CN110639587B - Preparation method and application of carbon-bridged modified carbon nitride photocatalytic material - Google Patents
Preparation method and application of carbon-bridged modified carbon nitride photocatalytic material 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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- B01J35/61—
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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 discloses a preparation method of a carbon-bridged modified carbon nitride photocatalytic material, which specifically comprises the following steps: and grinding and mixing the urea and the malonamide, putting the obtained mixture into an alumina crucible with a cover after uniformly mixing, and heating in a muffle furnace to obtain the urea-malonamide-containing crucible. The invention solves the problems of high photon-generated carrier recombination rate, poor sunlight absorption utilization rate and small comparative area of the traditional graphite-phase carbon nitride.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalytic materials, and particularly relates to a preparation method of a carbon-bridged modified carbon nitride photocatalytic material, and an application of the catalytic material.
Background
Social development and population increase bring a series of environmental problems and also greatly improve the demand of human beings on energy. Environmental pollution and energy shortage have become two major problems facing mankind today. The development of clean, environmentally friendly and sustainable new energy sources is urgent. Since the photocatalytic technology can convert low-density solar energy into high-density electric energy and chemical energy, the semiconductor photocatalytic material with simple design and synthesis, high efficiency and stable structure is considered to be one of the most effective ways to solve the problems of the future environment and energy. Graphite phase carbon nitride (g-C) 3 N 4 ) As an organic nonmetal polymer photocatalytic material, the material is simple to prepare, low in cost, stable in structure and appropriate in energy band structure, can quickly become a hot spot material in the field of photocatalysis, and shows a huge potential application prospect (chem.Rev., 2016,116, 7159-7329). But do notIn g-C 3 N 4 In which the nitrogen atom linking the 3-s-triazine units is sp 3 Hybridized and has larger electronegativity, and the g-C is limited to a certain extent 3 N 4 The separation of the conjugated system and the photogenerated carriers of (1) results in a lower photocatalytic performance (appl. Catal. B: environ, 2018,229, 114-120).
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-bridged modified carbon nitride photocatalytic material, which solves the problems of high recombination rate of photon-generated carriers, poor sunlight absorption utilization rate and small comparative area of the traditional graphite-phase carbon nitride.
The technical scheme adopted by the invention is that the preparation method of the carbon bridged modified carbon nitride photocatalytic material specifically comprises the following processes: and grinding and mixing the urea and the malonamide, putting the obtained mixture into an alumina crucible with a cover after uniformly mixing, and heating in a muffle furnace to obtain the urea-malonamide-containing crucible.
The present invention is also characterized in that,
the dosage of the malonamide is 10-50 mg.
The amount of urea used was 5g.
The mixing time of urea and malonamide was 20min.
The heating time in the muffle furnace is 2h, and the heating rate is 5K min -1 。
The method has the beneficial effects that the method takes malonamide as a novel polymeric micromolecule, and adopts a one-step copolymerization method to carry out g-C 3 N 4 And carrying out carbon bridging modification. The obtained material not only improves g-C 3 N 4 The original conjugated system optimizes the energy band structure and induces charge redistribution, thereby improving g-C 3 N 4 Separation efficiency of photon-generated carriers and sunlight utilization rate. In addition, the malonamide monomer can also be used as an end-capping agent, more structural edge defects and surface inner holes are generated in the thermal polymerization process, and the g-C is greatly increased 3 N 4 The specific surface area of (2). The photocatalysis test result shows that the obtained material shows excellent performance in the aspects of photodegradation of organic dye and hydrogen production by photolysis of water.
Drawings
FIG. 1 (A) is an XPS survey of samples of comparative example 1 and example 2 in a method of preparing a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, with the abscissa being binding energy and the ordinate being intensity;
FIG. 1 (B) is a C1s high power spectrum of samples of comparative example 1 and example 2 in a preparation method of a carbon-bridged modified carbon nitride photocatalytic material of the present invention, the abscissa is binding energy, and the ordinate is intensity;
FIG. 1 (C) is a high-power spectrum of N1s of samples of comparative example 1 and example 2 in the preparation method of the carbon-bridged modified carbon nitride photocatalytic material of the present invention, the abscissa is binding energy, and the ordinate is intensity;
FIG. 1 (D) is a solid-state nuclear magnetic spectrum of samples of comparative example 1 and example 2 in a preparation method of a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, with the abscissa being binding energy and the ordinate being intensity;
FIG. 2 (A) is a graph showing N in samples of comparative example 1 and examples 1 to 3 in the preparation method of a carbon-bridged modified carbon nitride photocatalytic material according to the present invention 2 An adsorption-desorption curve chart, wherein the abscissa is relative pressure, and the ordinate is adsorption volume;
FIG. 2 (B) is a graph showing pore size distribution curves of the samples of comparative example 1 and examples 1 to 3 in the method for preparing a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, the abscissa being the pore size and the ordinate being the rate of change in pore volume;
FIG. 3 (A) is a graph showing the UV-visible diffuse reflectance spectra of the samples of comparative example 1 and examples 1-3 in the preparation method of a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, with the abscissa being the wavelength of light and the ordinate being the absorption of light;
FIG. 3 (B) is a graph showing the steady-state photoluminescence spectra of the samples of comparative example 1 and examples 1 to 3 in the method for preparing a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, wherein the abscissa is the wavelength of light and the ordinate is the intensity;
FIG. 4 is a graph showing the RhB performance of the photodegradable organic dyes of the samples of comparative examples 1-2 and examples 1-3 in the preparation method of the carbon-bridged modified carbon nitride photocatalytic material of the present invention, with the abscissa being time and the ordinate being the change in concentration;
fig. 5 is a graph showing hydrogen production performance by photocatalytic decomposition of water of the samples of comparative example 1 and example 2 in the preparation method of a carbon-bridged modified carbon nitride photocatalytic material according to the present invention, with the abscissa as time and the ordinate as hydrogen amount.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a carbon-bridged modified carbon nitride photocatalytic material, which takes malonamide as a novel copolymerization micromolecule of urea and adopts a simple and feasible one-step thermal induction copolymerization method to prepare carbon-bridged modified g-C 3 N 4 Nanosheets. 5g of urea and 10-50 mg of malonamide are ground and mixed uniformly for 20min. After being mixed evenly, the obtained mixture is put into an alumina crucible with a cover and heated in a muffle furnace for 2 hours at 823K with the heating rate of 5K min -1 . The resulting orange-yellow sample was collected and ground into a powder for further use.
The preparation method of the carbon-bridged modified carbon nitride photocatalytic material is characterized by comprising the following steps: (1) The first time, the one-step thermal induction copolymerization method is adopted to successfully prepare the carbon-bridged modified g-C by taking malonamide as a comonomer of urea 3 N 4 A nanosheet; (2) The method has the advantages of simple process, cheap and easily-obtained raw materials and good application prospect; (3) The obtained carbon-bridged modified g-C 3 N 4 The nanosheet has excellent photoelectrochemical properties, and shows high activity in the fields of photocatalytic degradation of organic dyes and hydrogen production by photolysis of water.
The invention can successfully introduce bridging carbon into g-C through specific chemical reaction between organic micromolecular amide groups 3 N 4 In the structure, not only the g-C is improved 3 N 4 The original conjugated system optimizes the energy band structure and improves the g-C 3 N 4 Separation efficiency of photon-generated carriers and sunlight utilization rate. In addition, the malonamide monomer can also be used as an end-capping agent, more structural edge defects and surface inner holes are generated in the thermal polymerization process, and the g-C is greatly increased 3 N 4 Specific surface area of (2). Photocatalytic assayTest results show that the obtained material shows excellent performance in the aspects of photodegradation of organic dyes and hydrogen production by photolysis of water.
Example 1
The invention adopts malonamide as a novel copolymerization micromolecule to carry out one-step thermal induction copolymerization with urea to prepare carbon-bridged modified g-C 3 N 4 Nanosheets. 5g of urea was mixed with 10mg of malonamide by trituration for 20min. After being mixed evenly, the obtained mixture is put into an alumina crucible with a cover and heated in a muffle furnace for 2 hours at 823K with the heating rate of 5K min -1 . The resulting orange-yellow sample was collected and ground into a powder for further use.
Example 2
5g of urea and 30mg of malonamide were ground and mixed for 20min. After being mixed evenly, the obtained mixture is put into an alumina crucible with a cover and heated in a muffle furnace for 2 hours at 823K with the heating rate of 5K min -1 . The resulting orange-yellow sample was collected and ground into a powder for further use.
Example 3
5g of urea and 50mg of malonamide were ground and mixed for 20min. After being mixed evenly, the obtained mixture is put into an alumina crucible with a cover and heated in a muffle furnace for 2 hours at 823K with the heating rate of 5K min -1 . The resulting orange-yellow sample was collected and ground into a powder for further use.
Comparative example 1
5g of urea was placed in an alumina crucible with a lid and heated in a muffle furnace at 823K for 2h at a heating rate of 5K min -1 . The resulting yellow sample was collected and ground to a powder for further use.
Comparative example 2
Commercial photocatalyst titanium dioxide (P25) was purchased from the national pharmaceutical group chemical agents limited.
The materials obtained in the above examples 1 to 3 and comparative examples 1 to 2 were subjected to a photocatalytic degradation organic dye test; in addition, the photolytic hydrogen production activity test was performed on the samples of example 2 and comparative example 1, and the specific test process was as follows:
mixing 30mg of the sampleDispersed acoustically in 50mL of RhB aqueous solution (10 mg L) -1 ) In (1). A500W xenon lamp was used as a light source to provide visible light. Before illumination, the resulting suspension was stirred for 40min in the dark to ensure that the adsorption-desorption equilibrium was reached. In the course of the photocatalytic test, 3mL of the suspension was taken out at 30, 60 and 90min of reaction, respectively, and centrifuged at 10000rpm/min for 5 min at high speed to remove the photocatalyst. And finally, monitoring the degradation result by adopting a UV-vis near infrared spectrum (Shimadzu, UV-2450). The test without any catalyst addition was a blank experiment.
The photolysis water test process comprises the following steps: 20mg of the sample was ultrasonically dispersed into 50mL of triethanolamine solution (10 vol%). Then, the solution and the reactor were degassed for 30min with 3wt% Pt supported as a promoter. Using a 500W xenon lamp as a light source and high-purity N 2 (99.99%) as carrier gas, H was finally produced 2 The measurement was carried out by a gas chromatograph equipped with a Thermal Conductivity Detector (TCD). The test without any catalyst addition was a blank experiment.
FIG. 1 (A) shows XPS survey spectra of comparative example 1 and example 2. It can be seen from the figure that the samples obtained in comparative example 1 and example 2 both consist of elements C and N, but in the sample of example 2 the C/N ratio increased from 0.89 for the sample of comparative example 1 to 1.04, indicating that the introduction of bridging carbon increased the carbon content of the sample of example 2.
Fig. 1 (B) is a C1s high power spectrum of comparative example 1 and example 2. As can be seen from the graph, the characteristic peak of C-C group and the characteristic peak of C-NHx group of the sample of example 2 are both significantly enhanced as compared with the sample of comparative example 1, indicating that the bridging carbon is successfully introduced into g-C 3 N 4 In the structure of (1).
Fig. 1 (C) is a high-power spectrum of N1s for comparative example 1 and example 2. The test result shows that the characteristic peak of the N-Hx group of the sample of the example 2 is obviously enhanced compared with the sample of the comparative example 1, and the malonamide can be used as a blocking reagent at g-C 3 N 4 More structural defects are introduced into the structure. Furthermore, N 3C The reduction of characteristic peaks of the radicals can also indicate that the preparation process according to the invention can be carried out at g-C 3 N 4 The structure of (2) is introduced with bridging carbon.
Fig. 1 (D) is a solid-state nuclear magnetic spectrum of comparative example 1 and example 2. For the sample obtained in example 2, the newly added characteristic peak at 150.26ppm in the solid-state nuclear magnetic spectrum was due to carbon in the new chemical environment, further indicating that carbon bridging was successfully introduced into g-C 3 N 4 In the structure.
FIG. 2 (A) is N in comparative example 1 and examples 1 to 3 2 Adsorption-desorption curve chart. The results show that the samples related to the invention are IV-type isotherms and have H 3 The type hysteresis loop shows that the material is mesoporous. The specific surface areas of the samples of examples 1-3 and comparative example 1 were 63.16, 71.34, 116.56, and 109.61m 2 g -1 It follows that the malonamide comonomer can increase the specific surface area of the product.
FIG. 2 (B) is a plot of the pore size distribution of comparative example 1 and examples 1-3. The results show that the samples of examples 1-3 have a more abundant pore structure than the sample of comparative example 1.
FIG. 3 (A) shows diffuse reflectance spectra of comparative example 1 and examples 1 to 3, respectively, as indicated by arrows;
fig. 3 (a) is an ultraviolet-visible diffuse reflection spectrum of comparative example 1 and examples 1 to 3. The characterization results show that the solar absorption and utilization rate of the samples in the examples 1 to 3 are remarkably improved, and the forbidden bandwidths of the comparative example 1 and the examples 1 to 3 are 2.60, 2.23, 1.88 and 1.70eV.
Fig. 3 (B) is a steady-state photoluminescence spectrum of comparative example 1 and examples 1 to 3. The test results show that the emission peak intensities of the samples of examples 1-3 are gradually reduced compared with the sample of comparative example 1, which means that the introduction of carbon bridges can obviously improve the original g-C 3 N 4 Thereby improving the separation efficiency of the photon-generated carriers of the sample.
FIG. 4 is a graph showing the RhB properties of the photodegradable organic dyes of comparative examples 1-2 and examples 1-3. The test results show that after 90min of visible light irradiation, the samples of comparative example 1 and comparative example 2 can remove only 45% and 21% of RhB dye, while the samples of examples 1-3 have the light degradation rate of RhB increased to 76%, 90% and 69% under the same conditions, respectively.
FIG. 5 shows hydrogen production by photocatalytic water splitting of comparative example 1 and example 2A performance map. The hydrogen production test result shows that the hydrogen production rate of the sample of the comparative example 1 is 0.79mmol g after the visible light irradiation for 120min -1 h -1 While the hydrogen production rate of the sample of the example 2 can be improved to 2.72mmol g -1 h -1 . Further proves that the introduction of the carbon bridging pair g-C 3 N 4 The important role of modification.
Claims (3)
1. A preparation method of a carbon bridged modified carbon nitride photocatalytic material is characterized by comprising the following steps: the method specifically comprises the following steps: grinding and mixing urea and malonamide, putting the obtained mixture into an alumina crucible with a cover after uniform mixing, and heating in a muffle furnace to obtain the urea-malonamide composite material;
the dosage of the malonamide is 10-50 mg;
the dosage of the urea is 5g;
the mixing time of the urea and the malonamide is 20min;
the heating time in the muffle furnace is 2h, and the heating rate is 5K min -1 。
2. The use of the carbon photocatalytic material prepared by the method for preparing a carbon-bridged modified carbon nitride photocatalytic material according to claim 1, wherein the method comprises the following steps: the application in photocatalytic degradation of organic dyes.
3. The use of the carbon photocatalytic material prepared by the method for preparing a carbon-bridged modified carbon nitride photocatalytic material according to claim 1, wherein the method comprises the following steps: the application in photolysis of water to produce hydrogen.
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