CN113842939B - Photocatalyst and preparation method thereof - Google Patents
Photocatalyst and preparation method thereof Download PDFInfo
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- CN113842939B CN113842939B CN202111120395.5A CN202111120395A CN113842939B CN 113842939 B CN113842939 B CN 113842939B CN 202111120395 A CN202111120395 A CN 202111120395A CN 113842939 B CN113842939 B CN 113842939B
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- quantum dots
- photocatalyst
- graphite
- red phosphorus
- carbon nitride
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
A photocatalyst and a preparation method thereof belong to the field of hydrogen production by the photocatalyst. The photocatalyst is of a lamellar structure, and comprises graphite-phase carbon nitride, carbon quantum dots and red phosphorus quantum dots, wherein the carbon quantum dots and the red phosphorus quantum dots are arranged in a framework of the graphite-phase carbon nitride. The preparation method of the photocatalyst comprises the following steps: calcining the mixture of the carbon quantum dots and the graphite phase carbon nitride precursor at the temperature of 400-600 ℃ in an inert atmosphere to obtain a carbon quantum dot/graphite phase carbon nitride compound; mixing the carbon quantum dot/graphite phase carbon nitride compound with red phosphorus quantum dots, and performing heat treatment at a preset temperature to obtain a photocatalyst; the preset temperature is lower than the boiling point of the red phosphorus quantum dots. The photocatalyst has good photocatalytic hydrogen production performance.
Description
Technical Field
The application relates to the field of hydrogen production by a photocatalyst, in particular to a photocatalyst and a preparation method thereof.
Background
Hydrogen is an ideal clean energy source, is produced by decomposing water by solar energy, and plays a vital role in solving the energy and environmental problems. As a powerful solution, photocatalysis is an energy conversion process that uses inexhaustible green solar energy to produce ideal hydrogen fuel.
In the prior art, graphite-phase carbon nitride is utilized to decompose water under the irradiation of visible light in a photocatalysis manner, however, in the actual photocatalysis process, the forbidden band width of the graphite-phase carbon nitride is larger, the visible light is difficult to fully utilize, and the photo-generated electron-hole recombination is serious, so that the feasibility of the graphite-phase carbon nitride serving as a high-efficiency photocatalyst is limited.
Disclosure of Invention
The application provides a photocatalyst and a preparation method thereof, which have good photocatalytic hydrogen production performance.
Embodiments of the present application are implemented as follows:
in a first aspect, an embodiment of the present application provides a photocatalyst, where the photocatalyst has a sheet structure, and the photocatalyst includes graphite-phase carbon nitride, carbon quantum dots, and red phosphorus quantum dots, and at least some of the carbon quantum dots and the red phosphorus quantum dots are in a framework of the graphite-phase carbon nitride.
In a second aspect, an embodiment of the present application provides a method for preparing a photocatalyst according to the embodiment of the first aspect, including:
calcining the mixture of the carbon quantum dots and the graphite phase carbon nitride precursor at the temperature of 400-600 ℃ in an inert atmosphere to obtain a carbon quantum dot/graphite phase carbon nitride compound;
mixing the carbon quantum dot/graphite phase carbon nitride compound with red phosphorus quantum dots, and performing heat treatment at a preset temperature to obtain a photocatalyst; the preset temperature is lower than the boiling point of the red phosphorus quantum dots.
The photocatalyst and the preparation method thereof have at least the following beneficial effects:
the photocatalyst of the embodiment of the application has a lamellar structure, at least part of carbon quanta and red phosphorus quanta dots are in the framework of graphite phase carbon nitride, the carbon quanta dots and the red phosphorus quanta dots are firmly combined with the graphite phase carbon nitride, and the photocatalyst is not easy to fall off from the framework of the graphite phase carbon nitride in the process of carrying out photocatalysis hydrogen production on water. According to the photocatalyst provided by the embodiment of the application, through the synergistic effect of the carbon quantum dots and the red phosphorus quantum dots, the photocatalyst has good photocatalytic hydrogen production performance.
In the preparation method of the photocatalyst, the mixture of the carbon quantum dots and the graphite-phase carbon nitride precursor is calcined at the temperature of 400-600 ℃, the graphite-phase carbon nitride precursor becomes graphite-phase carbon nitride after being calcined, so that the carbon quantum dots/graphite-phase carbon nitride composite is prepared, then the carbon quantum dots/graphite-phase carbon nitride composite is mixed with red phosphorus quantum dots, heat treatment is carried out at the temperature lower than the boiling point of the red phosphorus quantum dots, the red phosphorus quantum dots cannot volatilize, and the carbon quantum dots/red phosphorus quantum dots/graphite-phase carbon nitride photocatalyst is prepared, and at least part of the carbon quantum dots and the red phosphorus quantum dots are arranged in a framework of graphite-phase carbon nitride.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of the red phosphorus quantum dots RPDs prepared in the steps S1 and S3 of example 2;
FIG. 2 is a TEM image of NCDs-en of the carbon quantum dots prepared in step S1 of example 2 of the present application;
FIG. 3 is a TEM image of the red phosphorus quantum dots RPDs prepared in step S3 of example 2 of the present application;
FIG. 4 is an XRD pattern of the CN/RPDs/NCDs-en photocatalyst prepared in example 2 of the present application;
FIG. 5 is a TEM image and elemental distribution diagram of the CN/RPDs/NCDs-en photocatalyst prepared in example 2 of the present application;
FIG. 6 is a graph showing the evaluation of the photocatalytic hydrogen production performance of the photocatalyst prepared in example 1 of the present application;
FIG. 7 is a graph showing the evaluation of the photocatalytic hydrogen production performance of the photocatalyst prepared in example 2 of the present application;
FIG. 8 is a graph showing the evaluation of the photocatalytic hydrogen production performance of the photocatalyst prepared in example 3 of the present application;
FIG. 9 is a graph showing evaluation of photocatalytic hydrogen production performance of the photocatalyst produced in comparative example 1 of the present application;
FIG. 10 is a graph showing evaluation of photocatalytic hydrogen production performance of the photocatalyst produced in comparative example 2 of the present application;
FIG. 11 is a graph showing evaluation of photocatalytic hydrogen production performance of the photocatalyst produced in comparative example 3 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a photocatalyst and a preparation method thereof according to an embodiment of the present application:
in a first aspect, an embodiment of the present application provides a photocatalyst, where the photocatalyst has a sheet structure, and the photocatalyst includes graphite-phase carbon nitride, carbon quantum dots, and red phosphorus quantum dots, and at least some of the carbon quantum dots and the red phosphorus quantum dots are in a framework of the graphite-phase carbon nitride.
The carbon quantum dot is a carbon material with the particle size below 10nm, can emit fluorescence under the illumination condition, and has the characteristics of good charge transmission capability and easiness in processing and modification due to the conjugated pi structure and rich surface functional groups. The red phosphorus quantum dots are red phosphorus particles with the particle size smaller than 10nm, have good visible light absorption capacity, and can be used for photocatalytic decomposition of water under the irradiation of visible light. According to the photocatalyst provided by the embodiment of the application, the carbon quantum dots and the red phosphorus quantum dots are arranged in the framework of graphite-phase carbon nitride, and the photocatalyst has good photocatalytic hydrogen production performance through the synergistic effect of the carbon quantum dots and the red phosphorus quantum dots. At least part of the carbon quantum dots and the red phosphorus quantum dots are in the framework of graphite phase carbon nitride, the carbon quantum dots and the red phosphorus quantum dots are firmly combined with the graphite phase carbon nitride, and the carbon quantum dots and the red phosphorus quantum dots are not easy to fall off from the framework of the graphite phase carbon nitride in the process of carrying out photocatalytic hydrogen production on water.
At least part of the carbon quantum dots and the red phosphorus quantum dots are in the framework of the graphite-phase carbon nitride, which means that all of the carbon quantum dots and the red phosphorus quantum dots are in the framework of the graphite-phase carbon nitride, or that part of the carbon quantum dots and the red phosphorus quantum dots are in the framework of the graphite-phase carbon nitride.
In a second aspect, an embodiment of the present application provides a method for preparing a photocatalyst according to the embodiment of the first aspect, including:
(1) And calcining the mixture of the carbon quantum dots and the graphite phase carbon nitride precursor at the temperature of 400-600 ℃ in an inert atmosphere to obtain the carbon quantum dot/graphite phase carbon nitride compound.
In the preparation method of the photocatalyst, the mixture of the carbon quantum dots and the graphite-phase carbon nitride precursor is calcined in an inert atmosphere at the temperature of 400-600 ℃, and the graphite-phase carbon nitride precursor becomes graphite-phase carbon nitride after calcination, so that the carbon quantum dot/graphite-phase carbon nitride compound is prepared, and the carbon quantum dots are doped in the framework of the graphite-phase carbon nitride and firmly combined with the graphite-phase carbon nitride. Alternatively, the calcination temperature is in a range between any one or any two of 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
Optionally, the inert atmosphere comprises at least one of nitrogen, helium, and argon.
In some embodiments, the graphite-phase carbon nitride precursor includes at least one of urea, thiourea, mono-cyanamide, dicyandiamide, and melamine.
In some embodiments, the mass of the carbon quantum dots is 0.01 to 20% of the mass of the graphite phase carbon nitride precursor.
When the dosage of the carbon quantum dots and the graphite phase carbon nitride precursor meets the proportion, the photocatalytic hydrogen production effect of the photocatalyst is more beneficial to improvement.
Illustratively, the mass of the carbon quantum dots is 0.01%, 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 15%, 18%, or 20% of the mass of the graphite phase carbon nitride precursor.
In some embodiments, the preparing step of the mixture of carbon quantum dots and graphite-phase carbon nitride precursor comprises: and mixing the carbon quantum dots with the graphite-phase carbon nitride precursor with water, and drying to obtain a mixture of the carbon quantum dots and the graphite-phase carbon nitride precursor.
And mixing the carbon quantum dots with the graphite-phase carbon nitride precursor and water to ensure that the carbon quantum dots and the graphite-phase carbon nitride precursor are mixed more uniformly, and the carbon quantum dots and the graphite-phase carbon nitride precursor are distributed more uniformly in the dried mixture of the carbon quantum dots and the graphite-phase carbon nitride precursor, so that the photocatalytic stability of the photocatalyst is improved.
In other embodiments, the carbon quantum dots and the graphite phase carbon nitride precursor may also be directly mixed and stirred to improve the uniformity of mixing the carbon quantum dots and the graphite phase carbon nitride precursor.
Further, in some embodiments, the preparing step of the carbon quantum dot comprises: mixing a carbon source with water, reacting at the temperature of 80-240 ℃ to obtain a first solution, and extracting carbon quantum dots from the first solution after the reaction is completed.
In the preparation method of the carbon quantum dot, other impurities are not introduced, and the prepared carbon quantum dot is purer. Illustratively, the above reaction may be carried out under water bath conditions.
Alternatively, the carbon source includes polyhydroxycarboxylic acids, carbohydrates, amino acid compounds. The polyhydroxycarboxylic acids include at least one of citric acid, malic acid, gluconic acid, and tartaric acid. The saccharide compound includes at least one of glucose, fructose, sucrose and cellulose. The amino acid compound includes at least one of glycine, alanine, tryptophan, and serine.
Alternatively, the temperature at which the reaction is carried out after the carbon source is mixed with water is in a range between any one or any two of 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃ and 240 ℃.
Alternatively, the carbon source is mixed with water and reacted for a period of time ranging from 5 to 20 hours, for example, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours or 20 hours.
In some embodiments, the step of extracting the carbon quantum dots from the first solution comprises: and cooling the first solution, dialyzing and drying to obtain the carbon quantum dots. The drying method is, for example, freeze drying or natural drying.
In the embodiment of the application, the carbon quantum dots can be directly purchased.
Further, in some embodiments, the carbon quantum dots are doped with at least one of nitrogen, sulfur, and phosphorus.
When the carbon quantum dots are doped with at least one of nitrogen, sulfur and phosphorus, the carbon source is doped with at least one of a nitrogen source, a sulfur source and a phosphorus source when the carbon quantum dots are prepared.
When the carbon quantum dots are doped with at least one of nitrogen, sulfur and phosphorus, the photocatalytic hydrogen production effect of the photocatalyst is improved. In addition, the inventors of the present application have found in the study that when at least one of a nitrogen source, a sulfur source, and a phosphorus source is doped in a carbon source when preparing the carbon quantum dots, the yield of the carbon quantum dots is higher.
Optionally, the nitrogen source comprises at least one of ethylenediamine, dicyandiamide, urea, thiourea, and cystine. Optionally, the sulfur source comprises at least one of thiourea and cystine. Optionally, the phosphorus source comprises at least one of phosphorous acid and phytic acid.
(2) Mixing the carbon quantum dot/graphite phase carbon nitride compound with red phosphorus quantum dots, and performing heat treatment at a preset temperature to obtain a photocatalyst; the preset temperature is lower than the boiling point of the red phosphorus quantum dots.
The carbon quantum dot/graphite phase carbon nitride compound is mixed with red phosphorus quantum dots, heat treatment is carried out at a temperature lower than the boiling point of the red phosphorus quantum dots, and the red phosphorus quantum dots cannot volatilize, so that the carbon quantum dot/red phosphorus quantum dot/graphite phase carbon nitride photocatalyst is prepared, and the carbon quantum dot and the red phosphorus quantum dot are arranged in a framework of graphite phase carbon nitride. Alternatively, the preset temperature is 150 to 250 ℃, for example 150 ℃, 180 ℃, 200 ℃, 220 ℃ or 250 ℃.
The inventor of the present application found in the study that if the graphite-phase carbon nitride precursor is first mixed with red phosphorus quantum dots and calcined, in order to ensure that the graphite-phase carbon nitride precursor is converted into graphite-phase carbon nitride during the calcination process, the calcination temperature should also be maintained at 400-600 ℃, the red phosphorus quantum dots will volatilize at this temperature, and finally the prepared photocatalyst does not contain red phosphorus quantum dots.
In addition, if red phosphorus is crushed into nano-scale red phosphorus particles by ultrasonic treatment, the nano-scale red phosphorus particles are loaded on graphite-phase carbon nitride to form a red phosphorus/graphite-phase carbon nitride compound, and the active sites of the carbon nitride are covered by the red phosphorus particles with larger particle size, so that the catalytic activity is affected. The photocatalyst is formed by adopting the red phosphorus quantum dots and the carbon quantum dots/graphite phase carbon nitride compound, the carbon quantum dots and the red phosphorus quantum dots are arranged in the framework of the graphite phase carbon nitride, the active sites of the carbon nitride cannot be affected, and the obtained carbon quantum dots/red phosphorus quantum dots/graphite phase carbon nitride photocatalyst has good catalytic activity.
Illustratively, the heat treatment is performed in an inert atmosphere. Wherein the inert atmosphere is optionally at least one of nitrogen, helium and argon.
In some embodiments, the mass of red phosphorus quantum dots is 0.1 to 20% of the mass of the carbon quantum dot/graphite phase carbon nitride composite.
When the dosage of the red phosphorus quantum dot and the carbon quantum dot/graphite phase carbon nitride compound meets the proportion, the photocatalytic hydrogen production effect of the photocatalyst is more beneficial to improvement.
Illustratively, the mass of red phosphorus quantum dots is 0.1%, 0.3%, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18% or 20% of the mass of the carbon quantum dot/graphite phase carbon nitride composite.
In some embodiments, the carbon quantum dot/graphite phase carbon nitride composite, red phosphorus quantum dot, and solvent are mixed, then dried, and then heat treated after drying. Optionally, the solvent comprises ethanol and/or water.
Because the carbon quantum dots are doped in the framework of the graphite phase carbon nitride in the carbon quantum dot/graphite phase carbon nitride compound, and are firmly combined with the graphite phase carbon nitride, the carbon quantum dots are not easy to fall off when being mixed with solvent alcohol. Alternatively, the drying mode is freeze drying or natural drying.
In some embodiments, the red phosphorus quantum dot preparation step includes: dispersing red phosphorus in water, reacting at 120-240 ℃ to obtain a second solution, and extracting red phosphorus quantum dots from the second solution after the reaction is completed.
According to the preparation method of the red phosphorus quantum dot, other impurities are not introduced, and the prepared red phosphorus quantum dot is purer. Illustratively, the above reaction may be carried out under water bath conditions.
Alternatively, the red phosphorus is dispersed in water and reacted at a temperature ranging between any one or any two of 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃ and 240 ℃.
Alternatively, the red phosphorus is dispersed in water and reacted for a period of time ranging from 12 to 36 hours, for example, 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, 30 hours, 33 hours or 36 hours.
In some embodiments, the step of extracting red phosphorus quantum dots from the second solution comprises: and cooling the second solution, performing ultrasonic treatment, standing, taking supernatant, and drying to obtain the red phosphorus quantum dot. Alternatively, the drying means is, for example, freeze drying or vacuum drying.
Compared with the heat treatment drying mode, the freeze drying and vacuum drying mode can avoid the oxidation of the red phosphorus quantum dots in the drying process.
It can be appreciated that the steps of ultrasonic treatment and taking the supernatant after standing can be sequentially and circularly performed, for example, the steps of first standing for taking the supernatant, then performing ultrasonic treatment for the second time, then performing standing for the second time for taking the supernatant, sequentially and circularly performing drying after taking the supernatant for the last time to obtain the red phosphorus quantum dot.
The photocatalyst of the present application and the preparation method thereof are described in further detail below with reference to examples.
Example 1
The present embodiment provides a method for preparing a photocatalyst, which includes:
s1: adding 0.02mol of citric acid into 40mL of water to uniformly disperse to obtain a dispersion liquid, placing the dispersion liquid into a 100mL reaction kettle to perform hydrothermal reaction at 180 ℃ for 5 hours, cooling to room temperature to obtain a pale yellow first solution, dialyzing the first solution, and freeze-drying to obtain white carbon quantum dots which are marked as CDs.
S2: mixing 0.5mg of CDs, 3.0g of urea and 20mL of water, freeze-drying to obtain white powder, placing the white powder in a tube furnace at 550 ℃ for calcination for 3 hours under the argon atmosphere, and cooling to room temperature to obtain dark yellow powder, namely a carbon quantum dot/graphite phase carbon nitride compound, which is marked as CN/CDs.
S3: 2.0g of the commercial red phosphorus after grinding is taken to be placed in 80mL of deionized water, the commercial red phosphorus is placed in a hydrothermal reaction kettle to react for 24 hours at 200 ℃ to obtain a second solution, the second solution is cooled and then subjected to ultrasonic treatment for 2 hours, then the second solution is kept stand for 1 hour, the supernatant fluid is taken to be subjected to ultrasonic treatment again, the cycle is carried out for 4 times, finally the supernatant fluid is taken to be subjected to vacuum drying, and finally red phosphorus quantum dots which are marked as RPDs are obtained.
S4: 100mg of CN/CDs and 2mg of RPDs are dispersed in 50% ethanol aqueous solution, ultrasonic stirring is carried out for 2 hours, red-yellow powder is obtained after rotary evaporation, and the powder is placed in a tube furnace under the atmosphere of argon and is subjected to heat treatment at the temperature of 250 ℃ for 2 hours, so that the carbon quantum dot/red phosphorus quantum dot/graphite phase carbon nitride photocatalyst is obtained, and the carbon quantum dot/red phosphorus quantum dot/graphite phase carbon nitride photocatalyst is recorded as CN/RPDs/CDs.
Example 2
The present embodiment provides a method for preparing a photocatalyst, which includes:
s1: adding 0.02mol of citric acid and 0.02mol of ethylenediamine into 40mL of water to uniformly disperse to obtain a dispersion liquid, placing the dispersion liquid into a 100mL reaction kettle to carry out hydrothermal reaction at 180 ℃ for 5 hours, cooling to room temperature to obtain a brownish black first solution, dialyzing the first solution, and freeze-drying to obtain golden-yellow nitrogen-doped carbon quantum dots which are marked as NCDs-en.
S2: mixing 0.5mg of NCDs-en, 3.0g of urea and 20mL of water, freeze-drying to obtain white powder, placing the white powder in a tube furnace under an argon atmosphere, calcining at 550 ℃ for 3 hours, and cooling to room temperature to obtain dark yellow powder, namely the nitrogen doped carbon quantum dots/graphite phase carbon nitride compound, which is marked as CN/NCDs-en.
S3: 2.0g of commercial red phosphorus after grinding is taken to be placed in a proper amount of deionized water, the commercial red phosphorus is placed in a hydrothermal reaction kettle to react for 24 hours at 200 ℃ to obtain a second solution, the second solution is cooled and then subjected to ultrasonic treatment for 2 hours, then the second solution is kept stand for 1 hour, the supernatant fluid is taken to be subjected to ultrasonic treatment again, the cycle is carried out for 4 times, finally the supernatant fluid is taken to be subjected to vacuum drying, and finally red phosphorus quantum dots which are marked as RPDs are obtained.
S4: 100mg of CN/NCDs-en and 2mg of RPDs are dispersed in 50% ethanol aqueous solution, the mixture is ultrasonically stirred for 2 hours, yellow red powder is obtained after rotary evaporation, and the yellow red powder is placed in a tube furnace under the argon atmosphere and is subjected to heat treatment at the temperature of 250 ℃ for 2 hours, so that the nitrogen-doped carbon quantum dot/red phosphorus quantum dot/graphite-phase carbon nitride photocatalyst is obtained, and the photocatalyst is recorded as CN/RPDs/NCDs-en.
Example 3
The present embodiment provides a method for preparing a photocatalyst, which includes:
s1: adding 0.02mol of citric acid and 0.02mol of urea into 40mL of water to uniformly disperse to obtain a dispersion liquid, placing the dispersion liquid into a 100mL reaction kettle to carry out hydrothermal reaction at 180 ℃ for 5 hours, cooling to room temperature to obtain a black and green first solution, dialyzing the first solution, and freeze-drying to obtain black nitrogen doped carbon quantum dots which are marked as NCDs-ur.
S2: mixing 0.5mg of NCDs-ur, 3.0g of urea and 20mL of water, freeze-drying to obtain white powder, calcining the white powder in a tubular furnace at 550 ℃ for 3 hours under the argon atmosphere, and cooling to room temperature to obtain dark yellow powder, namely the nitrogen-doped carbon quantum dots/graphite-phase carbon nitride composite, which is marked as CN/NCDs-ur.
S3: 2.0g of commercial red phosphorus after grinding is taken to be placed in a proper amount of deionized water, the commercial red phosphorus is placed in a hydrothermal reaction kettle to react for 24 hours at 200 ℃ to obtain a second solution, the second solution is cooled and then subjected to ultrasonic treatment for 2 hours, then the second solution is kept stand for 1 hour, the supernatant fluid is taken to be subjected to ultrasonic treatment again, the cycle is carried out for 4 times, finally the supernatant fluid is taken to be subjected to vacuum drying, and finally red phosphorus quantum dots which are marked as RPDs are obtained.
S4: 100mg of CN/NCDs-ur and 2mg of RPDs are dispersed in 50% ethanol aqueous solution, ultrasonic stirring is carried out for 2 hours, yellow red powder is obtained after rotary evaporation, and the powder is placed in a tube furnace under the atmosphere of argon and is subjected to heat treatment at the temperature of 250 ℃ for 2 hours, so that the nitrogen-doped carbon quantum dot/red phosphorus quantum dot/graphite-phase carbon nitride photocatalyst is obtained, and the photocatalyst is recorded as CN/RPDs/NCDs-ur.
Examples 4 to 7
Examples 4 to 7 each provide a method for preparing a photocatalyst, which differs from example 2 only in the amount of NCDs-en used in step S2, and in examples 4 to 7, the amounts of NCDs-en used were 0.2mg, 1mg, 3mg and 5mg, respectively.
Examples 8 to 11
Examples 8 to 11 each provide a method for preparing a photocatalyst, which differs from example 2 only in the amount of RPDs used in step S4, and in examples 8 to 11, the amounts of RPDs used are 0.5mg, 1mg, 3mg and 4mg, respectively.
Comparative example 1
This comparative example provides a photocatalyst, the preparation steps of which include:
3.0g of urea is placed in a corundum porcelain boat with a cover, the corundum porcelain boat is sealed for multiple times by adopting aluminum foil, the corundum porcelain boat is placed in a tube furnace under the protection of argon gas for calcining for 3 hours at 550 ℃, and light yellow powder, namely graphite-phase carbon nitride photocatalyst which is marked as CN, is obtained after cooling to room temperature.
Comparative example 2
This comparative example provides a method for preparing a photocatalyst, which differs from example 1 only in that steps S3 and S4 of example 1 are omitted.
Comparative example 3
The comparative example provides a method for preparing a photocatalyst, comprising the following steps:
s1: 3.0g of urea is placed in a corundum porcelain boat with a cover, the corundum porcelain boat is sealed for multiple times by adopting aluminum foil, the corundum porcelain boat is placed in a tube furnace under the protection of argon gas for calcining for 3 hours at 550 ℃, and light yellow powder, namely graphite phase carbon nitride which is marked as CN, is obtained after cooling to room temperature.
S2: 2.0g of commercial red phosphorus after grinding is taken to be placed in a proper amount of deionized water, the commercial red phosphorus is placed in a hydrothermal reaction kettle to react for 24 hours at 200 ℃ to obtain a second solution, the second solution is cooled and then subjected to ultrasonic treatment for 2 hours, then the second solution is kept stand for 1 hour, the supernatant fluid is taken to be subjected to ultrasonic treatment again, the cycle is carried out for 4 times, finally the supernatant fluid is taken to be subjected to vacuum drying, and finally red phosphorus quantum dots which are marked as RPDs are obtained.
S3: 100mg of CN and 2mg of RPDs are dispersed in 50% ethanol water solution, ultrasonic stirring is carried out for 2 hours, yellow red powder is obtained after rotary evaporation, and the powder is placed in a tube furnace under argon atmosphere and is subjected to heat treatment at the temperature of 250 ℃ for 2 hours, so that red phosphorus quantum dots/graphite phase carbon nitride photocatalyst which is recorded as CN/RPDs is obtained.
Test example 1
(1) XRD tests are carried out on the carbon quantum dots NCDs-en prepared in the step S1 in the example 2 and the red phosphorus quantum dots RPDs prepared in the step S3, and the obtained XRD patterns are shown in figure 1.
As can be seen from FIG. 1, there is a diffraction peak at 23℃in the XRD pattern of NCDs-en, which corresponds to the (002) crystal plane of the carbon quantum dot; the XRD pattern of RPDs has a diffraction peak at 15 °, which corresponds to the (102) crystal plane of the red phosphorus quantum dot.
(2) The carbon quantum dots NCDs-en prepared in step S1 and the red phosphorus quantum dots RPDs prepared in step S3 in example 2 were observed under a transmission electron microscope, and the obtained TEM images are shown in fig. 2 and 3, respectively.
As can be seen from fig. 2 and 3, the carbon quantum dots NCDs-en and the red phosphorus quantum dots RPDs are spherical particles with a size of <10nm, which illustrates that the carbon quantum dots and the red phosphorus quantum dots were successfully prepared in example 1.
(3) XRD testing was performed on the CN/RPDs/NCDs-en photocatalyst prepared in example 2, and the obtained XRD pattern was shown in FIG. 4.
As can be seen from FIG. 4, the XRD pattern of the CN/RPDs/NCDs-en photocatalyst has a weak diffraction peak at 13℃corresponding to the (100) crystal plane of graphite-phase carbon nitride and a slightly stronger diffraction peak at 27℃corresponding to the (002) crystal plane of graphite-phase carbon nitride.
(4) The obtained TEM images of the CN/RPDs/NCDs-en photocatalyst prepared in example 2 were observed under a transmission electron microscope, respectively, as shown in FIG. 5.
As can be seen from fig. 5, the basic morphology of the CN/RPDs/NCDs-en photocatalyst prepared in example 2 is lamellar, and some quantum dots are found, wherein the lamellar structure is graphite-phase carbon nitride, and the black small particles attached in the circles of the lamellar structure are quantum dots. In addition, the carbon element, the nitrogen element, the oxygen element and the phosphorus element are uniformly distributed in the element map, which indicates that the carbon quantum dots and the red phosphorus quantum dots are successfully doped into the graphite phase carbon nitride.
Test example 2
10mg of each of the photocatalysts of examples 1 to 11 and comparative examples 1 to 3 was taken, and each of the photocatalysts was mixed with 5mL of triethanolamine and 1.0mL of H having a concentration of 0.8mg/mL 14 Cl 6 O 6 The Pt solutions were mixed to obtain 14 sets of dispersion solutions, and then the 16 sets of solutions were subjected to photocatalytic reduction for 30min, and then catalytic evaluation was continuously performed for 4 hours, to finally obtain hydrogen production capacity of each photocatalyst, and the results are shown in table 1. The photocatalytic hydrogen production performance evaluation graphs corresponding to the photocatalysts of examples 1 to 3 are shown in fig. 6 to 8, and the photocatalytic hydrogen production performance evaluation graphs corresponding to the photocatalysts of comparative examples 1 to 3 are shown in fig. 9 to 11.
TABLE 1 photocatalytic Hydrogen production Performance of the photocatalyst
| Hydrogen production Performance/. Mu.mol g -1 h -1 | |
| Example 1 | 2874 |
| Example 2 | 3731 |
| Example 3 | 3576 |
| Example 4 | 2803 |
| Example 5 | 3272 |
| Example 6 | 2726 |
| Example 7 | 2175 |
| Example 8 | 2251 |
| Example 9 | 3361 |
| Example 10 | 2647 |
| Example 11 | 2156 |
| Comparative example 1 | 570 |
| Comparative example 2 | 2037 |
| Comparative example 3 | 2447 |
From the results in table 1, it can be seen that the photocatalysts of the embodiments of the present application all have better photocatalytic hydrogen production capability. In addition, as can be seen from the results of comparative examples 1, 2 and 3, doping nitrogen in the carbon quantum dots can enhance the photocatalytic hydrogen production capability of the photocatalyst.
As can be seen from the results of example 2 and examples 4 to 7, the hydrogen production effect of the photocatalyst of example 4 is inferior to that of example 2 and example 5, demonstrating that the photocatalytic hydrogen production capability of the photocatalyst is more advantageous when the mass of the nitrogen-doped carbon quantum dots is 0.01 to 1% of that of the graphite-phase carbon nitride precursor.
As can be seen from comparing the results of example 2 and examples 8 to 11, the hydrogen production effect of the photocatalysts of examples 2 and 9 is better than that of examples 8, 10 and 11, and it is illustrated that the photocatalytic hydrogen production capability of the photocatalysts is more advantageous when the mass of red phosphorus quantum dots is 1 to 2% of that of the carbon quantum dots/graphite phase carbon nitride composite.
The above description is only of specific embodiments of the application and is not intended to limit the application, but various modifications and variations can be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. The photocatalyst is characterized by being of a sheet structure, and comprises graphite-phase carbon nitride, carbon quantum dots and red phosphorus quantum dots, wherein at least part of the carbon quantum dots and the red phosphorus quantum dots are arranged in a framework of the graphite-phase carbon nitride; the preparation method of the photocatalyst comprises the following steps:
calcining the mixture of the carbon quantum dots and the graphite phase carbon nitride precursor at the temperature of 400-600 ℃ in an inert atmosphere to obtain a carbon quantum dot/graphite phase carbon nitride compound;
mixing the carbon quantum dot/graphite phase carbon nitride compound with red phosphorus quantum dots, and performing heat treatment at a preset temperature to obtain the photocatalyst; the preset temperature is lower than the boiling point of the red phosphorus quantum dots; the preset temperature is 150-250 ℃.
2. The photocatalyst of claim 1, wherein the heat treatment is performed in an inert atmosphere.
3. The photocatalyst of claim 1, wherein the mass of the carbon quantum dots is 0.01-20% of the mass of the graphite phase carbon nitride precursor.
4. The photocatalyst according to claim 1, wherein the mass of the red phosphorus quantum dot is 0.1 to 20% of the mass of the carbon quantum dot/graphite phase carbon nitride composite.
5. The photocatalyst of claim 1, wherein the preparing step of the mixture of carbon quantum dots and graphite phase carbon nitride precursor comprises: and mixing the carbon quantum dots with the graphite-phase carbon nitride precursor with water, and drying to obtain a mixture of the carbon quantum dots and the graphite-phase carbon nitride precursor.
6. The photocatalyst of claim 5, wherein the drying is freeze drying.
7. The photocatalyst of claim 1, wherein the carbon quantum dots are doped with at least one of nitrogen, sulfur, and phosphorus.
8. The photocatalyst of claim 1, wherein the graphite-phase carbon nitride precursor comprises at least one of urea, thiourea, mono-cyanamide, dicyandiamide, and melamine.
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| CN107899593A (en) * | 2017-11-21 | 2018-04-13 | 陕西科技大学 | The preparation method and application of carbon quantum dot/silver phosphate composite photocatalyst |
| CN108355696A (en) * | 2018-02-05 | 2018-08-03 | 中国科学院深圳先进技术研究院 | Black phosphorus/g-C3N4Composite visible light catalysis material and its preparation method and application |
| CN108704657A (en) * | 2018-05-31 | 2018-10-26 | 广东工业大学 | A kind of red phosphorus/graphite phase carbon nitride composite nano plate and its preparation method and application |
| WO2019229255A1 (en) * | 2018-05-31 | 2019-12-05 | Cambridge Enterprise Limited | Photocatalyst and photocatalytic methods for producing hydrogen |
| CN109603879A (en) * | 2018-12-24 | 2019-04-12 | 新疆工程学院 | A kind of preparation method of the graphite phase carbon nitride catalysis material of carbon quantum dot modification |
| CN110841669A (en) * | 2019-11-21 | 2020-02-28 | 湖南大学 | Method for treating heavy metals and organic pollutants by using zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst |
| CN110841670A (en) * | 2019-11-21 | 2020-02-28 | 湖南大学 | Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof |
| CN111215112A (en) * | 2020-01-17 | 2020-06-02 | 华侨大学 | Preparation method and application of composite photocatalyst |
| CN111808610A (en) * | 2020-03-19 | 2020-10-23 | 广东两山科技有限公司 | Carbon nitride-like phosphorus-rich quantum dot fluorescent probe and preparation method and application thereof |
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