CN109304204B - Phosphorus-doped cobaltosic oxide quantum dot modified graphite phase nitrogen carbide composite material, and preparation method and application thereof - Google Patents
Phosphorus-doped cobaltosic oxide quantum dot modified graphite phase nitrogen carbide composite material, and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 30
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002096 quantum dot Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
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- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims abstract description 13
- 239000011715 vitamin B12 Substances 0.000 claims abstract description 13
- 235000019163 vitamin B12 Nutrition 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 21
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- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001699 photocatalysis Effects 0.000 abstract description 6
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- 229910002804 graphite Inorganic materials 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- 239000010949 copper Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- LIDGFHXPUOJZMK-UHFFFAOYSA-N 2,6-dimethyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=CC(C)=[N+]1[O-] LIDGFHXPUOJZMK-UHFFFAOYSA-N 0.000 description 1
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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—
-
- 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
-
- 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
-
- 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
Abstract
The invention belongs to the field of photocatalytic application of composite materials, and particularly relates to a phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material, and a preparation method and application thereof. The preparation method comprises the steps of taking vitamin B12 and melamine as raw materials, taking micromolecular alcohol as a solvent, drying, heating to 500-600 ℃, keeping the temperature for 2-6 hours, cooling and grinding to obtain a target product. The graphite-phase nitrogen carbide composite material prepared by the method shows excellent catalytic activity in photocatalytic degradation of AO 7. Has great application prospect in the field of photocatalytic degradation of organic matters.
Description
Technical Field
The invention belongs to the field of photocatalytic application of composite materials, and particularly relates to a phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material, and a preparation method and application thereof.
Background
In recent years, with the deterioration of the environment, green chemistry has become an inevitable demand for sustainable development of human society. The semiconductor photocatalysis technology can utilize light to catalyze and degrade organic pollutants in water, has no secondary pollution, and can be rapidly developed in the field of environmental protection.
Graphite phase carbon nitride (g-C)3N4) The polymer semiconductor is a typical polymer semiconductor composed of non-metallic elements, and raw materials required by the preparation are cheap and easy to obtain, and the polymer semiconductor has better physical and chemical stability. At the same time, g-C3N4The forbidden band width is 2.7 eV, and the material has better absorption in a visible light region, so that the material becomes a novel photocatalytic material with wide application prospect. However, study onIt is found that g-C3N4The high recombination rate of the photo-generated electron holes leads to the reduction of the photo-catalytic activity of the photo-generated electron holes, and limits the wide application of the photo-generated electron holes.
Disclosure of Invention
The invention aims to provide a preparation method of a phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material, and the graphite-phase nitrogen carbide composite material prepared by the method shows excellent catalytic activity in photocatalytic degradation of AO 7.
The preparation method of the phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material comprises the steps of taking vitamin B12 and melamine as raw materials, taking small molecular alcohol as a solvent, drying, heating to 500-600 ℃, preserving heat for 2-6 hours, cooling and grinding to obtain a target product.
Preferably, the mass ratio of the vitamin B12 to the melamine is 0.1-2.0: 100.
Preferably, the small molecule alcohol is methanol, ethanol or propanol, preferably methanol. When the solvent methanol is removed by drying, the drying temperature is 90-100 ℃.
Preferably, the preparation method comprises the following specific steps:
(1) weighing vitamin B12 and melamine according to a ratio, adding solvent micromolecule alcohol, performing ultrasonic treatment, heating to dissolve, drying to remove the solvent, and cooling to obtain intermediate powder;
(2) and heating the intermediate powder to 500-600 ℃, preserving heat for 2-6 hours, cooling and grinding to obtain the target product.
Preferably, in the step (1), the ultrasonic time is 20min, and more preferably, the heating temperature when heating to dissolve is 75 ℃.
Preferably, in the step (2), the temperature increase rate of heating the intermediate powder is 5 ℃/min.
Preferably, in the step (2), the holding time is 4 h.
The graphite phase nitrogen carbide composite material of the phosphorus-doped cobaltosic oxide quantum dots prepared by the preparation method also belongs to the protection scope of the invention.
The application of the graphite-phase nitrogen carbide composite material of the phosphorus-doped cobalt tetroxide quantum dots in degrading organic pollutants is more preferable, and the application is the application in degrading organic pollutants AO 7.
The invention adopts the method that the vitamin B12 is added into the precursor melamine to generate the C3N4Is doped with phosphorus, broadens C3N4The photoresponse range of (d); meanwhile, through a high-temperature polymerization process, the formed cobaltosic oxide is tightly combined with the graphite-phase carbon nitride in a quantum dot form, so that the phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material is obtained; the specific surface area of the composite material is as high as 52.58m2And g, doping phosphorus in a grid structure of the nitrogen carbide in an atomic mode, wherein cobaltosic oxide quantum dots uniformly grow on the surface of the graphite-phase nitrogen carbide, and the size of the quantum dots is 2.5-4.5 nm. The incorporated phosphorus makes C original3N4The forbidden bandwidth is reduced, the energy required for photoproduction electron transfer is reduced, the cobaltosic oxide quantum dots enable the material to obtain a periscopic quantum effect, the transmission efficiency of photoelectrons is also improved, and the cobaltosic oxide quantum dots and the common g-C quantum dots cooperate to enable the material to be compared with the common g-C quantum dots3N4The photocatalytic degradation capability is obviously improved.
Drawings
FIG. 1 is a transmission electron micrograph of a graphite phase nitrogen carbide composite prepared in example 4;
FIG. 2 is a high resolution transmission electron micrograph of a graphite phase nitrogen carbide composite prepared in example 4;
FIG. 3 is an EDX spectrum of a graphite phase nitrogen carbide composite prepared in example 4;
FIG. 4 is a dark field elemental scan of a high angle ring image of a graphite phase nitrogen carbide composite prepared in example 4;
FIG. 5 is a graph of the UV-VIS diffuse reflectance spectrum of the graphite phase nitrogen carbide composite prepared in example 4;
figure 6 is a graph of the forbidden bandwidth of the graphite phase nitrogen carbide composite prepared in example 4;
FIG. 7 is a graph of photocatalytic degradation of AO7 for conventional graphite phase nitrogen carbide and graphite phase nitrogen carbide composites of the present invention;
FIG. 8 is a diagram of a generalThe generation of graphite phase nitrogen carbide in the light state at different time points
An electron spin resonance spectrum of the active species;
FIG. 9 shows the generation of graphite-phase carbonitride composite materials prepared in example 4 at different time points in the light state
Electron spin resonance spectroscopy of the active species.
Detailed Description
The invention is further described below with reference to the figures and examples. Reagents, materials and apparatus used in the present invention are commercially available unless otherwise specified.
Example 1
Adding 0.01 g of vitamin B12 and 10 g of melamine into 30 mL of methanol, carrying out ultrasonic treatment for 20-30 min, stirring at 75 ℃ until the vitamin B and the melamine are completely dissolved, transferring the solution into an electrothermal blowing drying oven, drying at 95 ℃ until the methanol is completely evaporated to dryness, and naturally cooling to room temperature to collect the obtained intermediate powder; and collecting the obtained intermediate powder, placing the intermediate powder in a muffle furnace, heating to 520-580 ℃, controlling the heating rate at 5 ℃/min during heating, and carrying out heat preservation reaction for 3-4 h. And cooling, taking out the polycondensation block product, grinding by using an agate mortar, and sieving by using a 200-mesh sieve to obtain the target product 1.
Example 2
Adding 0.03 g of vitamin B12 and 10 g of melamine into 30 mL of methanol, carrying out ultrasonic treatment for 20-30 min, stirring at 75 ℃ until the vitamin B and the melamine are completely dissolved, transferring the solution into an electrothermal blowing drying oven, drying at 95 ℃ until the methanol is completely evaporated to dryness, and naturally cooling to room temperature to collect the obtained intermediate powder; and collecting the obtained intermediate powder, placing the intermediate powder in a muffle furnace, heating to 520-580 ℃, controlling the heating rate at 5 ℃/min during heating, and carrying out heat preservation reaction for 3-4 h. And cooling, taking out the polycondensation block product, grinding by using an agate mortar, and sieving by using a 200-mesh sieve to obtain the target product 2.
Example 3
Adding 0.05 g of vitamin B12 and 10 g of melamine into 30 mL of methanol, carrying out ultrasonic treatment for 20-30 min, stirring at 75 ℃ until the vitamin B and the melamine are completely dissolved, transferring the solution into an electrothermal blowing drying oven, drying at 95 ℃ until the methanol is completely evaporated, naturally cooling to room temperature, and collecting the obtained intermediate powder; and collecting the obtained intermediate powder, placing the intermediate powder in a muffle furnace, heating to 520-580 ℃, controlling the heating rate at 5 ℃/min during heating, and carrying out heat preservation reaction for 3-4 h. And cooling, taking out the polycondensation block product, grinding by using an agate mortar, and sieving by using a 200-mesh sieve to obtain the target product 3.
Example 4
Adding 0.1 g of vitamin B12 and 10 g of melamine into 30 mL of methanol, carrying out ultrasonic treatment for 20-30 min, stirring at 75 ℃ until the vitamin B and the melamine are completely dissolved, transferring the solution into an electrothermal blowing drying oven, drying at 95 ℃ until the methanol is completely evaporated, naturally cooling to room temperature, and collecting the obtained intermediate powder; and collecting the obtained intermediate powder, placing the intermediate powder in a muffle furnace, heating to 520-580 ℃, controlling the heating rate at 5 ℃/min during heating, and carrying out heat preservation reaction for 3-4 h. And cooling, taking out the polycondensation block product, grinding by using an agate mortar, and sieving by using a 200-mesh sieve to obtain the target product 4.
Example 5
Adding 0.2 g of vitamin B12 and 10 g of melamine into 30 mL of methanol, carrying out ultrasonic treatment for 20-30 min, stirring at 75 ℃ until the vitamin B and the melamine are completely dissolved, transferring the solution into an electrothermal blowing drying oven, drying at 95 ℃ until the methanol is completely evaporated to dryness, and naturally cooling to room temperature to collect the obtained intermediate powder; and collecting the obtained intermediate powder, placing the intermediate powder in a muffle furnace, heating to 520-580 ℃, controlling the heating rate at 5 ℃/min during heating, and carrying out heat preservation reaction for 3-4 h. And cooling, taking out the polycondensation block product, grinding by using an agate mortar, and sieving by using a 200-mesh sieve to obtain the target product 5.
The composite material prepared in example 4 is subjected to transmission electron microscopy and high-resolution transmission electron microscopy, see FIGS. 1 and 2, and the composite material shows typical g-C as can be seen from the edge characteristics of the photograph of FIG. 13N4The sheet structure of (A) shows that the addition of B12 in the preparation process does not change the original productMicroscopic morphology; from the high-resolution electron micrograph shown in FIG. 2, it can be confirmed that the composite Co3O4The red circle region is Co in the presence of quantum dots3O4The quantum dots have the size of about 2-3, the region has obvious metal lattice arrangement characteristics, the lattice spacing of each row is 0.243 nm, and the quantum dots and Co have the same size3O4The 311 crystal planes in the unit cell coincide.
The composite material prepared in example 4 was subjected to EDX test, see FIG. 3, for which the following test results are shown except for C3N4C, N element and Cu element of the copper net carrying the sample, as well as response signals of P, Co and O exist, which proves that P, Co element in B12 enters the composite material through thermal polycondensation, and Co should be in an oxidation state Co through combination of energy position comparison3O4The form exists.
The composite material prepared in example 4 is subjected to transmission electron microscope high-angle ring image dark field element scanning, and referring to fig. 4, the existence of P, Co element in the composite material can be further confirmed by observing the region, and the distribution of the P, Co element is relatively uniform.
The composite material prepared in example 4 and common graphite phase nitrogen carbide are subjected to ultraviolet-visible diffuse reflection spectrum detection, and referring to fig. 5, the visible composite material has higher absorbance, and the ultraviolet absorption edge of the visible composite material is red-shifted compared with the common graphite phase nitrogen carbide.
And calculating the data obtained by the corresponding detection of the figure 5 according to a Kubelka-Munk formula, and drawing a figure 6 according to the calculation result, wherein the figure can reflect the forbidden band characteristics of the material. It can be seen that the ratio is compared with pure g-C3N4The forbidden band width of the composite material B12-C is 2.68eV3N4The forbidden band width of the crystal is reduced to 2.25eV, which is caused by the doping of P and Co3O4The reduction of the forbidden band width also reduces the energy required for transferring the photo-generated electrons, which is one of the reasons for improving the catalytic degradation performance of the photo-generated electrons.
The composite material prepared in the embodiment 1-5, common graphite phase nitrogen carbide and graphite phase nitrogen carbide modified by cobaltosic oxide are subjected to photocatalytic degradation AO7 test, and the specific experimental parameters are as follows: a 250W xenon lamp light source with a 420 nm cut-off sheet and a tubular photocatalysis reactor, wherein the dosage of the catalyst is 1 g/L, the initial concentration of AO7 is 10 mg/L, the initial pH is 6.8, and the interference of the adsorption effect of the catalyst is eliminated by oscillating for 40 min in the dark before the light source is started; the AO7 concentration during the process was reflected by measuring the absorbance of the solution after filtration through a 0.22 μm filter at 484 nm using a spectrophotometer. Therefore, the degradation effect of the composite material of be is obviously better than that of common graphite-phase nitrogen carbide, and after 180 min illumination, the concentration of a target pollutant AO7 is reduced to 1/10.
The measurement tests of fig. 8 and 9 were performed on the composite material prepared in example 4 and ordinary graphite-phase nitrogen carbide, using an AXM-09 electron paramagnetic resonance spectrometer from Albutran corporation, usa, and 0.1 g of the two materials were ultrasonically dispersed in 10 mL of methanol and a certain amount of lutidine N-oxide (DMPO) as a spin resonance reagent was added before the start of the measurement so as to capture the spin signal released by the complexation of the free radical with it, and the spin signal value of the system 10 min after the start of the reaction was recorded by the instrument after the light source was turned on, and plotted as a spectrogram.
Claims (11)
1. The preparation method of the phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material is characterized by comprising the steps of taking vitamin B12 and melamine as raw materials, taking small molecular alcohol as a solvent, drying, heating to 500-600 ℃, preserving heat for 2-6 hours, cooling and grinding to obtain a target product.
2. The method according to claim 1, wherein the mass ratio of vitamin B12 to melamine is 0.1-2.0: 100.
3. The method of claim 2, wherein the small molecule alcohol is methanol, ethanol, or propanol.
4. The preparation method according to any one of claims 1 to 3, comprising the specific steps of:
(1) weighing vitamin B12 and melamine according to a ratio, adding solvent micromolecule alcohol, performing ultrasonic treatment, heating to dissolve, drying to remove the solvent, and cooling to obtain intermediate powder;
(2) and heating the intermediate powder to 500-600 ℃, preserving heat for 2-6 hours, cooling and grinding to obtain the target product.
5. The method according to claim 4, wherein the sonication time in step (1) is 20 min.
6. The method according to claim 4, wherein the heating temperature for dissolving in the step (1) is 75 ℃.
7. The production method according to claim 4, wherein in the step (2), the temperature increase rate for heating the intermediate powder is 5 ℃/min.
8. The method according to claim 4, wherein in the step (2), the holding time is 4 hours.
9. The phosphorus-doped cobaltosic oxide quantum dot modified graphite-phase nitrogen carbide composite material is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. Use of the composite material of claim 9 for degrading organic contaminants.
11. The use according to claim 10, wherein said use is in the degradation of the organic contaminant AO 7.
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| CN110182773A (en) * | 2019-07-02 | 2019-08-30 | 济南大学 | 0 dimension vanadate quantum dot/two dimension graphitic carbonaceous nitrogen nanometer sheet preparation |
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|---|---|---|---|---|
| CN105344369A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof |
| CN106622324A (en) * | 2016-12-07 | 2017-05-10 | 福建医科大学 | Graphite-phase nitrogen carbide nanosheet/cobaltosic oxide nanosheet composite nanomaterial of scale-shaped structure and preparation method and application thereof |
| CN106732774A (en) * | 2017-03-03 | 2017-05-31 | 辽宁大学 | A kind of vitamin B12Functionalization graphene composite and its preparation method and application |
| KR20170064586A (en) * | 2015-12-01 | 2017-06-12 | 인하대학교 산학협력단 | Composite for photocatalystic and method of preparing the same |
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| CN105344369A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof |
| KR20170064586A (en) * | 2015-12-01 | 2017-06-12 | 인하대학교 산학협력단 | Composite for photocatalystic and method of preparing the same |
| CN106622324A (en) * | 2016-12-07 | 2017-05-10 | 福建医科大学 | Graphite-phase nitrogen carbide nanosheet/cobaltosic oxide nanosheet composite nanomaterial of scale-shaped structure and preparation method and application thereof |
| CN106732774A (en) * | 2017-03-03 | 2017-05-31 | 辽宁大学 | A kind of vitamin B12Functionalization graphene composite and its preparation method and application |
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