CN111762764A - Carbon nitride material prepared by using cage-type polysilsesquioxane as template and preparation method and application thereof - Google Patents
Carbon nitride material prepared by using cage-type polysilsesquioxane as template and preparation method and application thereof Download PDFInfo
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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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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- B01J35/56—
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 provides a carbon nitride material prepared by taking cage type polysilsesquioxane as a template, a preparation method and application thereof, wherein the preparation method comprises the following steps: grinding and uniformly mixing the carbon-nitrogen precursor and the template to obtain a mixture; calcining the mixture under inert atmosphere to obtain a carbon nitride material; the template is cage-type polysilsesquioxane. The preparation method of the invention has no carbon residue, does not need post-treatment, completes the reaction in one step, simplifies the production process and reduces the pollution to the environment; the raw materials used in the invention are cheap and easily available, the template can be recycled, and the production cost is low; the preparation method is carried out under normal pressure, does not need to use complex equipment, and is easy for industrial production. The carbon nitride material prepared by the preparation method has large specific surface area, has higher catalytic activity and better repeatability when being used as a catalyst for photodegradation of water or dye, and has potential utilization value in the aspects of solar energy conversion and sewage treatment.
Description
Technical Field
The invention relates to a carbon nitride material prepared by using cage type polysilsesquioxane as a template, a preparation method and application thereof, belonging to the field of material chemistry.
Background
With the coming of the world energy crisis, the exhaustion of fossil energy is inevitable, so the development of new energy, especially the conversion of solar energy, will be the key direction of future scientific research and economic growth. The photocatalytic technology can convert low-density solar energy into high-density chemical energy through processes of hydrogen production by water cracking, carbon dioxide reduction and the like, and is concerned. As the core of the photocatalysis technology, developing a photocatalyst which is simple to prepare, cheap and easy to obtain, high-efficiency and stable is particularly critical.
From 2009, graphite phase carbon nitride materials (g-C)3N4) Due to the unique photolysis performance, the material can be recycled, is green and pollution-free, and the like. However, researchers have found that g-C is prepared by high temperature thermal polymerization3N4Most of the materials are bulk materials, and have the defects of small surface area, narrow visible light absorption range, easy recombination of photo-generated electron holes and the like, so that the photo-catalytic activity of the materials is low.
Therefore, by constructing the porous structure, the reaction active site can be effectively increased, the reaction mass transfer can be promoted, and the carrier recombination can be reduced, so that the g-C is improved3N4The photocatalytic activity of the material. Currently porous g-C3N4The preparation of the material mainly comprises a soft template method and a hard template method. The soft template method is to prepare g-C by introducing a template degradable at high temperature during thermal polymerization3N4Materials, for example: wang et al prepared porous g-C by introducing Triton-X100 into the thermal shrinkage system of dicyandiamide3N4Improve g-C3N4Specific surface area of the material (see: ChemSus Chem,2010,3, 435-439); yan et al also improved g-C by incorporating Pluronic 123 block copolymers in melamine heat-shrinkable systems3N4The surface area and the visible light absorption capacity of the material (see: chem. Commun.,2012,48, 3430-. Chinese patent document CN106423243A provides a rod-shaped porous carbon nitride photocatalyst and a preparation method thereof, which uses phenolic resin spheres as a template to polymerize melamine at high temperature to obtain rod-shaped porous carbon nitride. However, researchers at home and abroad Zhang and Schnepp found (see: J. Mater. chem. A., 2015,3,14081-Should cause carbon residue problems, resulting in the production of g-C3N4Material carbon nitrogen ratio imbalance, effective C3N4The components of the material are reduced, and finally the photocatalytic performance of the material is reduced.
To prevent carbon residue, it has been reported that porous g-C is prepared using a silica template method3N4A material. Vinu (see: adv. Mater.,2005,17, 1648-1652) reports porous g-C prepared from ethylene diamine and carbon tetrachloride as precursors and SBA-15 type silica as a template3N4A material. Zhao (see: Nano Res.,2010,3, 632-642) prepares g-C with high specific surface area by using porous spherical silica3N4A material. Chinese patent document CN109126852A provides a method for preparing an ordered graded porous graphite phase carbon nitride photocatalyst, which uses silica nanospheres as a template and cyanamide as a precursor, and removes the silica template after high-temperature polymerization to obtain the ordered graded porous graphite phase carbon nitride. Although the porous carbon nitride material is prepared by virtue of the nondegradable thermal stability of the silica template, the specific surface area of the prepared material is improved, and carbon residue is prevented, the silica template is required to pass NH subsequently4HF2Or hydrofluoric acid, etc., resulting in tedious experiments and environmental pollution.
In conclusion, the g-C is prepared by the template method reported at home and abroad at present3N4The material method limits the industrial conversion of the template synthesis technology due to the carbon residue of the carbon-containing template at high temperature and the tedious post-treatment of the silica template system.
Polyhedral oligomeric silsesquioxanes (POSS) as a siloxane excellent in high temperature resistance can maintain a stable chemical structure in an inert atmosphere, and foreign researchers Fina (see: Thermochimica Acta, 2006, 400, 36-42) report that the thermal sublimation temperature of POSS is more than 300 ℃ in an inert atmosphere and that the POSS is nearly free of residues in a condition of more than 500 ℃ with the change of a substituent group on a silicon atom.
Currently, g-C is prepared using cage polysilsesquioxane as a template3N4Of materialsThe method is not reported.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the synthesis of g-C by the prior template method3N4The invention provides a carbon nitride material prepared by using cage-type polysilsesquioxane as a template, and a preparation method and application thereof. The preparation method of the invention has no carbon residue, no post-treatment is needed, the template can be recovered, and the g-C prepared by the method3N4The material has the advantages of large specific surface area, high catalytic performance, wide visible light absorption range and the like, is applied to photocatalytic degradation of water to produce hydrogen, and has high catalytic activity.
The technical scheme of the invention is as follows:
summary of The Invention
The carbon nitride material is prepared by taking cage-type polysilsesquioxane which can be thermally sublimated in inert atmosphere as a template, taking micromolecular carbon-containing nitrogen compounds such as melamine or urea and the like as carbon-nitrogen precursors and performing thermal shrinkage and reaction on the carbon-nitrogen precursors.
Detailed Description
A method for preparing a carbon nitride material by using cage-type polysilsesquioxane as a template comprises the following steps:
grinding and uniformly mixing the carbon-nitrogen precursor and the template to obtain a mixture; calcining the mixture under inert atmosphere to obtain a carbon nitride material; the template is cage type polysilsesquioxane.
According to the present invention, preferably, the carbon-nitrogen precursor is melamine or urea.
According to the present invention, preferably, the cage polysilsesquioxane is octamethyl cage polysilsesquioxane or octaisooctyl cage polysilsesquioxane.
According to the invention, the structural formula of the octamethyl cage polysilsesquioxane or the octaisooctyl cage polysilsesquioxane is shown as the following formula I:
in the formula I, when R is methyl, octamethyl cage polysilsesquioxane is used; when R is isooctyl, octaisooctyl cage polysilsesquioxane is used.
According to the invention, preferably, when the carbon-nitrogen precursor is melamine, the mass ratio of the template to the carbon-nitrogen precursor is 1-5: 10; when the carbon-nitrogen precursor is urea, the mass ratio of the template to the carbon-nitrogen precursor is 3-15: 100.
according to the present invention, preferably, the inert atmosphere is nitrogen or argon.
According to the invention, preferably, the calcination temperature is 500-580 ℃, more preferably 540-550 ℃, and the temperature rise rate is 1-10 ℃/min, more preferably 5 ℃/min; the calcination time is 3 to 6 hours, and more preferably 4 hours.
According to the invention, the template can be recycled after thermal sublimation.
According to the invention, the micro-morphology of the obtained graphite phase carbon nitride material is a honeycomb structure.
The invention also provides the carbon nitride material prepared by the method.
According to the invention, the carbon nitride material prepared by the method is applied as a photocatalyst for photocatalytic degradation of water to produce hydrogen.
The invention has the following technical characteristics and beneficial effects:
1. the preparation method of the invention uses the thermally sublimed cage-type polysilsesquioxane as a template, uses the micromolecule carbon-containing nitrogen compound such as melamine or urea as a raw material, directly obtains the carbon nitride after calcining, has no carbon residue on the template, does not need post-treatment, completes the reaction in one step, simplifies the production process and reduces the pollution to the environment.
2. The raw materials containing the carbon and nitrogen compounds used in the preparation method are cheap and easy to obtain, and the cage-type polysilsesquioxane template can be recycled, so that the production cost is reduced.
3. The preparation method is carried out under normal pressure, does not need to use complex equipment, and is easy for industrial production.
4. The graphite phase carbon nitride material obtained by the preparation method has large specific surface area, has higher catalytic activity and better repeatability when being used as a catalyst for photodegradation of water or dye, and has potential utilization value in the aspects of solar energy conversion and sewage treatment.
Drawings
Fig. 1 is an X-ray diffraction pattern of the carbon nitride material prepared in example 1 and comparative example 1.
FIG. 2 is a graph showing UV-VIS absorption spectra of carbon nitride materials prepared in example 1 and comparative example 1.
FIG. 3 is N of carbon nitride materials prepared in example 1 and comparative example 12Isothermal adsorption-desorption curve.
Fig. 4 is a scanning electron micrograph of the carbon nitride material prepared in example 1 and comparative example 1, in which (a) is a scanning electron micrograph of the carbon nitride material prepared in comparative example 1, and (b) is a scanning electron micrograph of the carbon nitride material prepared in example 1.
Fig. 5 is a graph showing the hydrogen production performance from water by photocatalytic degradation of the carbon nitride materials prepared in example 1 and comparative example 1.
FIG. 6 is a spectrum of solid nuclear magnetic silicon before and after recovery of the template used in example 1.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the following examples, but is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A method for preparing a carbon nitride material by using cage-type polysilsesquioxane as a template comprises the following steps:
melamine and octamethyl cage type polysilsesquioxane are mixed according to the mass ratio of 10: 3, grinding in a mortar, uniformly mixing to obtain a mixture, transferring the mixture into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain the carbon nitride material.
Octamethyl cage polysilsesquioxane adhering to the tube wall was recovered at a recovery rate of 93%.
Comparative example 1
A method of nitriding a carbon material comprising the steps of:
grinding 10g of melamine in a mortar for 5min, transferring the obtained solid into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain the carbon nitride material.
The materials prepared in example 1 and comparative example 1 were characterized by elemental analysis, X-ray diffractometry, ultraviolet-visible light spectroscopy, nitrogen adsorption (BET), and scanning electron microscopy.
The yield of carbon nitride obtained in comparative example 1 was 71%, and the mass contents of nitrogen and carbon in the obtained carbon nitride material were 61.5% and 35.1% by elemental analysis, respectively, from which it was estimated that the mass ratio of both substances was about 1.5: 1.
The yield of carbon nitride obtained in example 1 was 70%, and the mass contents of nitrogen and carbon in the obtained carbon nitride material were 60.1% and 34.3% by elemental analysis, respectively, from which the mass ratio of both substances was estimated to be about 1.5: 1.
The element analysis data show that the nitrogen-carbon substance quantity ratio of the carbon nitride material prepared by the common method and the template method is stabilized at 1.5: 1. it can thus be demonstrated that the templates employed in the present invention are free of carbon residues during the reaction.
The X-ray diffraction patterns of the carbon nitride materials prepared in example 1 and comparative example 1 are shown in fig. 1, and it can be seen from fig. 1 that the material prepared in comparative example 1 without adding a template and the material prepared in example 1 with adding a template have two distinct diffraction peaks at 13.5 ° and 27.4 °, which are characteristic peaks of the carbon nitride material and correspond to the (100) and (002) crystal faces of carbon nitride, respectively, indicating that the prepared materials are porous carbon nitride materials.
The uv-vis absorption spectra of the carbon nitride materials prepared in example 1 and comparative example 1 are shown in fig. 2, and it can be seen from fig. 2 that the uv-vis absorption of the carbon nitride prepared after adding the template is significantly shifted toward the visible light, which demonstrates that the template method of the present invention improves the visible light absorption properties of the carbon nitride material.
N of carbon nitride Material prepared in example 1 and comparative example 12The isothermal adsorption-desorption curve is shown in FIG. 3, and from FIG. 3, it can be calculated that the BET specific surface area of the carbon nitride material prepared in example 1 is 34.1m2(g) the carbon nitride material prepared in comparative example 1 had a BET specific surface area of 9.4m2The fact that the carbon nitride material prepared by the invention has higher specific surface area is proved. N of carbon nitride Material prepared in example 1 and comparative example 12A hysteresis loop exists in an isothermal adsorption-desorption curve, which indicates the existence of a mesoporous structure.
The scanning electron micrographs of the carbon nitride materials prepared in example 1 and comparative example 1 are shown in fig. 4, and it can be seen from fig. 4 that the nitrogen carbide material prepared in comparative example 1 is a bulk solid; example 1 the carbon nitride material prepared in example 1 had a honeycomb structure in which a large number of pores were present.
The carbon nitride materials prepared in the example 1 and the comparative example 1 are used for the reaction of photocatalytic degradation of hydrogen produced by water, and the photocatalytic activity of the carbon nitride materials is tested, and the specific application steps are as follows: 30mg of carbon nitride was dispersed ultrasonically in 100mL of an aqueous solution containing 10 vol% of triethanolamine, 9mg of platinum deposited with light was used as a cocatalyst, a 300W xenon lamp (equipped with a filter having a wavelength of > 420 nm) was used as a visible light source at room temperature, a hydrogen production experiment was performed in a closed glass reaction system, and the produced hydrogen was analyzed by gas chromatography.
The hydrogen production performance of carbon nitride materials prepared in example 1 and comparative example 1 by photocatalytic degradation water is shown in fig. 5, and it can be seen from fig. 5 that the hydrogen production efficiency in 6h of the carbon nitride material prepared in example 1 by the template method is 534mmol/g, the hydrogen production efficiency in 6h of the carbon nitride material prepared in comparative example 1 by the common method is 118mmol/g, and the photocatalytic hydrogen production performance of the carbon nitride prepared in example 1 is obviously superior to that of the carbon nitride material prepared in comparative example 1. The carbon nitride material prepared by the method has higher photocatalytic activity.
In order to test the stability of the template used in example 1 before and after recovery, the solid nuclear magnetic silicon spectrum of the template before and after recovery is shown in fig. 6, and solid nuclear magnetic data prove that the chemical shift of the solid silicon spectrum of the octamethyl cage polysilsesquioxane after recovery is about-74 ppm, which also proves that the template does not have chemical change in the preparation process, and further proves that the template method of the invention has no carbon residue. Although the recovery rate is about 90%, this is due to a loss at the time of recovery.
Example 2
A method for preparing a carbon nitride material by using cage-type polysilsesquioxane as a template comprises the following steps:
urea and octamethyl cage type polysilsesquioxane are mixed according to the mass ratio of 10: grinding the mixture in a mortar according to the proportion of 0.3, uniformly mixing to obtain a mixture, transferring the mixture into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain the carbon nitride material.
The yield of carbon nitride was found to be 32% by calculation, the quantitative ratio of nitrogen to carbon in the obtained carbon nitride material was found to be 1.5:1, and the recovery rate of octamethyl cage polysilsesquioxane was found to be 91%.
Example 3
A method for preparing a carbon nitride material by using cage-type polysilsesquioxane as a template comprises the following steps:
melamine and octaisooctyl cage polysilsesquioxane are mixed according to the mass ratio of 10: 3.2, grinding in a mortar, uniformly mixing to obtain a mixture, transferring the mixture into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain the carbon nitride material.
The yield of carbon nitride was found to be 71% by calculation, the quantitative ratio of nitrogen to carbon in the obtained carbon nitride material was found to be 1.5:1, and the recovery of octaisooctyl cage polysilsesquioxane was found to be 91%.
Claims (10)
1. A method for preparing a carbon nitride material by using cage-type polysilsesquioxane as a template comprises the following steps:
grinding and uniformly mixing the carbon-nitrogen precursor and the template to obtain a mixture; calcining the mixture under inert atmosphere to obtain a carbon nitride material; the template is cage type polysilsesquioxane.
2. The method for preparing carbon nitride material by using cage type polysilsesquioxane as template according to claim 1, wherein the carbon-nitrogen precursor is melamine or urea.
3. The method for preparing carbon nitride material by using cage type polysilsesquioxane as template according to claim 1, wherein said cage type polysilsesquioxane is octamethyl cage type polysilsesquioxane or octaisooctyl cage type polysilsesquioxane.
4. The method for preparing the carbon nitride material by using the cage-type polysilsesquioxane as the template according to claim 1, wherein when the carbon-nitrogen precursor is melamine, the mass ratio of the template to the carbon-nitrogen precursor is 1-5: 10; when the carbon-nitrogen precursor is urea, the mass ratio of the template to the carbon-nitrogen precursor is 3-15: 100.
5. the method for preparing carbon nitride material by using cage-type polysilsesquioxane as template according to claim 1, wherein said inert atmosphere is nitrogen or argon.
6. The method for preparing carbon nitride material by using cage-type polysilsesquioxane as template according to claim 1, wherein the calcination temperature is 500-580 ℃, and the temperature rise rate is 1-10 ℃/min; the calcination time is 3-6 h.
7. The method for preparing carbon nitride material by using cage-type polysilsesquioxane as template according to claim 6, wherein said calcination temperature is 540-550 ℃, said temperature-increasing rate is 5 ℃/min, and said calcination time is 4 h.
8. The method for preparing carbon nitride material by using cage-type polysilsesquioxane as template according to claim 1, wherein said template is recovered for reuse after thermal sublimation.
9. A carbon nitride material produced by the method according to any one of claims 1 to 8.
10. Use of the catalyst carbon nitride material according to claim 9 as a photocatalyst for the photocatalytic degradation of water to produce hydrogen.
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