CN113145151A - Modified N-GQDs @ CdS nano-catalyst and preparation and application thereof - Google Patents
Modified N-GQDs @ CdS nano-catalyst and preparation and application thereof Download PDFInfo
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- 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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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Abstract
The invention relates to a modified N-GQDs @ CdS nano-catalyst and preparation and application thereof. The N-GQDs @ CdS nano-catalyst takes CdS as a core, N-GQDs grow on the surface of the CdS as the core, the N-GQDs and the CdS are connected through a covalent bond, and the N-GQDs are nitrogen element doped graphene quantum dots. The preparation method specifically comprises the following steps: (a) dissolving citric acid and ammonium carbonate in water, performing ultrasonic dispersion, transferring to a reactor for hydrothermal reaction, and sequentially cooling, rotary steaming and drying to obtain N-GQDs; (b) dissolving the N-GQDs obtained in the step (a) in water, adding cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide, mixing, performing ultrasonic dispersion, transferring to a reactor for hydrothermal reaction, and then sequentially cooling, washing and drying to obtain the N-GQDs @ CdS. Compared with the prior art, the photocatalyst can expand the light absorption range, is beneficial to hole-electron separation, can improve the catalytic efficiency, and has good degradation capability on methylene blue and methyl orange under the condition of ultraviolet light.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a modified N-GQDs @ CdS nano-catalyst, and preparation and application thereof.
Background
With the development of global society and industrial progress, environmental issues are becoming important matters of social widespread concern, wherein water pollution is becoming serious. At present, organic dye wastewater becomes one of main water pollution sources, and the wastewater has the characteristics of large water quantity, high concentration, complex components, deep chromaticity, difficult degradation and the like. Methylene blue and methyl orange are important organic chemical synthetic cationic dyes, have wide industrial application, but have toxic, carcinogenic, teratogenic and mutagenic effects, and inhibit photosynthesis of plants in aquatic systems; the COD value is high, which can lead to eutrophication of the water body. Common treatment methods include adsorption method, membrane separation method, common oxidation method, biological method and the like, but the methods have the defects of complex process flow, high equipment requirement, high cost, damage to microenvironment and the like. In recent years, photocatalytic degradation of toxic and harmful pollutants by semiconductor materials has become an important research direction. The photocatalysis technology has the advantages of low energy consumption, simple and convenient operation, mild reaction conditions and no secondary pollution, and can effectively convert organic pollutants into inorganic micromolecules to achieve the aim of complete inorganization.
The semiconductor photocatalyst is TiO2Silver-based semiconductors, tungsten-based semiconductors, ZnO, CdS and other semiconductor materials as a general term of substances for photocatalytic degradation. The photocatalyst mainly utilizes the fact that the energy of the emission of sunlight and ultraviolet light is larger than the energy gap of a semiconductor material, and valence band electrons in the semiconductor are excited to jump to a high-energy conduction band during illumination, so that electrons and holes are left in the valence band, and a part of photogenerated electrons (e) are generated-) And a cavity (h)+) Diffusing to the surface of the photocatalyst and finally adsorbing on the surface of the photocatalystThe electron or electron acceptor has oxidation-reduction reaction to form a series of chemical reactions initiated by active groups of the photocatalyst, and the photocatalyst has the advantages of proper energy band potential, high chemical stability, no toxicity, no harm, high photoelectric conversion efficiency, low cost, high activity and the like, so that the photocatalyst becomes an irreplaceable preferred material in chemical production and is mainly applied to the fields of organic synthesis, catalytic chemistry, environmental management, electrochemistry, biochemistry and the like.
However, the conventional photocatalyst is generally a single photocatalyst, and photo-generated electrons and holes generated in the process of illumination are easily self-recombined, which can reduce the number of the photo-generated electrons and holes, further cause the loss of active sites on the surface of the catalyst, reduce the photocatalytic efficiency, and hinder the further development of the photocatalyst. The modified graphene quantum dots integrate quantum confinement, size effect and edge effect, have the advantages of good water solubility, low biotoxicity, excellent chemical inertness, stable fluorescence, easy surface modification performance, excellent luminescence performance, adjustable band gap and the like, and have wide application prospects in the fields of chemical sensing, biological imaging, medical treatment and energy correlation. Therefore, it is imperative to modify the traditional photocatalyst to prepare a high-efficiency photocatalyst, and how to improve the effective active sites by the mutual combination of the modified photocatalyst or multiple photocatalysts, reduce the recombination rate of the photogenerated electrons and holes generated in the illumination process, and improve the photocatalytic efficiency has become a hotspot of research at present.
Patent CN111682222A discloses a preparation method and catalytic application of a Pt-CdS-nitrogen doped graphene quantum dot composite material. The Pt-CdS-nitrogen doped graphene quantum dot composite material is prepared from soluble cadmium salt, thiourea, citric acid and urea serving as raw materials by a solvothermal method, and is in a nanowire shape. (the following differences exist between this patent and the present invention: 1. the cadmium sulfide prepared by the patent is in a nanowire shape, but the cadmium sulfide prepared by the invention is in a spherical shape, so the specific surface area is greatly increased, the speed of transferring photo-generated electrons and holes on the surface of cadmium sulfide is increased when the light is irradiated, which is beneficial to increasing the photocatalytic efficiency.2. N-GQDs prepared by the patent need to react for 48 hours, but the invention can be completed only by 4 hours.3. the composite material prepared by the patent is prepared in parts and has complicated steps, but the experiment of the invention is completed in a one-pot hydrothermal method, which is convenient and fast.4. the composite material prepared by the patent is used for electrochemistry, and how the material is degraded in photocatalysis, and the catalyst can be used as a photocatalyst and can be used for degrading organic dyes, and is completely two different applications.
Disclosure of Invention
The invention aims to provide a modified N-GQDs @ CdS nano catalyst and preparation and application thereof.
The purpose of the invention is realized by the following technical scheme:
the catalyst takes CdS as a core, and N-GQDs grow on the surface, namely cadmium sulfide is the core, the N-GQDs load the surface of the N-GQDs, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the CdS are connected through a covalent bond, wherein the GQDs represent Graphene quantum dots (Graphene quantum dot), the N-GQDs are nitrogen element doped Graphene quantum dots, the specific surface area of the spherical CdS is greatly increased, the transmission rate of photogenerated electrons and holes on the surface of the cadmium sulfide is increased during illumination, and the photocatalytic efficiency is increased.
The preparation method of the modified N-GQDs @ CdS nano-catalyst specifically comprises the following steps:
(a) dissolving citric acid and ammonium carbonate in water, performing ultrasonic dispersion, transferring to a reactor for hydrothermal reaction, and sequentially cooling, rotary steaming and drying to obtain N-GQDs presenting blue fluorescent response;
(b) dissolving the N-GQDs obtained in the step (a) in water, adding cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide, mixing, ultrasonically dispersing, transferring to a reactor for hydrothermal reaction, and then sequentially cooling, washing and drying to obtain N-GQDs @ CdS, wherein the polyvinylpyrrolidone has a cross-linking polymerization effect, N-GQDs quantum dots can be better loaded on the surface of cadmium sulfide, the dimethyl sulfoxide has a sulfur source providing effect, and the CdS is obtained by reacting with the cadmium acetate, and the specific reaction process is as follows: cadmium sulfide is generated by reaction of cadmium acetate and dimethyl sulfoxide under the conditions of high temperature and high pressure in a hydrothermal reaction kettle, and N-GQDs grow on the surface of the cadmium sulfide under the action of polyvinylpyrrolidone and are finally anchored on the surface of the cadmium sulfide.
In the step (a), the molar ratio of citric acid to ammonium carbonate is 1:3, and the nitrogen-doped graphene quantum dots generated in the ratio have uniform particle size, uniform distribution and good water solubility.
In the step (a), the power of the ultrasonic wave is 150W, and the time of the ultrasonic wave is 0.1h, so that the reaction raw materials are uniformly dispersed to fully react.
In the step (a), the temperature of the hydrothermal reaction is 140-180 ℃, preferably 160 ℃, and the time is 2-6h, preferably 4 h.
In the step (b), the adding amount ratio of N-GQDs, cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide is (0.01-0.03) g to (0.133) g and (0.06-0.12) g to 40 mL.
In the step (b), the addition ratio of N-GQDs, cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide is preferably 0.02g:0.133g:0.1g:40 mL.
In the step (b), the power of the ultrasonic wave is 150W, and the time of the ultrasonic wave is 0.5h, so that the reaction raw materials are uniformly dispersed to fully react.
In the step (b), the temperature of the hydrothermal reaction is 160-180 ℃, and the time is 12-18 h.
In the step (b), the temperature of the hydrothermal reaction is 180 ℃ and the time is 15 h.
In step (b), the reaction mixture was cooled to room temperature, washed with absolute ethanol, and dried at 60 ℃ overnight.
The application of the N-GQDs @ CdS nano catalyst in the aspect of degrading dye wastewater is disclosed. Under the irradiation of ultraviolet light, the N-GQDs @ CdS has excellent degradation effect on methylene blue and methyl orange.
The invention provides a N-GQDs @ CdS nano catalyst, and adopts a one-pot hydrothermal method to regulate and control the performance of the catalyst by controlling the reaction time and the reaction temperature of hydrothermal reaction, the using amount of a precursor N-GQDs and the using amount of polyvinylpyrrolidone, so that the N-GQDs can be stably loaded on the surface of CdS under proper conditions, and finally the N-GQDs @ CdS catalyst is obtained, and the N-GQDs in the catalyst can emit blue fluorescence under 365 nm. The invention introduces N-GQDs into the CdS surface of the carrier, which can expand the light absorption range, is beneficial to the separation of holes and electrons, can improve the catalytic efficiency, can stably transmit electrons during the ultraviolet irradiation, and has good catalytic activity on methylene blue and methyl orange under the ultraviolet condition, probably because the synergistic action between N and GQDs leads to the increase of partial defects on the CdS surface of the catalyst, thereby forming a lower energy gap, and electrons can be transferred and retained under the ultraviolet light, thereby improving the catalytic efficiency. Compared with the traditional single N-GQDs and CdS, the N-GQDs @ CdS nano-catalyst obtained by the method overcomes the problems of instability and CdS light defects of the single catalyst, remarkably improves the catalytic efficiency, and expands the application of the N-GQDs @ CdS nano-catalyst in photocatalytic degradation of organic pollutants. According to the invention, through selecting the used raw materials, temperature and other conditions, the obtained final product is used for degrading two pollutants under a certain illumination condition, and the difference of the treatment effects of different catalysts prepared under different material doping conditions on the pollutants is explored, so that more ideas are provided for degrading dye wastewater.
Drawings
FIG. 1 is an infrared spectrum of the N-GQDs @ CdS nanocatalyst of example 1;
FIG. 2 is a Raman spectrum of the N-GQDs @ CdS nanocatalyst of example 1;
FIG. 3 is an SEM electron micrograph of the N-GQDs @ CdS nanocatalyst of example 1 at 10.0 μm;
FIG. 4 is SEM electron micrograph of N-GQDs @ CdS nanocatalyst of example 1 at 1.00 μm;
FIG. 5 is a graph showing the substantial comparison between the non-fluorescence of N-GQDs under natural light irradiation and the blue fluorescence under 365nm light irradiation in example 1;
FIG. 6 is a graph of the efficiency of N-GQDs @ CdS nanocatalyst in example 3 for degrading methylene blue and methyl orange as a function of time and light conditions;
FIG. 7 is a graph showing the efficiency of N-GQDs nanocatalyst degrading methylene blue in comparative example 1 as a function of time and light conditions;
fig. 8 is a graph showing the efficiency of the CdS nanocatalyst degrading methylene blue in comparative example 2 as a function of time and illumination conditions.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The raw materials used in the invention can be purchased in the market, are analytically pure, do not need further treatment and can be directly used, wherein, the used citric acid, ammonium carbonate, cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide are purchased from chemical reagents of national drug group, Inc.
Example 1
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.06g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
a preparation method for preparing N-GQDs @ CdS nano-catalyst based on controlling hydrothermal reaction time, temperature, N-GQDs and polyvinylpyrrolidone dosage comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at 150W, transferring into a 50mL hydrothermal reaction kettle, placing the reaction kettle into a drying box, keeping the temperature at 160 ℃ for 4h, cooling, carrying out rotary evaporation, and drying (cooling to room temperature is enough, the whole process of rotary evaporation is troublesome, firstly carrying out dialysis, then carrying out rotary evaporation, and finally drying at 60 ℃ for 12 h), preparing N-GQDs capable of emitting blue fluorescence under 365nm irradiation, and irradiating the N-GQDs under natural light, wherein the compound does not emit fluorescence, as shown in the right graph in FIG. 5, and the N-GQDs emits blue fluorescence under 365nm light, as shown in the left graph in FIG. 5;
(2) and (2) putting 10mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.06g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 15h at 180 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst. The infrared spectrogram and the Raman spectrogram of the catalyst are respectively shown in figures 1 and 2, characteristic peaks 1100C-N single bond and C-C single bond in the infrared spectrogram indicate that nitrogen elements are successfully doped into graphene quantum dots, 1400C ═ S bond indicates that the nitrogen-doped graphene quantum dots and cadmium sulfide are connected by C ═ S covalent bond, and the electron micrograph of the catalyst is shown in figures 3 and 4, and as can be seen from figure 3, a layer of coating on the surface of the cadmium sulfide can be seen in the electron micrograph, the nitrogen-doped graphene quantum dots loaded to the surface of the cadmium sulfide under the action of polyvinyl pyrrolidone are just above the cadmium sulfide, and as can be seen from figure 4, CdS particles are full and are basically round, and the particle size is 803-894 nm.
The catalyst is used for catalyzing methylene blue and methyl orange, and specifically comprises the following components: respectively putting 20mgN-GQDs @ CdS nano-catalysts into 150mL quartz tubes, respectively adding 10mg/L methylene blue and methyl orange solutions into the two quartz tubes, respectively adding the two rotors into the two quartz tubes, opening a photocatalytic reactor, stirring for 90min under a dark condition to achieve adsorption-desorption balance, opening a water circulation system, carrying out photocatalytic degradation under the condition of a 500w mercury lamp, taking samples every 10min, filtering by using a 0.22 mu m microporous filter head to remove residual catalysts, and then measuring absorbance in an ultraviolet spectrophotometer. The degradation efficiency calculation formula is as follows: eta is At/A0Eta: degradation efficiency; a. thet: absorbance at a certain time: a. the0: initial absorbance (same below). The degradation efficiency and the photocatalytic efficiency are specifically as followsAs shown in Table 1, the degradation efficiency of N-GQDs @ CdS nano-catalyst to methylene blue and methyl orange under the condition of ultraviolet light is known as follows: when the content of polyvinylpyrrolidone and N-GQDs is insufficient, the N-GQDs cannot be completely loaded on the surface of CdS and cannot provide enough effective active sites, so that the degradation efficiency of methylene blue and methyl orange is not high.
Example 2
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.08g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, cooling, rotary evaporating and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 20mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.08g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at the power of 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 15h at 180 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
The catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, and the degradation efficiency of the N-GQDs @ CdS nano catalyst to the methylene blue and the methyl orange under the ultraviolet light condition can be known as follows: when the consumption of the polyvinylpyrrolidone is insufficient, the N-GQDs loaded on the CdS surface are easy to fall off and are not enough to provide enough effective active sites, so that the degradation efficiency of the methylene blue and the methyl orange is not high.
Example 3
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, cooling, rotary evaporating and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 20mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at the power of 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 15h at 180 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
When the catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, the change situation of the degradation efficiency along with time is shown in fig. 6, and the degradation efficiency of the N-GQDs @ CdS nano catalyst on the methylene blue and the methyl orange under the ultraviolet light condition can be known: when the amounts of polyvinylpyrrolidone and N-GQDs are sufficient, the N-GQDs are loaded on the CdS surface stably enough to provide effective active sites, so that the degradation efficiency of methylene blue and methyl orange is better.
Example 4
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.12g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, cooling, rotary evaporating and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 30mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.12g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 15h at 180 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
The catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, and the degradation efficiency of the N-GQDs @ CdS nano catalyst to the methylene blue and the methyl orange under the ultraviolet light condition can be known as follows: when the amounts of polyvinylpyrrolidone and N-GQDs are too large, the N-GQDs are easy to agglomerate on the surface of CdS, but it is difficult to provide enough effective active sites, so that the degradation efficiency of methylene blue and methyl orange is not high.
Example 5
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, cooling, rotary evaporating and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 20mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at the power of 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature at 180 ℃ for 12h, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
The catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, and the degradation efficiency of the N-GQDs @ CdS nano catalyst to the methylene blue and the methyl orange under the ultraviolet light condition can be known as follows: when the amount of polyvinylpyrrolidone and N-GQDs is sufficient and the reaction time is insufficient, the N-GQDs cannot be completely loaded on the CdS surface and cannot provide enough effective active sites, so that the degradation efficiency of methylene blue and methyl orange is not high.
Example 6
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, cooling, rotary evaporating and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 20mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at the power of 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 15h at 160 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
The catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, and the degradation efficiency of the N-GQDs @ CdS nano catalyst to the methylene blue and the methyl orange under the ultraviolet light condition can be known as follows: when the hydrothermal reaction temperature is insufficient, the N-GQDs are loaded on the CdS surface unstably and cannot provide enough effective active sites, so that the degradation efficiency of methylene blue and methyl orange is not high.
Example 7
The modified N-GQDs @ CdS nano catalyst takes CdS as a core, N-GQDs grow on the surface, the particle size of the N-GQDs is 3-8nm, the CdS is spherical, the particle size of the CdS is 800-900nm, and the N-GQDs and the CdS are connected through a covalent bond. The preparation method comprises the following steps of preparing raw materials, wherein the raw materials comprise 0.21g of citric acid, 0.237g of ammonium carbonate, 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide. The method comprises the following specific steps:
(1) weighing 0.21g of citric acid and 0.237g of ammonium carbonate, dissolving in 40mL of deionized water, ultrasonically dispersing for 0.1h at the power of 150W, transferring into a 50mL hydrothermal reaction kettle, putting the reaction kettle into a drying box, preserving heat for 4h at 160 ℃, and then cooling, rotary steaming and drying to prepare blue fluorescent N-GQDs;
(2) and (2) putting 20mg of the prepared N-GQDs into a beaker, adding 0.133g of cadmium acetate, 0.1g of polyvinylpyrrolidone and 40mL of dimethyl sulfoxide into the beaker, ultrasonically dispersing for 0.5h at the power of 150W, transferring the beaker into a 50mL hydrothermal reaction kettle, preserving the temperature for 18h at 180 ℃, cooling to room temperature, washing with absolute ethyl alcohol, and drying at 60 ℃ overnight to prepare the N-GQDs @ CdS nano catalyst.
The catalyst is used for catalyzing methylene blue and methyl orange, the degradation efficiency and the photocatalytic efficiency are specifically shown in table 1, and the degradation efficiency of the N-GQDs @ CdS nano catalyst to the methylene blue and the methyl orange under the ultraviolet light condition can be known as follows: when the amount of polyvinylpyrrolidone and N-GQDs is sufficient and the reaction time is too long, agglomeration can occur between CdS, the load of N-GQDs is influenced, and sufficient effective active sites are difficult to provide, so that the degradation efficiency of methylene blue and methyl orange is not high.
TABLE 1 degradation efficiency summary of the N-GQDs @ CdS nanocatalysts prepared in each example and the methylene blue and methyl orange degradation efficiency of the two comparative examples
In conclusion, when the molar ratio of citric acid to ammonium carbonate is 1:3, the adding amount ratio of N-GQDs, cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide is 0.02g to 0.133g to 0.1g to 40mL, the reaction temperature of hydrothermal reaction in the step (2) is 180 ℃, and the reaction time is 15h, the prepared N-GQDs CdS @ nano catalyst has the optimal performance, can be used for degrading methyl orange and methylene blue, the degradation efficiency of methyl orange can reach 100% under irradiation for 90min under the illumination condition, the degradation efficiency of methylene blue can reach 100%, the degradation efficiency of catalysts prepared under other conditions can also reach more than 78% under the illumination condition, the degradation efficiency of methylene blue is also more than 76%, and the catalyst effect is basically better than that of a single N-GQDs catalyst and a single CdS catalyst.
Comparative example 1
Respectively putting 20mg of N-GQDs (the N-GQDs catalyst is obtained by the preparation step (1) shown in example 3) into two 150mL quartz tubes, respectively adding 100mL of 10mg/L methylene blue and methyl orange solution into the quartz tubes, respectively adding two rotors into the two quartz tubes, opening a photocatalytic reactor, stirring for 90min under dark conditions to achieve adsorption-desorption balance, opening a water circulation system, performing photocatalytic degradation under the condition of a 500w mercury lamp, taking a sample every 10min, filtering with a 0.22 μm microporous filter head to remove residual catalyst, and then measuring absorbance in an ultraviolet spectrophotometer, specifically as shown in FIG. 7, wherein the degradation efficiency of 90min methyl orange under dark conditions is 21%, the degradation efficiency of 90min methyl orange under illumination conditions is 64%, and the degradation efficiency of 90min methylene blue under illumination conditions is 24%, the degradation efficiency of methylene blue is 68% when the material is irradiated for 90min under the illumination condition.
Comparative example 2
Respectively putting 20mg CdS (CdS catalyst is obtained by the same operation as the preparation step (2) shown in the example 3 except that N-GQDs and polyvinylpyrrolidone are not added) into two 150mL quartz tubes, respectively adding 100mL 10mg/L methylene blue and methyl orange solutions into the two quartz tubes, respectively adding two rotors into the two quartz tubes, opening a photocatalytic reactor, stirring for 90min under dark conditions to achieve adsorption-desorption balance, opening a water circulation system at the moment, performing photocatalytic degradation under the condition of a 500w mercury lamp, taking a sample every 10min, filtering by using a 0.22 mu m microporous filter head to remove residual catalyst, and then performing absorbance measurement in an ultraviolet spectrophotometer, specifically as shown in FIG. 8, wherein the degradation efficiency of 90min methyl orange under the condition is 23%, and the degradation efficiency of 90min methyl orange under the illumination condition is 74%, the degradation efficiency of methylene blue is 27% in 90min under dark condition, and 72% in 90min under illumination condition.
Example 8
A modified N-GQDs @ CdS nano-catalyst is prepared by the following preparation method, and the preparation method is the same as the preparation method of the embodiment 3 except that the hydrothermal temperature in the step (1) is 140 ℃ and the time is 6 hours.
Example 9
A modified N-GQDs @ CdS nano-catalyst is prepared by the following preparation method, except that the hydrothermal temperature in the step (1) is 180 ℃ and the time is 2 hours, and the preparation method is the same as the preparation method of the embodiment 3.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The modified N-GQDs @ CdS nano catalyst is characterized in that the catalyst takes CdS as a core, N-GQDs grow on the surface of the CdS as the core, the N-GQDs are connected through covalent bonds, and the N-GQDs are nitrogen element doped graphene quantum dots.
2. The preparation method of the modified N-GQDs @ CdS nanocatalyst as claimed in claim 1, wherein the preparation method specifically comprises the following steps:
(a) dissolving citric acid and ammonium carbonate in water, performing ultrasonic dispersion, transferring to a reactor for hydrothermal reaction, and sequentially cooling, rotary steaming and drying to obtain N-GQDs;
(b) dissolving the N-GQDs obtained in the step (a) in water, adding cadmium acetate, polyvinylpyrrolidone and dimethyl sulfoxide, mixing, performing ultrasonic dispersion, transferring to a reactor for hydrothermal reaction, and then sequentially cooling, washing and drying to obtain the N-GQDs @ CdS.
3. The method for preparing a modified N-GQDs @ CdS nanocatalyst as claimed in claim 2, wherein in step (a), the molar ratio of citric acid to ammonium carbonate is 1: 3.
4. The preparation method of the modified N-GQDs @ CdS nanocatalyst as claimed in claim 2, wherein in the step (a), the temperature of the hydrothermal reaction is 140-180 ℃ and the time is 2-6 h.
5. The preparation method of the modified N-GQDs @ CdS nanocatalyst as claimed in claim 2, wherein in the step (b), the adding amount ratio of the N-GQDs, the cadmium acetate, the polyvinylpyrrolidone and the dimethyl sulfoxide is (0.01-0.03) g:0.133g, (0.06-0.12) g:40 mL.
6. The preparation method of the modified N-GQDs @ CdS nanocatalyst as claimed in claim 5, wherein in the step (b), the adding amount ratio of the N-GQDs, the cadmium acetate, the polyvinylpyrrolidone and the dimethyl sulfoxide is 0.02g:0.133g:0.1g:40 mL.
7. The method for preparing the modified N-GQDs @ CdS nanocatalyst as claimed in claim 2, wherein in the step (b), the temperature of the hydrothermal reaction is 160-180 ℃ and the time is 12-18 h.
8. The method for preparing a modified N-GQDs @ CdS nanocatalyst as claimed in claim 7, wherein in step (b), the temperature of the hydrothermal reaction is 180 ℃ and the time is 15 h.
9. The method for preparing a modified N-GQDs @ CdS nanocatalyst as claimed in claim 2, wherein in step (b), the nanocatalyst is cooled to room temperature, washed with absolute ethanol, and dried at 60 ℃ overnight.
10. The use of the N-GQDs @ CdS nanocatalyst as defined in claim 1 for degrading dye wastewater.
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