, pre-freezing for 30min at-40 ℃, and then vibrating, smashing and grinding for 30min for 30 times, wherein each time is 60 s. The soft carbon powder was washed out with deionized water and dried under vacuum at 60 ℃. The AgNO with the volume of 25mL (removing oxygen in water by nitrogen gas) and the concentration of 1.848mmol/L is prepared3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate is increased to 600 ℃ and the constant temperature treatment is carried out for 3 hours. Reaction junctionAfter the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. G to C3N4Putting the granules into a vibration smashing type grinding machine, adding quaternary ammonium salt according to the ball material mass ratio of 90:1, pre-freezing for 40min at the temperature of minus 30 ℃, and then performing vibration smashing and grinding for 30min for 60s every time for 30 times. Obtaining a small layer g-C upon completion of the grinding3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 0.6mL of isopropyl titanate, 3.0mL of dispersant polyethylene glycol 400 and 17mL of absolute ethanol solution are measured in a grinding tank, and 0.05g of g-C is added3N4Addition of nanosheets to TiO2And (3) vibrating, smashing and grinding the precursor isopropyl titanate in an absolute ethanol solution for 30 min. Then, 0.2g of silver-doped quantum dot soft carbon is added to continue vibrating and smashing for 30min, and a mixed solution is obtained. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the container, then filling the container into a homogeneous reactor, reacting at the constant temperature of 120 ℃ for 4 hours at the rotating speed of 10r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water for 20min respectively, repeating for 3 times, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
Example 3
According to the bath ratio of 1: 40, weighing 5g of cotton fiber, cutting the cotton fiber into 3mm in length, soaking the cotton fiber in 200mL of NaOH solution with the molar concentration of 0.4M for 20min at 110 ℃, then soaking the cotton fiber in deionized water for 4 times, each time for 20min, and carrying out vacuum drying for 6h at 110 ℃. Soaking the washed cotton fiber in 50% N-methylmorpholine-N-oxide (NMMO) water solution, heating in 65 deg.C water bath for 30min, soaking in deionized water for 5 times, each for 30min, and vacuum drying at 120 deg.C for 4 h. Then preparing 80mL of KOH solution (12M) according to the bath ratio of 1:80, weighing 1g of alkali-treated cotton fibers, soaking the cotton fibers in the KOH solution, and adding the fibers and the solution into a 100mL polytetrafluoroethylene inner container. Then the inner container is placed in a stainless steel reaction kettle and covered and sealed, the stainless steel reaction kettle is heated to 130 ℃ and heated at the speed of 7r/minAnd (5) carrying out constant-temperature treatment at a speed for 3 hours. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 3 times by using deionized water, wherein each time is 20min, and finally soaking the fiber for 1 time by using the deionized water, and drying the fiber in a refrigerator. Placing the swollen cotton fiber into a quartz boat without cover, transferring into a tube furnace, and heating at 4 deg.C for min under nitrogen atmosphere-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 4 h. And after the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 30min by using absolute ethyl alcohol, soaking the quartz boat for 30min, soaking the quartz boat for 3 times by using deionized water for 10min each time, and drying the quartz boat for 5h in vacuum at 110 ℃ to obtain the soft carbon fiber. Weighing soft carbon fiber 2g, adding into a freezing grinding tank, pre-freezing at-35 deg.C for 30min, and vibration pounding for 25min for 30 times (60 s each time). The soft carbon powder was washed out with deionized water and dried in vacuo at 70 ℃. The AgNO with the volume of 50mL (removing oxygen in water by nitrogen gas) and the concentration of 1.848mmol/L is prepared3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. Taking g-C3N4Putting the granules into a vibration smashing type grinding machine, wherein the ball material mass ratio during grinding is 95:1, adding quaternary ammonium salt into the granules, pre-freezing the mixture for 30min at the temperature of minus 33 ℃, and then performing vibration smashing grinding for 35min for 35 times, wherein each time lasts for 60 s. Obtaining a small layer g-C upon completion of the grinding3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 0.6mL of isopropyl titanate, 4.0mL of dispersant polyethylene glycol 400 and 16mL of absolute ethanol solution are weighed into a grinding tank, and 0.05g of g-C is added3N4Addition of nanosheets to TiO2Vibrating and smashing precursor isopropyl titanate in absolute ethyl alcohol solutionAnd performing impact grinding for 40 min. Then, 0.15g of silver-doped quantum dot soft carbon is added to continue vibrating and pounding for 20min to obtain a mixed solution. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the container, then filling the container into a homogeneous reactor, reacting at the constant temperature of 120 ℃ for 4 hours at the rotating speed of 7r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water for 15min respectively, repeating for 5 times, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
Example 4
According to the bath ratio of 1: 50, weighing 5g of cotton fiber, cutting the cotton fiber into 2mm in length, soaking the cotton fiber in 250mL of NaOH solution with the molar concentration of 0.7M, carrying out water bath treatment at 120 ℃ for 15min, then soaking the cotton fiber in deionized water for 3 times, each time for 30min, and carrying out vacuum drying at 100 ℃ for 8 h. Soaking the washed cotton fiber in 55 wt% N-methylmorpholine-N-oxide (NMMO) water solution, heating in water bath at 6 deg.C for 25min, soaking in deionized water for 4 times (30 min each time), and vacuum drying at 110 deg.C for 5 h. Then 60mL of KOH solution (12M) is prepared according to the bath ratio of 1:80, then 0.75g of alkali-treated cotton fiber is weighed and soaked in the KOH solution, and the fiber and the solution are added into a 100mL polytetrafluoroethylene inner container. Then the inner container is placed in a stainless steel reaction kettle and covered and sealed, the stainless steel reaction kettle is heated to 120 ℃, and the constant temperature treatment is carried out for 5 hours at the speed of 10 r/min. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 3 times with deionized water, 10min each time, finally soaking the fiber for 1 time with the deionized water, and drying the fiber in a refrigerator. Placing the swollen cotton fiber into a quartz boat without cover, transferring into a tube furnace, and heating at 5 deg.C for min under nitrogen atmosphere-1The heating rate is increased to 600 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 30min by absolute ethyl alcohol, soaking the quartz boat for 30min, soaking the quartz boat for 3 times by deionized water for 10min each time, and drying the quartz boat for 5h in vacuum at 110 ℃ to obtain the soft carbon. Weighing 1.5g of soft carbon fiber, adding into a freezing and grinding tank, pre-freezing at-30 deg.C for 40min, and vibrating, smashing and grinding for 30min for 30 times, each time for 60 s. The soft carbon powder was washed out with deionized water and dried under vacuum at 65 ℃. The preparation volume is 25mL (oxygen in water is removed by nitrogen gas), and the concentration is 1.848mmol/LAgNO3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. Weighing g-C3N4Putting the granules into a vibration smashing type grinding machine, wherein the ball material mass ratio during grinding is 100:1, adding quaternary ammonium salt, pre-freezing at the temperature of 32 ℃ below zero for 40min, and then performing vibration smashing grinding for 40min for 60s each time for 40 times. Obtaining a small layer g-C upon completion of the grinding3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 1.2mL of isopropyl titanate, 2.0mL of dispersant polyethylene glycol 400 and 18mL of absolute ethanol solution are weighed into a grinding tank, and 0.1g of g-C is added3N4Addition of nanosheets to TiO2And (3) vibrating, smashing and grinding the precursor isopropyl titanate in an absolute ethanol solution for 40 min. Then, 0.1g of silver-doped quantum dot soft carbon is added to continue vibrating and smashing for 40min, and a mixed solution is obtained. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the inner container, then filling the inner container into a homogeneous reactor, reacting for 3 hours at the constant temperature of 130 ℃ at the rotating speed of 7r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water for 10min, repeating for 3 times, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
Comparative example 1
According to the bath ratio of 1: 50, weighing 5g of cotton fiber, cutting the cotton fiber into 2.0mm in length, soaking the cotton fiber in 250mL of NaOH solution with the molar concentration of 0.5M, treating the cotton fiber in water bath at 100 ℃ for 30min, and then soaking the cotton fiber in deionized water for 3 times, each time for 30min, and carrying out vacuum drying at 110 ℃ for 5 h. Soaking the washed cotton fiber in 50 wt%Heating in water bath at 60 deg.C for 30min, soaking in deionized water for 3 times (20 min each time), and vacuum drying at 80 deg.C for 5 h. Then 60mL of KOH solution (12M) is prepared according to the bath ratio of 1:80, then 0.75g of alkali-treated cotton fiber is weighed and soaked in the KOH solution, and the fiber and the solution are added into a 100mL polytetrafluoroethylene inner container. Then the liner is placed in a stainless steel reaction kettle and sealed by a cover, the stainless steel reaction kettle is heated to 130 ℃, and the constant temperature treatment is carried out for 3 hours at the speed of 10 r/min. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 3 times with deionized water, 30min each time, finally soaking the fiber for 1 time with the deionized water, and drying the fiber in a refrigerator. Finally weighing the swelling cotton fiber, putting the swelling cotton fiber into a quartz boat without a cover, transferring the swelling cotton fiber into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 30min by absolute ethyl alcohol, soaking the quartz boat for 30min, soaking the quartz boat for 3 times by deionized water for 10min each time, and drying the quartz boat for 5h in vacuum at 110 ℃ to obtain the soft carbon. Weighing 1.0g of soft carbon fiber, adding into a freezing and grinding tank, pre-freezing for 30min at-30 ℃, and then vibrating, smashing and grinding for 30min for 30 times, wherein each time is 60 s. The soft carbon powder was washed out with deionized water and dried under vacuum at 60 ℃. The AgNO with the volume of 50mL (removing oxygen in water by nitrogen gas) and the concentration of 1.848mmol/L is prepared3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. Weighing g-C3N4Putting the granules into a vibration smashing type grinding machine, wherein the ball material mass ratio during grinding is 100:1, adding quaternary ammonium salt into the grinding machine, pre-freezing for 30min at the temperature of minus 30 ℃, and then performing vibration smashing grinding for 30min for 60s every time for 30 times. Grinding to obtainAt least one layer g-C3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 0.6mL of isopropyl titanate, 2.0mL of dispersant polyethylene glycol 400 and 18mL of absolute ethanol solution are measured in a grinding tank, and 0.05g of g-C is added3N4Addition of nanosheets to TiO2And (3) vibrating, smashing and grinding the precursor isopropyl titanate in an absolute ethanol solution for 30 min. Then, 0.1g of silver-doped quantum dot soft carbon is added to continue vibrating and smashing for 30min, and a mixed solution is obtained. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the container, then filling the container into a homogeneous reactor, reacting at the constant temperature of 120 ℃ for 3h at the rotating speed of 10r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water for 15min respectively, repeating for 3 times, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
Comparative example 2
According to the bath ratio of 1: 50, weighing 5g of cotton fiber, cutting the cotton fiber into 5mm in length, soaking the cotton fiber in 250mL of NaOH solution with the molar concentration of 0.5M, treating the cotton fiber in water bath at 100 ℃ for 30min, then soaking the cotton fiber in deionized water for 3 times, each time for 30min, and carrying out vacuum drying at 110 ℃ for 5 h. Soaking the washed cotton fiber in 55 wt% N-methylmorpholine-N-oxide (NMMO) water solution, heating in water bath at 6 deg.C for 25min, soaking in deionized water for 4 times (30 min each time), and vacuum drying at 110 deg.C for 5 h. Then 60mL of KOH solution (12M) is prepared according to the bath ratio of 1:80, then 0.75g of alkali-treated cotton fiber is weighed and soaked in the KOH solution, and the fiber and the solution are added into a 100mL polytetrafluoroethylene inner container. Then the liner is placed in a stainless steel reaction kettle and sealed by a cover, the stainless steel reaction kettle is heated to 130 ℃, and the constant temperature treatment is carried out for 3 hours at the speed of 10 r/min. After the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 3 times with deionized water, 30min each time, finally soaking the fiber for 1 time with the deionized water, and drying the fiber in a refrigerator. Finally weighing a certain amount of swelling cotton fiber, putting the swelling cotton fiber into a coverless quartz boat, transferring the swelling cotton fiber into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of the furnace is increased to 550 ℃ and constantAnd (5) warming for 3 h. After the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 30min by absolute ethyl alcohol, soaking the quartz boat for 30min, soaking the quartz boat for 3 times by deionized water for 10min each time, and drying the quartz boat for 5h in vacuum at 110 ℃ to obtain the soft carbon. The AgNO with the volume of 25mL (removing oxygen in water by nitrogen gas) and the concentration of 1.848mmol/L is prepared3Solution (protected from light). Weighing 0.1g of soft carbon by mass, and adding the soft carbon into the prepared AgNO3And (3) ultrasonically oscillating the solution for 10min, soaking the solution for 20min (in the dark), centrifuging the solution to obtain soft carbon, and performing vacuum drying (in the dark) at the temperature of 60 ℃ to obtain the soft carbon doped with the silver quantum dots. Weighing 1.0g of soft carbon fiber, adding into a freezing and grinding tank, pre-freezing for 30min at-30 ℃, and then vibrating, smashing and grinding for 30min for 30 times, wherein each time is 60 s. The soft carbon powder was washed out with deionized water and dried under vacuum at 60 ℃. Putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere environment-1The heating rate of (2) is increased to 550 ℃ and the constant temperature treatment is carried out for 3 hours. After the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4And (3) granules. Weighing g-C3N4Putting the granules into a vibration smashing type grinding machine, wherein the ball material mass ratio during grinding is 100:1, adding quaternary ammonium salt into the grinding machine, pre-freezing for 30min at the temperature of minus 35 ℃, and then performing vibration smashing grinding for 30min for 60s every time for 30 times. Obtaining a small layer g-C upon completion of the grinding3N4Nanosheets. The obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 30min to strip out a single layer of g-C3N4Nanosheets. 0.6mL of isopropyl titanate, 2.0mL of dispersant polyethylene glycol 400 and 18mL of absolute ethanol solution are measured in a grinding tank, and 0.05g of g-C is added3N4Addition of nanosheets to TiO2And (3) vibrating, smashing and grinding the precursor isopropyl titanate in an absolute ethanol solution for 30 min. Then, 0.1g of silver-doped quantum dot soft carbon is added to continue vibrating and smashing for 30min, and a mixed solution is obtained. Adding the mixed solution into a 50mL polytetrafluoroethylene inner container, covering and sealing the container, then filling the container into a homogeneous reactor, reacting at the constant temperature of 120 ℃ for 3h at the rotating speed of 10r/min, and naturally cooling to the room temperature. Washing the obtained product with anhydrous ethanol and deionized water respectivelyRepeating for 3 times for 15min, and freeze drying. Obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
The invention is doped with the soft carbon/g-C of the silver quantum dot3N4/TiO2The performance test of the composite material photocatalytic degradation methylene blue dye adopts a photochemical reaction instrument, and the specific process is as follows: adding methylene blue solution with volume of 50mL and mass percent concentration of 5mg/L into a quartz glass dish with diameter of about 5cm, and adding 0.05g of silver-doped quantum dot soft carbon/g-C3N4/TiO2The composite material is prepared by ultrasonically oscillating a sample (28kHz, 100W) for 15min, placing the sample in a dark room for adsorption for 120min, placing a test tube filled with methylene blue solution in a photochemical reaction instrument after adsorption balance is achieved, and irradiating the test tube by using a 300W xenon lamp, wherein the distance between the test tube and a light source is 20 cm. Measuring photocatalytic activity under visible light irradiation with a filter of 400nm or more, centrifuging 5ml solution 11000rpm every 20min for 10min, and measuring the maximum absorbance at 664nm with UV-1601 spectrophotometer to obtain supernatant. And calculating the degradation rate D of the methylene blue dye according to the formula (1).
In the formula: c0Is the initial concentration of methylene blue solution after saturation of adsorption, CtIs the concentration of the methylene blue solution after a certain time of irradiation, and t is the irradiation time.
The test results are: silver-doped quantum dot soft carbon/g-C obtained in embodiment 1 of the invention3N4/TiO2The degradation rate of the composite material after 120min of visible light irradiation is 92.8 percent. Silver-doped quantum dot soft carbon/g-C obtained in embodiment 2 of the invention3N4/TiO2The degradation rate of the composite material after 120min of visible light irradiation is 87.9%. Silver-doped quantum dot soft carbon/g-C obtained in embodiment 4 of the invention3N4/TiO2The degradation rate of the composite material after 120min of visible light irradiation is 88.4 percent.
FIG. 1 shows the soft carbon/g-C doped with silver quantum dots obtained in example 1 of the present invention3N4/TiO2Scanning electron micrographs of the composite. It can be seen that uniform particles of nanometer order are deposited on the surface of the soft carbon. FIG. 2 shows the soft carbon/g-C doped with silver quantum dots obtained in example 4 of the present invention3N4/TiO2Scanning electron micrographs of the composite. It can be seen that the particle size of the nano-scale particles deposited on the surface of the soft carbon are close in size. FIG. 3 shows g-C obtained in example 1 of the present invention3N4Atomic force microscopy of nanoplatelets. It can be seen that g-C3N4The nano-meter is a sheet structure without fixed shape and with flat edge, the thickness is about 2.7nm, and the transverse dimension is between 2.5 μm. FIG. 4 shows the soft carbon/g-C of the silver-doped quantum dots obtained in examples 1 and 4 of the present invention3N4/TiO2X-ray diffraction pattern of the composite. It can be seen that the silver-doped quantum dots prepared in example 1 have soft carbon/g-C3N4/TiO2The composite material has obvious diffraction peaks at diffraction angles of 10.3 degrees, 25.3 degrees, 38.1 degrees, 41.7 degrees, 43.9 degrees, 46.3 degrees and 47.1 degrees. Silver-doped quantum dot soft carbon/g-C prepared in example 43N4/TiO2Diffraction Angle of the composite Material and the silver-doped Quantum dot Soft carbon/g-C prepared in example 13N4/TiO2The composite also shows diffraction peaks at the same positions, but with a reduced intensity. FIG. 5 shows the soft carbon/g-C of the silver-doped quantum dots obtained in examples 1 and 43N4/TiO2Raman plots of the composite materials. It can be seen that the silver-doped quantum dots prepared in example 1 have soft carbon/g-C3N4/TiO2The composite material is 1354.6cm-1，1591.7cm-1，2906.6cm-1Characteristic peaks appear at all. Silver-doped quantum dot soft carbon/g-C prepared in example 43N4/TiO2The composite material also exhibited characteristic peaks at the same locations, but with a reduced height. FIG. 6(a) is a diagram of the soft carbon/g-C doped with silver quantum dots obtained in example 1 of the present invention3N4/TiO2N of composite material2Adsorption-desorption isotherm diagram. It can be seen that there is a hysteresis loop in the adsorption-desorption isotherm curve, which is known from the International Union of Pure and Applied Chemistry (IUPAC) classificationBelongs to IV-type isotherms and is a typical mesoporous material. As can be seen from the pore size distribution curve of FIG. 6(b), there were three peaks at 35.7nm, 483.6nm and 1166.4nm, which are consistent with the isotherm results, indicating that g-C3N4The nano sheet has mesopores and macropores, and the powder is relatively loose, thus being beneficial to the absorption of degradation products. FIG. 7 is a graph showing the visible light irradiation photocatalytic degradation of methylene blue of the samples obtained in comparative example 1 and comparative example 2. It can be seen that the silver-doped quantum dot soft carbon g-C prepared in comparative example 1 degraded methylene blue under visible light irradiation photocatalysis3N4/TiO2The photocatalytic activity of the composite material is better than that of the silver-doped quantum dot soft carbon/g-C prepared in the comparative example 23N4/TiO2Composite materials, and are all compared with P25Good results are obtained.
Claims (7)
1. Preparation of silver-doped soft carbon-carbon nitride-TiO by using waste cotton2The method for preparing the composite material is characterized by comprising the following specific operation steps:
step 1, calcining waste cotton fibers into soft carbon fibers in a nitrogen environment after cleaning and swelling;
step 2, freezing and grinding the soft carbon fiber obtained in the step 1 into powder, and embedding the silver quantum dots into micropores of soft carbon under the conditions of light shielding and ultrasound to obtain silver quantum dot-doped soft carbon powder;
step 3, grinding graphite phase carbon nitride particles into few-layer nanosheets, performing ultrasonic oscillation treatment in isopropanol solution of polyvinylpyrrolidone, and stripping out single-layer g-C3N4Nanosheets;
step 4, the monolayer g-C3N4Addition of nanosheets to TiO2The precursor isopropyl titanate is vibrated, smashed and ground in absolute ethyl alcohol solution at the temperature of minus 30 ℃ to prepare g-C3N4/TiO2Compounding the solution;
step 5, adding the silver quantum dot-doped soft carbon powder into g-C3N4/TiO2Continuously vibrating, smashing and grinding the composite solution, and finally carrying out hydrothermal reaction on the mixed solution under the conditions of high temperature and high pressure to prepare the silver quantum dot doped soft carbon/g-C3N4/TiO2A composite material.
2. The method for preparing silver-doped soft carbon-carbon nitride-TiO from waste cotton according to claim 12A method of forming a composite material, characterized in that,
in the step 1, the specific processes of cleaning, swelling and calcining the waste cotton fibers in a nitrogen atmosphere to prepare the soft carbon are as follows:
step 1.1: cutting waste cotton fibers into fibers with the length of 2.0-5.0 mm, immersing the fibers into NaOH solution with the molar concentration of 0.3-0.6M, carrying out water bath treatment at 80-120 ℃ for 20-40 min, soaking the fibers in deionized water for 3-5 times, each time for 20-40 min, and carrying out vacuum drying at 80-120 ℃ for 4-8 h;
step 1.2: soaking the washed cotton fibers in 50-60% by mass of an N-methylmorpholine-N-oxide aqueous solution, heating in a water bath at 60-70 ℃ for 20-30 min, soaking in deionized water for 3-5 times, each time for 20-40 min, and vacuum drying at 80-120 ℃ for 4-8 h;
preparing a KOH solution with the molar concentration of 10-14M, then soaking the dried cotton fibers in the KOH solution, and adding the fibers and the solution into a 100ml polytetrafluoroethylene inner container; then placing the inner container in a stainless steel reaction kettle, covering and sealing the stainless steel reaction kettle, heating the stainless steel reaction kettle to 100-140 ℃, and carrying out constant temperature treatment at the speed of 5-10 r/min for 2-5 h; after the reaction kettle is naturally cooled after the reaction is finished, taking out the fiber, soaking the fiber for 2-3 times by using deionized water, wherein each time lasts for 10-30 min, and finally soaking the fiber for 1-2 times by using the deionized water, and drying the fiber in a refrigerator;
step 1.3: putting the fibers treated in the step 1.2 into a coverless quartz boat, transferring the fibers into a tube furnace, and carrying out nitrogen atmosphere environment at 1-5 ℃ for min-1Heating to 500-600 ℃ at a heating rate, and carrying out constant temperature treatment for 2-5 h; and after the reaction is finished, cooling the quartz boat to room temperature, ultrasonically oscillating the quartz boat for 10-30 min by using absolute ethyl alcohol, soaking the quartz boat for 10-30 min, soaking the quartz boat for 3-5 times by using deionized water for 10-20 min each time, and drying the quartz boat for 5-8 h at 80-130 ℃ in vacuum to obtain the soft carbon fiber.
3. The method for preparing silver-doped soft carbon-carbon nitride from waste cotton according to claim 2-TiO2A method of forming a composite material, characterized in that,
in the step 2, the soft carbon fiber is frozen and ground into powder, and the specific preparation process of the silver quantum dot doped soft carbon comprises the following steps:
step 2.1: adding the soft carbon fiber into a freezing and grinding tank, pre-freezing for 20-40 min at the temperature of-30-35 ℃, and then vibrating, pounding and grinding for 20-40 min for 20-40 times, wherein each time lasts for 60 s; washing out the soft carbon powder by using deionized water, and drying in vacuum at 60-80 ℃;
step 2.2: AgNO with the preparation concentration of 1-5 mmol/L3A solution; adding the soft carbon powder treated in the step 2.1 into AgNO3And in the solution, carrying out dark ultrasonic oscillation for 10-30 min at the frequency of 28-35 KHZ, soaking for 10-30 min, centrifuging for 15-20 min at 9000-11000 r/min, and carrying out vacuum drying at 50-80 ℃ to obtain the soft carbon doped with the silver quantum dots.
4. The method for preparing silver-doped soft carbon-carbon nitride-TiO from waste cotton according to claim 12A method of forming a composite material, characterized in that,
in step 3, a monolayer g-C is prepared3N4The specific process of the nano-sheet is as follows:
step 3.1: putting melamine into a quartz boat, covering the quartz boat, transferring the quartz boat into a tube furnace, and carrying out nitrogen atmosphere environment at 1-3 ℃ for min-1Heating to 500-600 ℃ at a heating rate, and carrying out constant temperature treatment for 2-5 h; after the reaction is finished and the quartz boat is cooled to room temperature, collecting the prepared light yellow product which is g-C3N4Particles;
step 3.2: g to C3N4Putting the particles into a vibration smashing type grinding machine, adding quaternary ammonium salt into the particles, pre-freezing for 20-40 min at the temperature of minus 30-35 ℃, and then performing vibration smashing and grinding for 20-40 min for 20-40 times, wherein each time lasts for 60 s; obtaining a small layer g-C upon completion of the grinding3N4Nanosheets; the obtained small layer g-C3N4The nanosheet is ultrasonically oscillated in isopropanol solution of polyvinylpyrrolidone for 10-30 min to strip out a single layer of g-C3N4Nanosheets.
5. The method for preparing silver-doped soft carbon-carbon nitride-TiO from waste cotton according to claim 42The method for preparing the composite material is characterized in that the mass ratio of the ball material during grinding in the step 3.2 is 80-100: 1.
6. The method for preparing silver-doped soft carbon-carbon nitride-TiO from waste cotton according to claim 12A method of forming a composite material, characterized in that,
in step 4, g-C3N4/TiO2The specific preparation process of the composite solution comprises the following steps:
and 4, step 4: measuring isopropyl titanate, dispersant polyethylene glycol 400 and absolute ethyl alcohol, and placing the mixture into a grinding tank to obtain TiO2Precursor isopropyl titanate anhydrous ethanol solution, and then monolayer g-C3N4Addition of nanosheets to TiO2Pre-freezing a precursor isopropyl titanate anhydrous ethanol solution at the temperature of minus 35-40 ℃ for 20-40 min, then vibrating, pounding and grinding for 20-40 min for 20-40 times for 60s each time to obtain g-C3N4/TiO2Compounding the solution;
the isopropyl titanate, the dispersant polyethylene glycol 400, the absolute ethyl alcohol and the monolayer g-C3N4The proportion of the nanosheets is 0.3-0.6 mL: 0.5-2.0 mL: 15-18 mL: 0.025 to 0.05 g.
7. The method for preparing silver-doped soft carbon-carbon nitride-TiO from waste cotton according to claim 12A method of forming a composite material, characterized in that,
in step 5, doping silver quantum dots with soft carbon/g-C3N4/TiO2The specific preparation process of the composite material comprises the following steps:
step 5.1: adding the soft carbon doped with the silver quantum dots in the step 2 into g-C3N4/TiO2Continuously vibrating, smashing and grinding the composite solution for 20-40 min to obtain a composite solution a;
step 5.2: adding the composite solution a into a polytetrafluoroethylene inner container, covering and sealing the inner container, then filling the inner container into a homogeneous reactor, and rotating at the speed of 5-10 r/min to 100 ℃ -Reacting at 140 ℃ for 2-5 h at constant temperature, and naturally cooling to room temperature; washing the obtained product with absolute ethyl alcohol and deionized water for 10-20 min respectively, repeating for 3-5 times, and freeze-drying; obtaining the silver-doped quantum dot soft carbon/g-C3N4/TiO2A composite material.
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| CN114367312A (en) * | 2022-01-25 | 2022-04-19 | 山东大学 | Ag+-Ag0Graphite-phase-doped carbon nitride coupled cobalt oxime molecule composite photocatalyst and preparation method and application thereof |
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