CN110639590A - Preparation method and application of carbon nitride/carbon nano composite photocatalytic material - Google Patents
Preparation method and application of carbon nitride/carbon nano composite photocatalytic material Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 63
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 41
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001338 self-assembly Methods 0.000 claims abstract description 38
- OWUDFCCCSKRXAN-UHFFFAOYSA-N oxalic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C(O)=O.NC1=NC(N)=NC(N)=N1 OWUDFCCCSKRXAN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
-
- B01J35/39—
-
- B01J35/61—
-
- 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
-
- 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
-
- 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 a preparation method and application of a carbon nitride/carbon nano composite photocatalytic material, wherein melamine and oxalic acid are reacted in a solution to form a melamine-oxalic acid supermolecule self-assembly body, and then the melamine-oxalic acid supermolecule self-assembly body is calcined to obtain the carbon nitride/carbon nano composite photocatalytic material, and the whole preparation process is simple and convenient; the photocatalytic material prepared by the method is efficient and stable, can be conveniently separated and recycled in a photocatalytic system, and has high practical value and wide application prospect; the organic solvent used in the invention can be recycled after dehydration, so that the pollution to the environment is reduced, the used raw materials are nontoxic and cheap, and the process flow is simple and easy to implement.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method and application of a carbon nitride/carbon nano composite photocatalytic material.
Background
With the increasing environmental pollution and energy crisis, people pay more attention to the replacement of fossil fuels by renewable clean energy. Hydrogen is an ideal clean energy source, and a photocatalytic technology for producing hydrogen by decomposing water with sunlight also becomes a hotspot of research. In recent years, the metal-free photocatalytic material carbon nitride shows excellent performance in hydrogen production by photolysis of water, and has stable chemical property and visible light response. However, the traditional carbon nitride directly prepared by thermal polycondensation of nitrogen-containing organic micromolecules such as melamine, dicyanodiamine or cyanamide also has obvious defects, such as small specific surface area, easy recombination of photon-generated carriers and the like, and the development of the traditional carbon nitride is severely limited.
The separation efficiency of photogenerated carriers can be effectively improved by compounding carbon nitride with other materials such as metals, metal oxides, metal sulfides, graphene and the like (see adv. energy mate, 2017,7: 1701503). Among the many materials that can be composited with carbon nitride, carbon material is a material of great interest, primarily due to its higher chemical and thermal stability, high electrical conductivity, and lower density (see chemsus chem,2014,7: 2303). However, in most carbon nitride/carbon composite materials, because the effective close contact between carbon nitride and carbon is insufficient, efficient transmission of photon-generated carriers cannot be realized, and the improvement of the photocatalytic activity is very limited; in addition, the problem of small specific surface area cannot be solved by merely compounding carbon nitride with carbon.
Disclosure of Invention
In order to improve the photocatalytic activity of the carbon nitride and carbon composite material and solve the technical problems of small specific surface area of the composite material, a preparation method and application of the carbon nitride/carbon nano composite photocatalytic material are provided. The method is characterized in that a precursor melamine of carbon nitride and oxalic acid are subjected to self-assembly to obtain a melamine-oxalic acid supermolecule self-assembly body with a specific micro-morphology, and then the supermolecule self-assembly body is calcined in an air atmosphere to prepare the carbon nitride/carbon nano composite photocatalytic material, so that the method is more beneficial to improving the separation efficiency of a photon-generated carrier; compared with the traditional carbon nitride, the carbon nitride/carbon nano composite photocatalytic material has larger specific surface area, higher photogenerated carrier separation efficiency and higher hydrogen production activity by decomposing water with visible light.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) dissolving melamine in an organic solvent to form a melamine solution; dissolving oxalic acid dihydrate in water to form an oxalic acid solution;
(2) adding an oxalic acid solution into a melamine solution at room temperature under the stirring condition, generating a white precipitate, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 1-3 h, performing suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace for calcining, and then fully grinding to obtain the carbon nitride/carbon nano composite photocatalytic material.
Further, the concentration of the melamine solution in the step (1) is 10-50 g/L; the concentration of the oxalic acid solution is 10-50 g/L; the mass ratio of the melamine to the oxalic acid dihydrate is 1 (1-1.5).
Preferably, the concentration of the melamine solution is 20 g/L; the concentration of the oxalic acid solution is 40 g/L; the mass ratio of melamine to oxalic acid dihydrate was 1: 1.
Further, the organic solvent in step (1) is dimethyl sulfoxide (DMSO). The melamine has better solubility in DMSO, so the amount of the solvent is less. If water is used as the solvent, the amount of the solvent is about 10 times that of DMSO; if ethanol is used as the solvent, melamine is hardly dissolved. It is to be noted that the melamine is "dissolved" in the solvent, and a clear and transparent solution is formed, whereas in the prior art, most of the melamine is "dispersed" and does not reach "dissolved". Because the melamine-oxalic acid supermolecule self-assembly body appears in a precipitation mode, the supermolecule self-assembly body and a solvent can be directly filtered and separated by adopting a filtering method, and most of the prior art can only obtain a solid by adopting a mode of evaporating the solvent.
Further, the stirring speed in the step (2) is more than or equal to 50 rpm. If the stirring speed is too slow, a large amount of precipitates may be formed, and thus the stirring may be impossible.
Further, the adding speed of the oxalic acid solution in the step (2) is 5-100 mL/min. The appearance of the melamine-oxalic acid supermolecule self-assembly body is deteriorated due to the excessively fast addition of the oxalic acid solution, the specific surface area of a final product is influenced, and the separation of photo-generated electrons and holes is influenced, so that the catalytic effect is poor.
Preferably, the oxalic acid solution is added at a rate of 10 mL/min.
Further, the calcining temperature in the step (3) is 520-600 ℃, and the calcining heat preservation time is 2-6 hours.
Preferably, the calcination temperature is 550 ℃ and the calcination holding time is 4 hours.
The invention also provides application of the carbon nitride/carbon nano composite photocatalytic material prepared by the method in preparation of hydrogen by decomposing water under visible light.
The beneficial technical effects are as follows: the invention carries out acid-base neutralization reaction on the melamine with alkalinity and the oxalic acid with acidity in the solution to form the melamine-oxalic acid supermolecule self-assembly body, and the supermolecule self-assembly body is calcined to obtain the carbon nitride/carbon nano composite photocatalytic material, and the whole preparation process is simple and convenient; the oxalic acid is used as a precursor of a carbon material in the product, and a large amount of gas is released in the calcining process, so that the product has a porous structure and the specific surface area is increased; the carbon nitride/carbon nano composite photocatalytic material prepared by the method has high efficiency and stability, can be conveniently separated and recycled in a photocatalytic system, has high practical value and wide application prospect, compared with the traditional carbon nitride photocatalyst, the carbon nitride and the carbon in the invention are generated while being thermally polymerized in calcination, compared with most of composite materials, the effective contact area between the two phases is larger, the transmission of a photo-generated carrier between the two phases is more facilitated, the separation efficiency of the photo-generated carrier is higher, and the composite photocatalyst has stronger photocatalytic performance, because a carbon-carbon nitride heterojunction is constructed in a supermolecular self-assembly body in the calcination process, photo-generated electrons and holes are respectively enriched on different materials, the spatial isolation of the carrier is formed, and the recombination of the photo-generated electrons and the holes is further inhibited to a certain degree, the separation efficiency of photogenerated carriers is higher compared to a single material, such as conventional carbon nitride. The organic solvent DMSO used in the invention can be recycled after dehydration, thereby reducing the cost and simultaneously reducing the pollution to the environment, and the used raw materials are nontoxic and cheap, and the process flow is simple and easy to implement.
Drawings
FIG. 1 is a scanning electron microscope of the supramolecular self-assembly of melamine-oxalic acid in example 1.
FIG. 2 is a scanning electron microscope photograph of the carbon nitride/carbon nanocomposite photocatalytic material in example 1.
FIG. 3 is an X-ray diffraction spectrum of the composite carbon nitride/carbon nano-composite photocatalytic material in example 1.
Fig. 4 is a scanning electron microscope photograph of the carbon nitride photocatalyst in comparative example 1.
Fig. 5 is a graph comparing the performance of the carbon nitride/carbon nano composite photocatalytic material in example 1 and the performance of the carbon nitride photocatalyst in comparative example 1 in photocatalytic hydrogen production under visible light, where a is the carbon nitride/carbon nano composite photocatalytic material and b is the carbon nitride photocatalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 2.00g of oxalic acid dihydrate in 50mL of distilled water to form an oxalic acid solution with the concentration of 40 g/mL;
(2) adding an oxalic acid solution into a melamine solution at the speed of 10mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 2 hours, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace, calcining for 4 hours at 550 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
And (3) observing the melamine-oxalic acid supermolecule self-assembly obtained in the step (2) by using a scanning electron microscope, wherein the appearance of the SEM is shown in figure 1, and as can be seen from figure 1, the supermolecule self-assembly is regular in appearance and is a rectangular nanoscale sheet.
And (3) observing the carbon nitride/carbon nano composite photocatalytic material obtained in the step (3) by using a scanning electron microscope, wherein the SEM appearance is shown in figure 2, and as can be seen from figure 2, the composite material is a nano-scale sheet with a porous structure.
The carbon nitride/carbon nano composite photocatalytic material obtained in the step (3) is subjected to X-ray diffraction, and an XRD spectrogram obtained is shown in figure 3, and 2 diffraction peaks which are respectively assigned to the (100) crystal face and the (002) crystal face of the carbon nitride appear at 13.1 degrees and 27.4 degrees in figure 3.
Example 2
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 3.00g of oxalic acid dihydrate in 100mL of distilled water to form an oxalic acid solution with the concentration of 30 g/mL;
(2) adding an oxalic acid solution into a melamine solution at a speed of 20mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 2 hours, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace, calcining for 4 hours at 550 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
The XRD spectrum of the carbon nitride/carbon nano composite photocatalytic material of the present example is the same as that of example 1.
Example 3
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 2.00g of oxalic acid dihydrate in 50mL of distilled water to form an oxalic acid solution with the concentration of 40 g/mL;
(2) adding an oxalic acid solution into a melamine solution at the speed of 5mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 1h, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace, calcining for 4 hours at 550 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
The XRD spectrum of the carbon nitride/carbon nano composite photocatalytic material of the present example is the same as that of example 1.
Example 4
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 2.00g of oxalic acid dihydrate in 50mL of distilled water to form an oxalic acid solution with the concentration of 40 g/mL;
(2) adding an oxalic acid solution into a melamine solution at a speed of 50mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 3 hours, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace, calcining for 4 hours at 550 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
The XRD spectrum of the carbon nitride/carbon nano composite photocatalytic material of the present example is the same as that of example 1.
Example 5
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 2.00g of oxalic acid dihydrate in 50mL of distilled water to form an oxalic acid solution with the concentration of 40 g/mL;
(2) adding an oxalic acid solution into a melamine solution at the speed of 10mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 2 hours, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and placing the dried melamine-oxalic acid supermolecule self-assembly in a muffle furnace, calcining for 6 hours at 550 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
The XRD spectrum of the carbon nitride/carbon nano composite photocatalytic material of the present example is the same as that of example 1.
Example 6
A preparation method of a carbon nitride/carbon nano composite photocatalytic material comprises the following steps:
(1) 2.00g of melamine is stirred and dissolved in 100mL of organic solvent DMSO to form a melamine solution with the concentration of 20 g/mL; dissolving 2.00g of oxalic acid dihydrate in 50mL of distilled water to form an oxalic acid solution with the concentration of 40 g/mL;
(2) adding an oxalic acid solution into a melamine solution at the speed of 10mL/min at room temperature under the condition that the stirring speed is not less than 50rpm, allowing a white precipitate to appear, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 2 hours, removing water after suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace, calcining for 4 hours at 520 ℃, naturally cooling to room temperature, and fully grinding to obtain the powdery carbon nitride/carbon nano composite photocatalytic material.
The XRD spectrum of the carbon nitride/carbon nano composite photocatalytic material of the present example is the same as that of example 1. Comparative example 1
And 2.00g of melamine is placed in a muffle furnace to be calcined for 4 hours at 550 ℃, then the temperature is naturally reduced to the room temperature, and the powdery product of the carbon nitride photocatalyst is obtained after full grinding.
When the product of the comparative example is observed by a scanning electron microscope, the SEM appearance is shown in FIG. 5, and compared with the SEM appearance of the carbon nitride/carbon nano composite photocatalytic material in FIG. 2, the bulk phase carbon nitride in FIG. 5 has no obvious pores.
Application example 1
Photolysis of water to produce hydrogen
The carbon nitride/carbon nano composite photocatalytic material prepared in example 1 and the carbon nitride photocatalyst prepared in comparative example 1 were usedAdding a catalyst (50mg) into a mixed solution of triethanolamine (10mL) and water (90mL), transferring the mixed solution to a reactor of a photolysis water hydrogen production system after ultrasonic short-time, and adding H2PtCl6(3 wt%). In the process of hydrogen production test, stirring is always kept and cooling water is connected to keep the reaction system at room temperature. And vacuumizing to remove all gas in the system. Turning on the light source (300W xenon lamp, filter lambda)>420nm) to carry out a photocatalytic reaction. Determination of H produced by the reaction by on-line gas chromatography2The results are shown in FIG. 5, in which a is carbon nitride/carbon nano composite photocatalytic material and b is carbon nitride photocatalyst.
As can be seen from FIG. 5, the hydrogen production rate by water decomposition of the carbon nitride/carbon nano composite photocatalytic material prepared in example 1 reaches 26 μmol/h under visible light, which is about 4.0 times that of the carbon nitride photocatalyst (6.5 μmol/h) prepared in comparative example 1, which indicates that the carbon nitride/carbon nano composite photocatalytic material prepared by the method of the present invention has higher hydrogen production activity by water decomposition under visible light.
And (3) centrifugally separating the carbon nitride/carbon nano composite photocatalytic material, collecting and drying the material, recycling the material for hydrogen production by photolysis of water, and reducing the hydrogen production rate to about 98.5 percent of the original rate after recycling for 4 times.
Claims (10)
1. A preparation method of a carbon nitride/carbon nano composite photocatalytic material is characterized by comprising the following steps:
(1) dissolving melamine in an organic solvent to form a melamine solution; dissolving oxalic acid dihydrate in water to form an oxalic acid solution;
(2) adding an oxalic acid solution into a melamine solution at room temperature under the stirring condition, generating a white precipitate, wherein the white precipitate is a melamine-oxalic acid supermolecule self-assembly body, continuously stirring and reacting for 1-3 h, performing suction filtration, recovering an organic solvent, and drying the melamine-oxalic acid supermolecule self-assembly body;
(3) and (3) placing the dried melamine-oxalic acid supermolecule self-assembly body in a muffle furnace for calcining, and then fully grinding to obtain the carbon nitride/carbon nano composite photocatalytic material.
2. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 1, wherein the concentration of the melamine solution in the step (1) is 10-50 g/L; the concentration of the oxalic acid solution is 10-50 g/L; the mass ratio of the melamine to the oxalic acid dihydrate is 1 (1-1.5).
3. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 2, wherein the concentration of the melamine solution is 20 g/L; the concentration of the oxalic acid solution is 40 g/L; the mass ratio of melamine to oxalic acid dihydrate was 1: 1.
4. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 1, wherein the organic solvent in the step (1) is dimethyl sulfoxide.
5. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 1, wherein the stirring speed in the step (2) is not less than 50 rpm.
6. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 1, wherein the adding speed of the oxalic acid solution in the step (2) is 5-100 mL/min.
7. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 6, wherein the adding speed of the oxalic acid solution is 10 mL/min.
8. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 1, wherein the calcination temperature in the step (3) is 520-600 ℃, and the calcination heat preservation time is 2-6 hours.
9. The method for preparing the carbon nitride/carbon nano composite photocatalytic material according to claim 8, wherein the calcination temperature is 550 ℃ and the calcination holding time is 4 hours.
10. The application of the carbon nitride/carbon nano composite photocatalytic material prepared by the preparation method according to any one of claims 1 to 9 in preparation of hydrogen by decomposing water under visible light.
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