CN112371161A - Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof - Google Patents
Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J35/39—
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- B01J35/51—
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- B01J35/61—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to preparation and application of a carbon point modified graphite-phase carbon nitride hollow sphere photocatalyst, and belongs to the technical field of material preparation and photocatalysis. The photocatalyst is obtained by using a mixture of a graphite-phase carbon nitride precursor and a carbon dot precursor as a precursor of a product and mesoporous silica as a hard template through in-situ thermal polymerization and template etching, and is applied to a photocatalytic reaction. The carbon dot modified graphite phase carbon nitride prepared by the method has a hollow sphere structure, uniform particle size and good visible light absorption capacity. Compared with the traditional carbon nitride material, the material has larger specific surface area and higher sunlight absorption utilization rate, and can show high-efficiency photocatalytic performance under visible light. The preparation method of the material is simple, high in catalytic efficiency and low in price, meets the actual production requirement, and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation and photocatalysis, and particularly relates to a carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst as well as a preparation method and application thereof.
Background
With the mass exploitation and use of fossil fuels, the problems of environmental pollution and energy shortage are becoming more serious. While there is a constant search for clean energy sources that can be used to replace fossil fuels, hydrogen has attracted a great deal of attention due to its green, renewable nature. The photocatalytic decomposition of water by utilizing solar energy in the nature to prepare hydrogen has become a hotspot of current research. In recent years, the graphite-like phase carbon nitride material as a metal-free photocatalyst shows good development prospect in the field of photocatalytic decomposition of water to produce hydrogen. However, the graphite-like carbon nitride still has major disadvantages, such as narrow light absorption range, high recombination rate of photo-generated load, small specific surface area, and the like, which severely limits the wide application of the graphite-like carbon nitride.
Carbon nitride and carbon materials, such as graphene, carbon nanotubes and the like, are subjected to composite modification, so that the light absorption and utilization capacity of the materials can be effectively improved, and the recombination efficiency of photo-generated electron hole pairs is improved (int. j. hydrogen. energy. 2019, 44, 10316). Among the carbon materials used for the composite with carbon nitride, carbon dots are a new material which has attracted much attention, mainly carbon dots having up-conversion photoluminescence characteristics, small size, simple synthesis method, and the like (appl. cat. B: environ. 2016, 180, 656). However, the specific surface area of most of the carbon dot/carbon nitride composite photocatalysts is still small, and efficient photocatalytic water splitting reaction cannot be realized. Therefore, it is necessary to prepare a carbon dot modified carbon nitride material having a large specific surface area by a simple method and apply it to a photocatalytic water splitting reaction.
The related research of introducing the carbon point modification means into the hollow sphere carbon nitride photocatalyst has not been reported. According to the invention, the carbon dots are introduced to modify the hollow sphere carbon nitride material, so that the light absorption range of the material can be further widened, and the electron-hole separation efficiency in the material is improved; due to the existence of the hollow sphere structure, the specific surface area of the photocatalyst is also obviously increased, so that the photocatalytic performance of the material is obviously improved. Experiments prove that the carbon dot modified hollow sphere carbon nitride photocatalyst is an efficient visible-light-induced photocatalyst and has wide application prospect in the field of photocatalysis.
Disclosure of Invention
The invention aims to provide a carbon point modified graphite-phase carbon nitride hollow sphere photocatalyst and a preparation method thereof, and also discloses an application of the photocatalyst in hydrogen production. The preparation method is simple and low in cost, and the prepared carbon point modified graphite-phase carbon nitride hollow sphere photocatalyst has excellent photocatalytic water decomposition hydrogen production capacity and good circulation stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is obtained by using a mixture of a graphite-like phase carbon nitride precursor and a carbon point precursor as a precursor of a product, using mesoporous silica as a hard template and adopting in-situ thermal polymerization and template etching methods.
The graphite-like phase carbon nitride precursor is one of cyanamide, dicyandiamide, melamine, urea and thiourea.
The carbon point precursor is one of glucose, maltose, glycogen, citric acid and ascorbic acid.
The preparation method of the carbon point modified graphite-phase carbon nitride hollow sphere photocatalyst comprises the following steps:
1) dissolving a graphite-like phase carbon nitride precursor and a carbon point precursor in an aqueous solution of silica sphere sol, stirring at 40-60 ℃ by ultrasound, centrifuging, washing and drying; the dosage ratio of the graphite-like phase carbon nitride precursor to the carbon point precursor to the silicon dioxide is 5 g (1-10) mg to 1 g;
2) preserving the heat of the product obtained in the step 1) in a tubular furnace at 400-550 ℃ for 2-4 h, naturally cooling to room temperature, and continuously introducing protective gas in the heat preservation process;
3) adding the product obtained in step 2) to NH4HF2Or stirring in HF water solution for 12-24 h, centrifuging, washing, and vacuum drying at 60-80 ℃ to obtain the NH4HF2Or the concentration of the HF aqueous solution is 4 mol/L.
In the step 2), the tubular furnace is replaced by a muffle furnace without introducing protective gas.
In the step 3), the protective gas is argon or nitrogen.
The carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is applied to hydrogen production.
According to the invention, the graphite-like phase carbon nitride precursor and the carbon point precursor mixture are roasted in the presence of a silicon dioxide template, and the carbon point modified graphite-like phase carbon nitride hollow sphere photocatalyst is obtained after the template is etched away. The prepared photocatalyst has a hollow sphere structure, so that the specific surface area of the material is obviously increased; and the carbon dots loaded on the carbon nitride have up-conversion photoluminescence effect and electron collection capability, so that the light absorption range of the material can be widened, and the separation efficiency of electron-hole pairs can be improved. The common modification of the carbon dots and the hollow spheres can obviously improve the water decomposition and hydrogen production performance of the photocatalyst. The carbon point modified graphite phase carbon nitride hollow sphere material is simple in preparation method and low in preparation cost. Meanwhile, the hollow sphere carbon nitride and the carbon dots are obtained by a one-step double in-situ method, so that the hollow sphere carbon nitride and the carbon dots are connected more closely, the stability of the material is improved, the preparation process is simpler, the prepared material has better performance of photocatalytic decomposition of the hydrogen in the water, and the material has high practical value and wide development prospect. Specifically, compared with the prior art, the invention has the following significant advantages:
1. the specific surface area of the traditional carbon dot modified carbon nitride material is small, so that the photocatalytic reaction efficiency is low, the material obtained by the invention has a hollow sphere structure, and the specific surface area of the photocatalyst can be obviously improved, so that the water decomposition and hydrogen production performance of the photocatalyst is obviously improved;
2. the single hollow sphere carbon nitride material has a narrow light absorption range, the absorption band edge of the single hollow sphere carbon nitride material is even lower than that of the bulk graphite-like phase carbon nitride, and the hollow sphere carbon nitride is compounded with the carbon dots, so that the up-conversion photoluminescence effect of the carbon dots can be utilized, the light absorption range of the material is remarkably widened, the absorption and utilization capacity of the photocatalyst on sunlight is improved, and the hydrogen production performance of the material through photocatalytic water decomposition is further improved;
3. the hollow sphere carbon nitride material has more defects due to low polymerization degree of carbon nitride, is not favorable for the migration of electron-hole pairs generated in the photocatalysis process to the surface of the photocatalyst, and limits the improvement of the hydrogen production efficiency of photocatalytic decomposition water. According to the invention, the carbon dots and the hollow sphere carbon nitride are compounded, and the collection capability of the carbon dots on electrons is utilized, so that photo-generated electrons generated by the hollow sphere carbon nitride are gathered to the carbon dots, the electron-hole pair compounding efficiency in the photocatalyst is reduced, and the photocatalytic performance of the photocatalyst is improved;
4. the graphite-like carbon nitride precursor such as cyanamide and the like and the carbon point precursor such as glucose and the like are connected together in a solution through hydrogen bonds, the cyanamide is converted into the graphite-like carbon nitride in the thermal polymerization process, the glucose is carbonized to form carbon points, the two materials are still connected through the hydrogen bonds, the connection between the carbon point and the hollow sphere carbon nitride in the obtained photocatalyst is more stable, and the long-time use and recovery of the materials are facilitated;
5. the invention firstly prepares the carbon point modified graphite-like phase carbon nitride hollow sphere material and applies the material to the field of hydrogen production by photocatalytic water decomposition, and finds that the carbon point modification can obviously improve the photocatalytic hydrogen production performance of the hollow sphere carbon nitride material, the prepared material shows good circulation stability, can be stably used for a long time, has higher repeated utilization rate, and the used raw materials are nontoxic and low in price, the material preparation process is simple and easy to implement, and has larger application prospect in the field of photocatalysis.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst a obtained in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the photocatalyst b of the graphite-like carbon nitride hollow sphere obtained in comparative example 1;
FIG. 3 is an X-ray powder diffraction XRD pattern of the photocatalyst of the carbon dot modified graphite phase carbon nitride hollow sphere obtained in example 1;
FIG. 4 is a graph of the ultraviolet-visible diffuse reflectance spectrum (UV-VisDRS) of the carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst obtained in example 1;
fig. 5 is a comparison graph of the performance of the carbon dot modified graphite phase carbon nitride hollow sphere photocatalyst a obtained in example 1 and the performance of the hollow sphere carbon nitride photocatalyst b obtained in comparative example 1 for visible light catalytic decomposition of water to generate hydrogen under the same conditions.
Detailed Description
The following are some specific examples of the present invention to further illustrate the present invention, but the scope of the present invention is not limited to these examples. In the invention, the silica sol is the prior art, and the preparation method can refer to: sun J, Zhang J, Zhang M, et al, bioinsed held semiconductor nanoparticles [ J ] Nature Communications, 2012, 3(1): 1139.
Example 1
A carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is prepared by taking a mixture of a graphite-like phase carbon nitride precursor and a carbon point precursor as a product precursor through a hard template method; the precursor of the graphite-like phase carbon nitride is cyanamide; the carbon point precursor is glucose.
The preparation method comprises the following steps:
(1) weighing 5 g of cyanamide and 5 mg of glucose, adding the cyanamide and the glucose into an aqueous solution in which 1g of silica sol is dissolved, and carrying out ultrasonic stirring at 60 ℃, centrifuging, washing and drying to obtain white powder;
(2) keeping the white powder in a tube furnace at 550 ℃ for 4h, continuously introducing argon gas as protective gas in the heat preservation process, and naturally cooling to room temperature to obtain yellow powder;
(3) adding yellow powder to 4 mol/L NH4HF2Stirring the mixture in the water solution for 12 hours, centrifuging, washing and drying in vacuum at the temperature of 80 ℃ to obtain the product.
Example 2
A carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is prepared by taking a mixture of a graphite-like phase carbon nitride precursor and a carbon point precursor as a product precursor through a hard template method; the precursor of the graphite-like phase carbon nitride is cyanamide; the carbon point precursor is glucose.
The preparation method comprises the following steps:
(1) weighing 5 g of cyanamide and 10 mg of glucose, adding the cyanamide and the glucose into an aqueous solution dissolved with 1g of silica sol, and obtaining white powder after ultrasonic stirring, centrifugation, washing and drying at 60 ℃;
(2) keeping the white powder in a tube furnace at 550 ℃ for 4h, continuously introducing argon gas as protective gas in the heat preservation process, and naturally cooling to room temperature to obtain yellow powder;
(3) adding yellow powder to 4 mol/L NH4HF2Stirring the mixture in the water solution for 12 hours, centrifuging, washing and drying in vacuum at the temperature of 80 ℃ to obtain the product.
Example 3
A carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is prepared by taking a mixture of a graphite-like phase carbon nitride precursor and a carbon point precursor as a product precursor through a hard template method; the precursor of the graphite-like phase carbon nitride is cyanamide; the carbon point precursor is maltose.
The preparation method comprises the following steps:
(1) weighing 5 g of cyanamide and 5 mg of maltose, adding the cyanamide and the maltose into an aqueous solution dissolved with 1g of silica sol, and carrying out operations such as ultrasonic treatment, stirring at 60 ℃, centrifuging, washing, drying and the like to obtain white powder;
(2) keeping the white powder in a tube furnace at 550 ℃ for 4h, continuously introducing argon gas as protective gas in the heat preservation process, and naturally cooling to room temperature to obtain yellow powder;
(3) adding yellow powder to 4 mol/L NH4HF2Stirring the mixture in the water solution for 12 hours, centrifuging, washing and drying in vacuum at the temperature of 80 ℃ to obtain the product.
Example 4
A carbon point modified graphite phase carbon nitride hollow sphere photocatalyst is prepared by taking a mixture of a graphite-like phase carbon nitride precursor and a carbon point precursor as a product precursor through a hard template method; the precursor of the graphite-like phase carbon nitride is cyanamide; the carbon dot precursor is glycogen.
The preparation method comprises the following steps:
(1) weighing 5 g of cyanamide and 5 mg of glycogen, adding into an aqueous solution dissolved with 1g of silica sol, and performing operations such as ultrasonic treatment, stirring at 60 ℃, centrifuging, washing, drying and the like to obtain white powder;
(2) keeping the white powder in a tube furnace at 550 ℃ for 4h, continuously introducing argon gas as protective gas in the heat preservation process, and naturally cooling to room temperature to obtain yellow powder;
(3) adding yellow powder to 4 mol/L NH4HF2Stirring the mixture in the water solution for 12 hours, centrifuging, washing and drying in vacuum at the temperature of 80 ℃ to obtain the product.
In other embodiments, in the step (1), the graphite-like phase carbon nitride precursor may also be one of dicyandiamide, melamine, urea and thiourea, and the carbon point precursor may also be one of citric acid and ascorbic acid, and the stirring temperature may be between 40 and 60 ℃. In the step (2), the temperature is kept at 400-550 ℃ for 2-4 hours. In step 3), the product obtained in step 2) is added to NH4HF2Or stirring in HF water solution for 12-24 h, centrifuging, washing, and vacuum drying at 60-80 ℃ to obtain the catalyst.
In other embodiments, step (2) the tube furnace is replaced with a muffle furnace and no shielding gas is required.
Comparative example 1
An unmodified graphite-like carbon nitride hollow sphere photocatalyst uses cyanamide as a precursor.
The preparation method comprises the following steps:
(1) weighing 5 g of cyanamide, adding the cyanamide into an aqueous solution dissolved with 1g of silica sol, and obtaining white powder after ultrasonic stirring at 60 ℃, centrifuging, washing and drying;
(2) keeping the white powder in a tube furnace at 550 ℃ for 4h, continuously introducing argon gas as a protective gas in the heat preservation process, and naturally cooling to room temperature to obtain light yellow powder;
(3) adding yellow powder to 4 mol/L NH4HF2Stirring in water solution for 12 hr, centrifuging, washing, and vacuum drying at 80 deg.C.
And (3) performance testing:
1. observation by electron microscope
The prepared photocatalysts were observed by electron microscopy using example 1 as an example and comparative example 1 as a control, and the results are shown in fig. 1 and 2, respectively.
From the figure, it can be seen that the graphite-like phase carbon nitride has a distinct hollow sphere structure with a wall thickness of about 80 nm and a particle size of about 392 nm, and the presence of carbon dots can be clearly observed. It was confirmed that it formed a carbon dot modified hollow sphere carbon nitride photocatalyst. FIG. 2 shows that the wall thickness of the hollow sphere carbon nitride photocatalyst prepared in comparative example 1 is about 78 nm, the particle size is about 368 nm, the hollow sphere photocatalyst has an obvious hollow sphere structure, and no carbon point is observed. The method proves that carbon points can be introduced into the hollow sphere carbon nitride material without changing the shape and structure of the hollow sphere carbon nitride.
2. Structural testing
The structure of the obtained carbon dot modified graphite phase carbon nitride hollow sphere photocatalyst was tested by taking example 1 as an example, and the results are shown in fig. 3.
From fig. 3, it can be found that two characteristic peaks ascribed to graphite phase carbon nitride appear at 13.3 ° and 27.3 °, respectively corresponding to the (100) and (002) crystal planes of graphite phase carbon nitride, confirming that the introduction of carbon dots does not change the phase structure of the hollow sphere carbon nitride.
3. Light absorption Capacity test
The obtained carbon dot modified graphite phase carbon nitride hollow sphere photocatalyst was subjected to a light absorption capacity test by taking example 1 as an example, and the result is shown in fig. 4.
From fig. 4, it can be seen that the prepared carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst has good light absorption capacity in a full spectrum range, which indicates that the absorption utilization efficiency of the prepared photocatalyst to sunlight is significantly enhanced.
4. Photocatalytic capability test
The obtained carbon dot modified graphite phase carbon nitride hollow sphere photocatalyst was subjected to a photocatalytic ability test using example 1 as an example, while the result is shown in fig. 5 using comparative example 1 as a control.
The test conditions were as follows: 50 mg of photocatalyst, 20 mL of triethanolamine as a sacrificial agent and 80 mL of water were added to the reactor, and about 1.5 mg (~ 3 wt.%) of Pt as a cocatalyst was added. A300W xenon lamp with a cut-off filter (more than 420 nm) is used for carrying out a photocatalytic decomposition water hydrogen production capability test.
As can be seen from FIG. 5, the photocatalytic decomposition efficiency of the photocatalyst a of the carbon point modified graphite-phase carbon nitride hollow sphere for producing hydrogen is about 2322 mu mol g-1 h-1The hydrogen yield efficiency (1289 mu mol g) of the photocatalyst is higher than that of the hollow sphere carbon nitride photocatalyst b-1 h-1) The improvement is about 1.8 times.
The above-described embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. The photocatalyst is characterized in that a mixture of a graphite-like carbon nitride precursor and a carbon point precursor is used as a precursor of a product, mesoporous silica is used as a hard template, and the photocatalyst is obtained by in-situ thermal polymerization and template etching.
2. The photocatalyst of the carbon point-modified graphite-phase carbon nitride hollow sphere, according to claim 1, is characterized in that the graphite-like carbon nitride precursor is one of cyanamide, dicyandiamide, melamine, urea and thiourea.
3. The carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst as claimed in claim 1, wherein the carbon dot precursor is one of glucose, maltose, glycogen, citric acid and ascorbic acid.
4. A method for preparing the carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst as claimed in any one of claims 1 to 3, which comprises the following steps:
1) dissolving a graphite-like phase carbon nitride precursor and a carbon point precursor in an aqueous solution of silica sphere sol, stirring at 40-60 ℃ by ultrasound, centrifuging, washing and drying; the dosage ratio of the graphite-like phase carbon nitride precursor to the carbon point precursor to the silicon dioxide is 5 g (1-10) mg to 1 g;
2) preserving the heat of the product obtained in the step 1) in a tubular furnace at 400-550 ℃ for 2-4 h, naturally cooling to room temperature, and continuously introducing protective gas in the heat preservation process;
3) adding the product obtained in step 2) to NH4HF2Or stirring in HF water solution for 12-24 h, centrifuging, washing, and vacuum drying at 60-80 ℃ to obtain the NH4HF2Or the concentration of the HF aqueous solution is 4 mol/L.
5. The method for preparing the carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst according to claim 4, wherein in the step 2), the tubular furnace is replaced by a muffle furnace without introducing a protective gas.
6. The carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst of claim 1, wherein in step 3), the shielding gas is argon or nitrogen.
7. The use of the carbon dot modified graphite-phase carbon nitride hollow sphere photocatalyst of any one of claims 1 to 3 in hydrogen production.
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