CN116371441A - Sulfur-containing carbon nitride material, preparation method thereof and application thereof in photocatalytic hydrogen production - Google Patents
Sulfur-containing carbon nitride material, preparation method thereof and application thereof in photocatalytic hydrogen production Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
- 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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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a sulfur-containing carbon nitride material, a preparation method thereof and application thereof in photocatalysis hydrogen production, wherein the sulfur-containing carbon nitride material is obtained by calcining cyanuric acid under inert atmosphere in indirect contact with melamine. The sulfur-containing carbon nitride material provided by the invention has the advantages of large specific surface area, strong light absorption capability, high photocatalytic hydrogen production activity, excellent cycle stability, good photocatalytic hydrogen production application prospect, good safety of the preparation method, simple synthetic raw materials, few operation steps, and low cost, and the sulfur-containing carbon nitride material can be obtained by respectively placing the two raw materials weighed in proportion into two porcelain boats which are placed in a tube furnace and keep a certain distance for one-step calcination.
Description
Technical Field
The invention belongs to the technical field of catalysts of nitrogen compounds containing sulfur, and particularly relates to a sulfur-containing carbon nitride material, a preparation method thereof and application thereof in photocatalytic hydrogen production.
Background
Reasonable resource development is particularly important. The water resources on the earth are rich, solar energy is inexhaustible, so the hydrogen production by utilizing the solar energy to decompose the water is one of the key ways for solving the energy problem.
The photocatalysis hydrogen production technology converts solar energy into hydrogen energy, is a low-cost, environment-friendly and pollution-free technology, has mild reaction conditions and wide application range, and has very wide development prospect. The photocatalysis hydrogen production technology needs the catalysis of a photocatalyst, researchers mainly focus on the research of oxide semiconductor photocatalytic materials, and the materials generally have the characteristic of being easily dissolved in an acid-base reagent and difficult to modify, so that the application development of the materials is limited.
In recent years, non-metal semiconductor photocatalyst graphite phase carbon nitride (g-C 3 N 4 ) The material enters the field of vision of people due to g-C 3 N 4 Sp in structure 2 The hybridized C and N atoms form a certain conjugated system, so that the conjugated system has excellent heat stability, chemical stability and other properties, and the g-C 3 N 4 The catalyst can absorb visible light, has simple preparation process and low cost, can catalyze and decompose water to prepare hydrogen under the condition that visible light irradiates and triethanolamine is used as a hole scavenger, and has a great development space in the field of photocatalysis hydrogen production. However, g-C 3 N 4 The specific surface area is low, the forbidden bandwidth is about 2.72eV, the photo-generated electron-hole is easy to be combined, the conductivity is low, and the like, so that the catalytic activity is limited, and the modification is needed. Currently by doping (metals, non-metals, noble metals etc.),
morphology regulation, semiconductor composite modification, cocatalyst loading and other means on g-C 3 N 4 Modifying, regulating the composition of material or changing specific surface area to improve the said disadvantages and raise the photocatalytic activity. When the reaction is carried out on g-C 3 N 4 By controlling g-C during sulfur doping 3 N 4 The composition, the electronic structure and the thin sheet layer thickness can increase the specific surface area and simultaneously cause certain defects to expose more living thingsSexual site, improve the performance of photocatalysis hydrogen production. Patent CN111185216a discloses a solution in which melamine and cyanuric acid are mixed in a solvent, then subjected to hydrothermal reaction to obtain a solid tubular composite, and then calcined with urea to obtain a hollow tubular sulfur-doped carbon nitride/graphite-phase carbon nitride homojunction photocatalyst. Patent CN107930667a discloses a method for preparing sulfur-doped carbon nitride by respectively dissolving melamine and cyanuric acid in hot water, uniformly mixing, performing hydrothermal reaction, and calcining. The preparation methods disclosed by the methods are complicated in steps, require post-treatment and have relatively high cost.
Therefore, some experimental methods with simpler operation, lower energy consumption cost and better effect are required to be developed, so that the method is applied to the field of photocatalytic hydrogen production. According to the invention, only two raw materials, namely cyanuric acid and melamine, are adopted, the raw materials are weighed separately and do not directly contact with each other, and the raw materials are put into a tube furnace for direct calcination to obtain the sulfur-containing carbon nitride material, so that the operation is simple and convenient, the energy consumption is low, the prepared sulfur-containing carbon nitride material has good photocurrent responsiveness, the hydrogen production rate reaches 165.4 mu mol/h, and the hydrogen production stability is good.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a sulfur-containing carbon nitride material, a preparation method thereof and application thereof in photocatalytic hydrogen production, wherein the sulfur-containing carbon nitride material has large specific surface area, is sensitive to visible light response, has high photocatalytic hydrogen production activity, and is simple and easy to operate and good in repeatability.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provided is a sulfur-containing carbon nitride material obtained by calcining cyanuric acid under an inert atmosphere in indirect contact with melamine.
According to the scheme, the specific surface area of the sulfur-containing carbon nitride material is 50-150 m 2 /g。
The invention also provides a preparation method of the sulfur-containing carbon nitride material, which comprises the following specific steps:
1) Weighing cyanuric acid and melamine according to a proportion for standby;
2) Uniformly spreading cyanuric acid on the surface of a No. 1 porcelain boat, uniformly spreading melamine on the surface of a No. 2 porcelain boat, then placing the No. 1 porcelain boat in the middle of a constant temperature area of a tubular furnace, placing the No. 2 porcelain boat in the tubular furnace close to an air inlet, introducing inert gas into the tubular furnace through the air inlet, heating for calcination, cooling to room temperature along with the furnace, and collecting samples in the No. 1 porcelain boat for grinding to obtain the sulfur-containing carbon nitride material.
According to the scheme, the purity of the cyanuric acid in the step 1) is more than or equal to 95 weight percent, and the purity of the melamine is more than or equal to
99wt％。
According to the scheme, the mass ratio of the cyanuric acid to the melamine in the step 1) is 0.5-2: 1.
according to the scheme, the distance between the centers of the No. 1 porcelain boat and the No. 2 porcelain boat in the step 2) is 10-20 cm.
According to the scheme, the inert atmosphere in the step 2) is nitrogen or argon, the gas purity is more than 99.99vol%, and the gas flow is 60-100 mL/min.
According to the scheme, the calcining process conditions in the step 2) are as follows: raising the temperature to 500-600 ℃ at the room temperature at the temperature raising rate of 5-15 ℃/min, and preserving the heat for 3-5 h.
The invention also comprises application of the sulfur-containing carbon nitride material in photocatalytic hydrogen production.
According to the invention, cyanuric acid and melamine are calcined in an inert atmosphere in a non-direct contact state to obtain the sulfur-containing carbon nitride material, the cyanuric acid is used as a precursor, ammonia gas generated by the melamine flows on the surface of the cyanuric acid in the calcining process, a certain stripping effect is realized in the process of generating sulfur-containing carbon nitride by polymerizing the cyanuric acid, the sulfur-containing carbon nitride material with high crystallinity and certain defects is generated, and the test result shows that the sulfur-containing carbon nitride material has excellent photocatalytic hydrogen production performance.
The invention has the beneficial effects that: 1. the sulfur-containing carbon nitride material provided by the invention has the advantages of large specific surface area, strong light absorption capacity, high photocatalytic hydrogen production activity, excellent cycling stability and good photocatalytic hydrogen production application prospect. 2. According to the invention, only two raw materials, namely cyanuric acid and melamine, are adopted, ammonia gas is generated by indirectly utilizing melamine to strip, a large amount of ammonia gas is not directly utilized to directly contact, the risk is reduced, the safety is good, the synthetic raw materials are simple, the operation steps are few, the two raw materials weighed according to the proportion are respectively put into two porcelain boats which are arranged in a tube furnace and keep a certain distance for one-step calcination, and the sulfur-containing carbon nitride material can be obtained, so that the cost is low.
Drawings
FIG. 1 is a comparative graph showing the effect of photocatalytic hydrogen production on sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 5 of the present invention;
FIG. 2 is a graph showing photocurrent measurements of sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-3;
FIG. 3 is a graph showing the photocurrent test of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1, 4, and 5;
FIG. 4 is a graph showing the comparison of hydrogen production at different wavelengths for the sulfur-containing carbon nitride material prepared in example 4;
FIG. 5 is a graph showing the stability of the photocatalytic hydrogen production cycle for 20 hours for the sulfur-containing carbon nitride material prepared in example 4;
FIG. 6 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1-3;
FIG. 7 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1, 4, and 5;
FIG. 8 is a graph showing isothermal adsorption and desorption of nitrogen from sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-3;
FIG. 9 is a graph showing isothermal adsorption and desorption of nitrogen from the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, and 5;
FIG. 10 is a graph showing pore size distribution of sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 3;
FIG. 11 is a graph showing pore size distribution of sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, and 5;
FIG. 12 is a graph showing the resistance of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 3;
FIG. 13 is a graph showing the impedance of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, and 5.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention.
Comparative example 1
A sulfur-containing carbon nitride material is prepared by the following steps:
1) Weighing 2g of cyanuric acid (purity 95 wt%) for standby;
2) Spreading cyanuric acid solid in a porcelain boat, putting the porcelain boat in the middle of a constant temperature area of a tube furnace, introducing nitrogen (99.99 vol%) into the tube furnace, setting the flow rate of the nitrogen to be 80mL/min, heating to 550 ℃ at room temperature at the heating rate of 10 ℃/min for calcination, naturally cooling to room temperature for 3 hours, and grinding into powder to obtain the sulfur-containing carbon nitride material (named SCN).
Example 1
A sulfur-containing carbon nitride material is prepared by the following steps:
1) 2g of cyanuric acid (purity 95 wt%) and 3g of melamine (purity 99 wt%) were weighed for use;
2) The cyanuric acid is flatly paved on a No. 1 porcelain boat, the cyanuric acid is placed in the middle of a constant temperature area of a tube furnace, the melamine is flatly paved on a No. 2 porcelain boat, the melamine is placed in the tube furnace and is close to an air inlet, the distance between the centers of the No. 1 porcelain boat and the No. 2 porcelain boat is 15cm, nitrogen (99.99 vol%) is introduced into the tube furnace, the flow rate of the nitrogen is 80mL/min, then the temperature is raised to 550 ℃ at the temperature rising rate of 10 ℃/min for calcination at the room temperature, the calcination time is 3h, and the sulfur-containing carbon nitride material (marked as A) is obtained by grinding the powder after the melamine is naturally cooled to the room temperature.
Example 2
A sulfur-containing carbon nitride material was prepared in a similar manner to example 1, except that in step 2), the flow rate of nitrogen gas was set to 100mL/min, and the resultant product was designated as B.
Example 3
A sulfur-containing carbon nitride material was prepared in a similar manner to example 1, except that in step 2), the flow rate of nitrogen gas was set to 60mL/min, and the resultant product was designated as C.
Example 4
A sulfur-containing carbon nitride material was prepared similarly to example 1 except that the distance between the centers of the No. 1 porcelain boat and the No. 2 porcelain boat in step 2) was 10cm, and the resultant product was designated as D.
Example 5
A sulfur-containing carbon nitride material was prepared similarly to example 1 except that the distance between the centers of the No. 1 porcelain boat and the No. 2 porcelain boat in step 2) was 20cm, and the resultant product was designated as E.
And (3) testing the photocatalytic hydrogen production performance: 20mg of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1 to 5 was added to 6 parts of 100mL of deionized water solution containing 10wt% of triethanolamine, respectively, and 0.33mL of H was added to each part of the solution 2 PtCl 4 Solution (mass fraction of Pt based on 20mg of photocatalyst supported was 3wt%, H) 2 PtCl 4 Playing a role of a catalyst promoter in a photocatalysis system), after ultrasonic dispersion of the mixed solution for 30min, testing in a photoreactor (Labsolar-6A, a 300W xenon lamp with a 420nm cutoff filter inserted as a light source) for 4H, and comparing the visible light photocatalysis hydrogen production effect of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-5 with that of FIG. 1, it can be seen that the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-5 produce H 2 The rates are respectively as follows: SCN 62.9. Mu. Mol/h, A144.9. Mu. Mol/h, B127.1. Mu. Mol/h, C108.1. Mu. Mol/h, D165.4. Mu. Mol/h, E119.9. Mu. Mol/h, wherein the photocatalytic hydrogen production rates of A to E are higher than those of SCN and D are the highest. Photocurrent testing: preparing the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-5 into 1.0g/L aqueous dispersion, sucking 8 μl of each aqueous dispersion, and dripping onto the surface of glassy carbon electrode (diameter of 3 mm), using Chen Hua electrochemical workstation, in>Under the illumination condition of 420nm, 0.5mol/L Na is added 2 SO 4 Photocurrent testing was performed in solution. The photo-current can reflect the photo-catalytic performance of the material, the higher the photo-current is, the more the photo-generated carriers can be promoted to be separated, the better the photo-catalytic effect of the material is, the photo-current test patterns of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1-3 are shown in figure 2, the comparative exampleThe photo-current test patterns of the sulfur-containing carbon nitride materials prepared in 1 and examples 1, 4 and 5 are shown in fig. 3, and the test results show that the SCN photo-current is minimum, and the comparison examples 1 to 3 show that the A photo-current prepared in example 1 is maximum when the porcelain boat distance is kept to be 15cm and the air flow is regulated. As can be seen from comparative examples 1, 4 and 5, the D photocurrent prepared in example 4 was maximized while maintaining the air flow at 80mL/min and adjusting the distance of the porcelain boat.
FIG. 4 is a graph showing the comparison of hydrogen production of the sulfur-containing carbon nitride material prepared in example 4 at different wavelengths, wherein several photocatalyst solutions were prepared, and each photocatalyst solution was prepared by the following method: 20mg of sulfur-containing carbon nitride material D prepared in example 4 was added to 100mL of deionized water solution containing 10wt% of triethanolamine, and 0.33mL of H was added 2 PtCl 4 The solution (mass fraction of Pt based on 20mg of photocatalyst-supported was 3 wt%) was obtained after ultrasonic dispersion of the mixed solution for 30 min. The prepared photocatalyst solution is placed in a photo-reactor (Labsolar-6A, light source is 300W xenon lamp) to be illuminated for 4 hours for hydrogen production test, and the wavelengths of light are 365nm, 420nm, 450nm, 500nm, 550nm and cut-off 420nm (namely>420 nm), as can be seen from fig. 4, there is a certain hydrogen production effect under each wavelength of illumination.
Testing the stability of the catalytic hydrogen production cycle of the sulfur-containing carbon nitride material: 20mg of sulfur-containing carbon nitride material D prepared in example 4 was added to 100mL of deionized water solution containing 10wt% of triethanolamine, and 0.33mL of H was added 2 PtCl 4 (mass fraction based on 20mg of photocatalyst-supported Pt is 3 wt%) after the mixed solution is ultrasonically dispersed for 30min, the cyclic hydrogen production stability test is carried out in a photoreactor (Labsolar-6A, a 300W xenon lamp with a 420nm cut-off filter inserted as a light source), the test is stopped once every 4h, the total time is 20h, the test chart of the continuous 20h photocatalytic hydrogen production cyclic stability of the sulfur-containing carbon nitride material prepared in the embodiment 4 is shown in fig. 5, and the cyclic stability of the sulfur-containing carbon nitride material is found to be good from the chart.
Fig. 6 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1 to 3, and fig. 7 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in comparative example 1 and examples 1, 4, 5. From fig. 6 and 7, it can be seen that there are two main peaks in the XRD pattern of the sample, and the peak of the (100) plane corresponding to about 13 ° represents the intra-layer structure stack of the material unit ring. Another peak at about 27.1 ° corresponds to an interlayer stack of conjugated aromatic units, which is attributed to the (002) plane. Compared with the positions and intensities of the corresponding peaks, the peak intensity of the corresponding (002) surface of SCN is the lowest, the peak intensity of the material prepared in the examples 1-5 is improved to some extent, which shows that the structure of the sulfur-containing carbon nitride material synthesized by introducing melamine as an ammonia source is more ordered, the crystallinity is higher, the (002) crystal faces of the material prepared in the examples 1-5 are all moved to a certain extent, the interlayer distance is reduced, the migration path of carriers is reduced, and the separation efficiency of carriers is improved.
Fig. 8 is a graph of isothermal adsorption and desorption of nitrogen from the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 3, fig. 9 is a graph of isothermal adsorption and desorption of nitrogen from the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, 5, fig. 10 is a graph of pore size distribution of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 3, and fig. 11 is a graph of pore size distribution of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, 5. As can be seen from fig. 8 and 9, a typical N 2 Adsorption and desorption isotherms show that the sulfur-containing carbon nitride material sample has a mesoporous structure, wherein the specific surface area of the sample D is maximum and reaches 135.75m 2 And/g, the specific surface area is large, and more active sites can be exposed, so that the photocatalytic hydrogen production activity is improved. From fig. 10, fig. 11 shows the pore size distribution graph that the sample of the sulfur-containing carbon nitride-like material contains mesopores.
Fig. 12 is a graph showing the resistance of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1 to 3, and fig. 13 is a graph showing the resistance of the sulfur-containing carbon nitride materials prepared in comparative example 1 and examples 1, 4, and 5. As can be seen from fig. 12 and 13, the sulfur-containing carbon nitride materials prepared in examples 1 to 5 have smaller semicircular arcs and the semicircular arc of the sample D is smallest, which indicates that SCN has the highest carrier transport resistance, and that the carrier transport resistance of D is relatively smallest, and that the transport efficiency is high and the electron transport capability is stronger, as compared with the comparative example SCN.
Claims (9)
1. The sulfur-containing carbon nitride material is characterized in that the sulfur-containing carbon nitride material is obtained by calcining cyanuric acid under inert atmosphere in indirect contact with melamine.
2. The sulfur-containing carbon nitride material according to claim 1, wherein the sulfur-containing carbon nitride material has a specific surface area of 50 to 150m 2 /g。
3. A method for preparing the sulfur-containing carbon nitride material according to claim 1 or 2, comprising the following specific steps:
1) Weighing cyanuric acid and melamine according to a proportion for standby;
2) Uniformly spreading cyanuric acid on the surface of a No. 1 porcelain boat, uniformly spreading melamine on the surface of a No. 2 porcelain boat, then placing the No. 1 porcelain boat in the middle of a constant temperature area of a tubular furnace, placing the No. 2 porcelain boat in the tubular furnace close to an air inlet, introducing inert gas into the tubular furnace through the air inlet, heating for calcination, cooling to room temperature along with the furnace, and collecting samples in the No. 1 porcelain boat for grinding to obtain the sulfur-containing carbon nitride material.
4. The method for producing sulfur-containing carbon nitride material according to claim 3, wherein the cyanuric acid in step 1) has a purity of 95 wt.% or more and the melamine has a purity of 99 wt.% or more.
5. The method for producing a sulfur-containing carbon nitride material according to claim 3, wherein the mass ratio of cyanuric acid to melamine in step 1) is 0.5 to 2:1.
6. the method for producing sulfur-containing carbon nitride material according to claim 3, wherein the distance between the centers of the No. 1 porcelain boat and the No. 2 porcelain boat in step 2) is 10-20 cm.
7. The method for producing a sulfur-containing carbon nitride material according to claim 3, wherein the inert atmosphere in step 2) is nitrogen or argon, the gas purity is 99.99 vol.% or more, and the gas flow rate is 60 to 100mL/min.
8. A method for preparing a sulfur-containing carbon nitride material according to claim 3, wherein the calcining process conditions of step 2) are: raising the temperature to 500-600 ℃ at the room temperature at the temperature raising rate of 5-15 ℃/min, and preserving the heat for 3-5 h.
9. Use of the sulfur-containing carbon nitride material according to claim 1 or 2 for photocatalytic hydrogen production.
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