CN111790425A - Graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material and application thereof - Google Patents
Graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- -1 carbon nitride modified aluminum-gallium Chemical class 0.000 title claims abstract description 21
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 27
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 claims abstract description 23
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 239000010439 graphite Substances 0.000 claims description 35
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011941 photocatalyst Substances 0.000 abstract description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 2
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- 229910018229 Al—Ga Inorganic materials 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 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—
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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 technical field of material preparation and photocatalysis, and relates to preparation and application of a graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite photocatalyst material. The preparation process comprises the following steps: respectively calcining precursors of the synthetic material to obtain the aluminum-gallium co-doped zinc oxide nano powder and graphite-phase carbon nitride, and synthesizing the aluminum-gallium co-doped zinc oxide nano powder and the graphite-phase carbon nitride modified composite photocatalyst material by a single-phase dispersion method. The catalyst shows high-efficiency degradation activity in photocatalytic degradation of organic dyes in wastewater, such as methylene blue.
Description
Technical Field
The invention belongs to the field of preparation technology and catalytic application of a material based on doping and composite modification of nano-structure zinc oxide, and particularly relates to a Z-shaped photocatalyst material modified by aluminum-gallium co-doped zinc oxide nano powder composite graphite phase carbon nitride prepared by a single-phase dispersion method and application of the material in photocatalytic degradation of organic dye in wastewater.
Background
According to 2015 reports of the world health organization, diseases caused by water pollution deprive nearly one million people each year of life, which undoubtedly has caused extremely bad influence on the ecological environment and daily life around human beings. The current measures taken by people to deal with the problem of water pollution mainly include biological treatment, physical treatment, chemical treatment and the like. 1. Biological treatment is to utilize the unique metabolism activity of organisms and to absorb, accumulate, decompose and convert pollutants in a series of ways to achieve the purpose of pollution cleaning and detoxification, but the treatment period of the method is generally longer (see the description in the specification)Water Research,2020,170:115316). 2. The physical treatment generally refers to using physical adsorbent, the molecular chain of the adsorbent material mostly has a hydrophilic group capable of adhering to pollutants, and the special structure of the entanglement and crosslinking of internal molecules can absorb and store the organic macromolecules in the liquid state. Activated carbon is a common adsorbent, and has the characteristics of multiple decontamination, high efficiency and reusability, but the high cost makes the activated carbon incapable of being used in large area (see the point that the activated carbon is used in large area)Journal of Water Process Engineering,2020,33:101040). 3. The chemical treatment is to add chemical into polluted water area and then to change the physical and chemical properties of pollutant itself or to react with pollutant to produce insoluble or insoluble matter and precipitate so as to achieve the effect of making target pollutant harmless and purifying waste water. Although the method has strong decontamination capability, the method can only treat specific pollutants and has the risk of secondary pollution (see the figure)Industrial Crops & Products,2019, 141:111726). Therefore, the severity of the global environmental crisis and the limitations of the existing technologies for human coping with the environmental crisis lead to the urgent need for developing a novel water quality restoration technology which is environmentally friendly, harmless, time-saving and efficient.
The semiconductor photocatalysis technology is a new water body remediation technology with the advantages of environmental protection, high mineralization efficiency and the like, and is extremely expected to become a new way for solving the current severe water pollution problem. The photocatalyst is irradiated by sunlight, and the photocatalyst generates hydroxyl, superoxide radical, etc. with high oxidation-reduction capabilityThe active factors further react with the adsorbed pollutants on the body surface to generate CO2And H2Zero pollutant emissions such as O. Among many oxide semiconductors, zinc oxide semiconductor photocatalytic technology has attracted extensive attention due to its characteristics of low cost, no toxicity, no harm, mild repair, and no generation of secondary pollutants. However, zinc oxide with a wide forbidden band gap (3.37 eV) can only absorb ultraviolet light (only 3% of sunlight), and the photo-generated electron-hole pairs are easy to recombine, so that the carrier transfer efficiency is low, and the photocatalytic effect is not good. By doping with metal elements, can be in the valence band (VB) And a conduction band (CB) And an intermediate energy level is established between the two, so that the forbidden bandwidth is reduced, and the response to the visible light wave band is realized.
In order to further broaden the spectral response range of zinc oxide and extend the lifetime of photogenerated carriers, semiconductor recombination has also been found to be another effective approach. As long as the semiconductors have matched energy levels, the semiconductors with different band gaps can be compounded to construct a heterojunction structure, and the composite material after the heterojunction structure is formed can inhibit the recombination of electron-hole pairs generated by excitation in the semiconductor body and improve the responsiveness to visible light, so that the multi-component composite material has excellent photoelectric properties which cannot be achieved by various semiconductors. The graphite phase carbon nitride is used as a pi-pi conjugated semiconductor material, the band gap of the graphite phase carbon nitride is only 2.7 eV, and the graphite phase carbon nitride has good visible light responsiveness. In addition, the unique structure can shorten the transmission distance of photogenerated carriers, and a larger surface area can load more active sites.
Therefore, in order to widen the visible light response range of the zinc oxide and improve the separation rate of photoproduction electron-hole pairs of the zinc oxide, the composite graphite phase carbon nitride is continuously modified on the basis of the metal element aluminum gallium codoped modified zinc oxide, so that the green, environment-friendly, stable and efficient photocatalyst material is prepared.
Disclosure of Invention
The invention aims to provide a graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide (AGZ/CN) composite photocatalyst material and a preparation method thereof, and the material is applied to photocatalytic degradation of organic dye in wastewater. The AGZ nano powder material is obtained by a sol-gel method, the graphite phase carbon nitride material is obtained by calcining melamine, and finally the AGZ nano powder material and the graphite phase carbon nitride material are synthesized into the AGZ/CN composite material by a single-phase dispersion method. The preparation method is simple, the visible light response range of the prepared composite material is widened, the recombination rate of the photo-generated electron-hole pairs is inhibited, and the efficiency of photocatalytic degradation of organic pollutants in wastewater, such as methylene blue, is improved. The result of each characterization means is combined, so that the photogenerated electron-hole pair in the AGZ/CN composite material is proved to be in a Z-shaped transmission path.
In order to achieve the purpose, the preparation method of the AGZ/CN composite material is a single-phase dispersion method; the surface appearance of the graphite-phase carbon nitride is of a lamellar structure; the nano powder material with the grain size of the aluminum-gallium co-doped zinc oxide being 20-25nm is uniformly attached to the surface of graphite-phase carbon nitride.
The preparation method of the AGZ/CN composite material comprises the following steps:
the AGZ nano powder is prepared by adopting a sol-gel method: the preparation method comprises the following steps of preparing sol with 1-4at% of Al and 1-4at% of Ga by using monoethanolamine as a stabilizer and ethylene glycol monomethyl ether as a solvent:
(1) adding a precursor of zinc oxide into ethylene glycol monomethyl ether solution, stirring, then adding an aluminum precursor, a gallium precursor and ethanolamine, reacting in a water bath at 50-60 ℃ for 2-3h, and standing at room temperature to obtain a light yellow colloid;
(2) drying the yellow colloid by air blast to obtain a deep yellow viscous colloid, annealing the deep yellow viscous colloid at 350-550 ℃ for 2-3h, cooling along with the furnace, and grinding to obtain the aluminum-gallium co-doped zinc oxide;
(3) calcining any one or more of melamine, dicyandiamide, urea, cyanamide and thiourea at the temperature of 500-600 ℃ for 3-5h to obtain graphite-phase carbon nitride;
(4) putting the graphite-phase carbon nitride material into alcohol (the mass fraction of the alcohol is over 99 percent of analytically pure alcohol), performing ultrasonic homogenization, adding the aluminum-gallium co-doped zinc oxide into the solution, stirring the solution at room temperature until the solution is viscous, and performing forced air drying at the temperature of 100-110 ℃ to obtain a white powder product, namely the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material.
The precursor of the zinc oxide comprises zinc acetate or zinc nitrate. The aluminum precursor includes aluminum chloride, or aluminum nitrate. The gallium precursor includes gallium nitrate.
The molar ratio of the added ethanolamine to the total metal ions of the aluminum, gallium and zinc is 1:0.8-1.5 (as a preferable scheme, the molar ratio of the ethanolamine to the metal ions is 1: 1).
In a preferable scheme, the annealing temperature in the step (2) is 400 ℃, the heating rate is 8 ℃/min, and the reaction is carried out for 2 hours under the condition of heat preservation.
Preferably, in the step (3), the annealing temperature is 500 ℃, 520 ℃, 540 ℃ and 560 ℃, the heating rate is 5 ℃/min, and the reaction is carried out for 4h under heat preservation.
The graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material prepared by the technical scheme of the invention is applied to photocatalytic degradation of methylene blue in wastewater.
The invention has the following advantages:
the precursor materials of the zinc oxide and the graphite-phase carbon nitride used in the preparation method are commercially available zinc acetate and melamine, and have the advantages of sufficient sources, low cost, high yield and mass production.
The method for preparing the AGZ/CN composite material is a single-phase dispersion method, is easy to operate and has short period.
Ga replaces Zn position in zinc oxide crystal lattice, new impurity energy level is formed near the lower end of zinc oxide conduction band, and band gap width is reduced. Under visible light irradiation, electrons are excited to transit from the valence band to the impurity level with less energy, while holes having high oxidation are left on the valence band, and the electron-hole transition rate is improved. During the electron-hole pair transfer process, recombination is encountered, leading to reductive and oxidative annihilation. So that the doped Al acts as a trap impurity, traps and occupies electron holes, and reacts to form extremely unstable Al2+And Al4+Ions of theseThe active ions continue to adsorb O on the surface of the catalyst2And HO-The reaction generates strong oxidizing superoxide radical and hydroxyl radical, which effectively inhibits electron hole pair recombination, improves quantum efficiency and finally improves the photocatalytic activity.
The technical scheme of the invention continues to synthesize the AGZ/CN composite material with graphite-phase carbon nitride. The composite material is prepared by irradiating with visible light and zinc oxideVBElectrons on are excited to leaveVBAfter a transition to zinc oxideCBAnd then transferred to the graphite phase carbon nitride through the intersection of the two phase interfacesVBThe above. Subsequently, the electrons are excited again by the light and undergo transition, finally moving to the graphite-phase carbon nitrideCBThe above. Therefore, the AGZ/CN composite material can promote the transmission of photogenerated carriers between two phase interfaces through a Z-type transfer path, thereby effectively inhibiting the recombination of photogenerated electron hole pairs and inducing more active species to participate in the photodegradation reaction.
Drawings
FIG. 1 is a graph of the degradation of MB in the visible light for ZnO and AGZ photocatalysts doped with varying amounts prepared in example 1.
FIG. 2 is an XRD pattern of an AGZ/CN composite material, graphite phase carbon nitride, at different temperatures obtained in example 2.
FIG. 3 is SEM images of different materials prepared in example 2, wherein (a) is ZnO, (b) is AlGaN-codoped ZnO, (c) is graphite-phase carbon nitride, and (d) is an AGZ/CN composite photocatalyst material
Fig. 4 shows Uv-vis spectra and optical band gap spectra of different materials obtained in example 1, wherein (a) shows Uv-vis spectra of AGZ/CN composites obtained by co-doping aluminum-gallium with zinc oxide and graphite-phase carbon nitride under different calcination temperature conditions, and (b) shows optical band gap spectra of AGZ/CN composites obtained by co-doping aluminum-gallium with zinc oxide and graphite-phase carbon nitride under different calcination temperature conditions.
FIG. 5 is a PL spectrum of the Al-Ga co-doped zinc oxide, graphite phase carbon nitride, AGZ/CN composite material prepared in example 2.
Fig. 6 is a diagram showing the activity of photocatalytic degradation of methylene blue of the AGZ/CN composite photocatalyst material prepared under the conditions of zinc oxide, aluminum-gallium co-doped zinc oxide, graphite-phase carbon nitride and different calcination temperatures in example 2.
FIG. 7 is a diagram showing the activity of degrading methylene blue by photocatalysis of AGZ/CN composite photocatalyst materials with different composite mass ratios prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples
Example 1:
the preparation method of the AGZ in the AGZ/CN composite material comprises the following steps:
(1) preparing aluminum-gallium co-doped zinc oxide: adding zinc acetate into ethylene glycol monomethyl ether solution, stirring for 30 min, adding gallium nitrate, aluminum chloride and ethanolamine stabilizer, wherein the molar ratio of the stabilizer to the total metal ions of aluminum, gallium and zinc is 1:1, the stabilizer and the metal ions of aluminum, gallium and zinc form a complex, and heating in a water bath at 60 ℃ for 2h to perform sol. Then standing for 24 h at room temperature to obtain a light yellow colloid for later use.
(2) Then placing the mixture in a muffle furnace for annealing, raising the temperature to 400 ℃ at the temperature rise rate of 8 ℃/min, and cooling the mixture along with the furnace after annealing for 2 hours. Finally, the light yellow block product, i.e., AGZ, is removed from the furnace.
In the step, 0.0588 mol of zinc acetate, 0.0006 mol of gallium nitrate, 0.0006 mol of aluminum chloride, 60ml of ethylene glycol monomethyl ether solution and 0.06mol of ethanolamine are used to obtain the aluminum-gallium co-doped zinc oxide which is named as AG1Z。
In the step, 0.0582 mol of zinc acetate, 0.0002 mol of gallium nitrate, 0.0006 mol of aluminum chloride, 60ml of ethylene glycol monomethyl ether solution and 0.06mol of ethanolamine are used to obtain the aluminum-gallium co-doped zinc oxide which is named as AG2Z。
In the step, 0.0576 mol of zinc acetate, 0.0018 mol of gallium nitrate, 0.0006 mol of aluminum chloride, 60ml of ethylene glycol monomethyl ether solution and 0.06mol of ethanolamine are used to obtain the aluminum-gallium co-doped zinc oxide named AG3Z。
In the step, 0.057 mol of zinc acetate, 0.0024 mol of gallium nitrate, 0.0006 mol of aluminum chloride and B60ml of glycol monomethyl ether solution and 0.06mol of ethanolamine to obtain the aluminum-gallium co-doped zinc oxide which is named as AG4Z。
In the step, zinc acetate 0.06mol, ethylene glycol monomethyl ether solution 60ml and ethanolamine 0.06mol are used to obtain zinc oxide named as ZnO.
In the step, 0.0594 mol of zinc acetate, 0.0006 mol of aluminum chloride, 60ml of ethylene glycol monomethyl ether solution and 0.06mol of ethanolamine are used to obtain the aluminum-doped zinc oxide which is named as AZ.
ZnO, AZ, AG prepared in this example1Z、AG2Z、AG3Z、AG4The application of Z in degrading organic dye in wastewater, such as methylene blue, specifically comprises the following steps: simulation of (CHF-XM500, hina) visible light source (using lambda) with 300 w xenon lamp>A 400 nm type cut-off filter filters the ultraviolet light), and the concentration of the residual pollutants in the solution is determined by an ultraviolet-visible spectrophotometer by taking Methylene Blue (MB) solution as a dye model. First, 20 mg of the photocatalyst was uniformly dispersed in a 30 mM MB (10 mg/L) solution, followed by stirring in the dark for 1 hour to reach an adsorption equilibrium. After the lamp was turned on, samples were taken every 15 min, 5 mL each time, and the reaction was carried out for 180 min. Centrifuging at 8000 r/min for 3min with high speed centrifuge after sampling, and recording its peak intensity change at 664 nm of maximum absorption wavelength with ultraviolet-visible spectrophotometer
Fig. 1 is a graph of the degradation of MB by ZnO and AGZ photocatalysts in the visible. The degradation rate of ZnO powder to methylene blue within 180 min is 78%, AZ and AG1Z、AG2Z、AG3Z、AG4The degradation rates of the Z powder to methylene blue are respectively 81%, 83%, 90%, 80% and 74%, wherein AG2Z has the highest photocatalytic activity.
Example 2:
the invention relates to a preparation method of an AGZ/CN composite material, which comprises the following steps:
(1) four groups of nitrogen-rich melamine with the weight of 50g are taken as raw materials, the heating rate is 5 ℃/min, and the raw materials are respectively placed in a muffle furnace for 500 DEG CoC、520oC、540oC、560oDirectly calcining melamine for 4h under the temperature condition of C to obtainThe light yellow block-shaped final product is the graphite phase carbon nitride.
(2) Respectively putting 0.1 g of each of the four groups of graphite-phase carbon nitride with sintering temperature in the step (1) into 50 ml of 99% analytical pure alcohol, and uniformly dispersing by ultrasonic treatment for 30 min; 0.9 g of AG prepared according to example 1 was weighed again2Z is poured into the solution, and the solution is continuously stirred for 24 hours at room temperature until the solution is viscous; finally, the viscous solution is put into a blast drying oven, and the temperature parameter is set to be 100oC. The time t is 15 min. And after the alcohol is dried and volatilized, obtaining a white powder product, namely the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material.
AG prepared in this step2The Z aluminum gallium codoped zinc oxide is abbreviated as AGZ.
In this step AG2The composite material formed by Z and graphite phase carbon nitride prepared at 500 ℃ is called AGZ/CN500 for short.
In this step AG2The composite material formed by Z and graphite phase carbon nitride prepared at 520 ℃ is called AGZ/CN520 for short.
In this step AG2The composite material formed by Z and the graphite phase carbon nitride prepared at 540 ℃ is called AGZ/CN540 for short.
In this step AG2The composite material formed by Z and the graphite phase carbon nitride prepared at 560 ℃ is abbreviated as AGZ/CN 560.
FIG. 2 is an XRD pattern of AGZ/CN500, AGZ/CN520, AGZ/CN540, AGZ/CN560 composite, and graphite phase carbon nitride. The red graphite-phase carbon nitride diffraction pattern showed the appearance of the characteristic peak of graphite-phase carbon nitride at 27.6 °, corresponding to its (002) crystal plane with an interplanar spacing of 0.326 nm. AGZ/CN500 samples at 31.6o、34.4o、36.1oThree strong diffraction peaks appear at the position respectively correspond to (100), (002) and (101) crystal faces of the zinc oxide with the hexagonal wurtzite structure; no hetero-peaks other than the characteristic peaks of ZnO and graphite phase carbon nitride were found in the AGZ/CN500 sample, which means that AGZ successfully complexes with graphite phase carbon nitride. FIG. 3 shows surface topography of zinc oxide, AGZ, graphite phase carbon nitride, and AGZ/CN560 composites from a sample of the AGZ/CN compositeAs can be seen, the AGZ nano-powder is uniformly attached to the surface of the platelet-shaped graphite-phase carbon nitride semiconductor, which can provide a favorable place for photocatalytic degradation reaction. FIG. 4 shows the Uv-vis and optical bandgap spectra of AGZ/CN500, AGZ/CN520, AGZ/CN540, AGZ/CN560 composites and graphite phase carbon nitride. The position of the light absorption edge of AGZ is around 375 nm, which means that AGZ, like the original zinc oxide, absorbs mostly still ultraviolet light and hardly absorbs visible light. The position of the light absorption edge of the graphite-phase carbon nitride extends to the 440 nm blue region, but the relative absorption intensity of the region is not as high as that of the AGZ sample. After compounding AGZ and graphite phase carbon nitride, although the relative intensities of the four sets of AGZ/CN composites absorbed light in the uv region decreased slightly. However, with the rise of the preparation temperature of the graphite-phase carbon nitride, the red shift phenomenon occurs on the light absorption edge of the composite material sample, and the visible light absorption rate of the 380-540 nm wavelength band is obviously improved. The forbidden band widths of the AGZ, the graphite phase carbon nitride, the AGZ/CN500, the AGZ/CN520, the AGZ/CN540 and the AGZ/CN560 are respectively 3.04eV, 2.71 eV, 2.82 eV, 2.78 eV, 2.75 eV and 2.74 eV, namely the forbidden band width of the aluminum-gallium co-doped zinc oxide is reduced after the composite graphite phase carbon nitride, so that the visible light absorption capability of the aluminum-gallium co-doped zinc oxide is improved, and the photocatalytic degradation capability of the aluminum-gallium co-doped zinc oxide is further improved by energy efficiency. FIG. 5 is a PL spectrum of AGZ, CN560, AGZ/CN 560. It can be seen from the figure that the two luminescence peak intensities at 435 nm and 467 nm of AGZ/CN560 are greatly reduced and are lower than those of AGZ and CN560 because the electrons have successfully transited to the graphite phase carbon nitride interface and to zinc oxide, resulting in a greatly reduced recombination rate of photo-generated electron-hole pairs, which means AGZ/CN560 is the most suitable photocatalyst material in these groups of samples.
The application of the AGZ/CN500, AGZ/CN520, AGZ/CN540 and AGZ/CN560 photocatalysts of the invention in degrading organic dyes in wastewater, such as methylene blue, has the same specific steps as the degradation reaction steps in the example 1.
FIG. 6 is a diagram showing the ability of the AGZ/CN composite material prepared in this example to degrade methylene blue. The results show that: the degradation rates of zinc oxide, AGZ, graphite phase carbon nitride, AGZ/CN500, AGZ/CN520, AGZ/CN540 and AGZ/CN560 photocatalyst to methylene blue are respectively 31%, 73%, 51%, 91%, 89%, 87% and 96%, wherein the AGZ/CN560 photocatalyst has the best performance, and the activities of the AGZ, the graphite phase carbon nitride and the zinc oxide are arranged in sequence from high to low except a composite sample group. Experimental results show that the capability of zinc oxide for degrading organic pollutants in water under visible light can be doubly enhanced by doping metal elements and compounding the graphite-phase carbon nitride semiconductor material.
Example 3:
the invention relates to a preparation method of an AGZ/CN composite material, which comprises the following steps:
(1) using 50g of nitrogen-enriched melamine as raw material, heating up at a rate of 5 ℃/min, and placing in a muffle furnace 560oAnd directly calcining the melamine for 4 hours at the temperature of C to obtain a light yellow blocky final product, namely the graphite-phase carbon nitride.
(2) Taking four groups of 0.1 g of graphite-phase carbon nitride prepared in the step (1) in the example 3, respectively putting the four groups into 50 ml of 99% analytical pure alcohol, and uniformly dispersing the four groups by ultrasonic treatment for 30 min; then, 1.9 g, 0.9 g, 0.567 g and 0.4 g of AG prepared in example 1 were weighed2Z, pouring the solution, and continuously stirring the four groups of samples for 24 hours at room temperature until the samples are viscous; finally, the viscous solution is put into a blast drying oven, and the temperature parameter is set to be 100oC. The time t is 15 min. And after the alcohol is dried and volatilized, obtaining a white powder product, namely the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material.
1.9 g AG in this step2Z and 0.1 g of graphite-phase carbon nitride (mass ratio AG)2Z: CN =95: 5) is abbreviated AGZ/CN 5.
0.9 g AG in this step2Z and 0.1 g of graphite-phase carbon nitride (mass ratio AG)2Z: CN =90: 10) is abbreviated AGZ/CN 10.
0.567 g AG in this step2Z and 0.1 g of graphite-phase carbon nitride (mass ratio AG)2Z: CN =85: 15) is abbreviated AGZ/CN 15.
0.4 g AG in this step2Z and 0.1 g stoneInk phase carbon nitride (mass ratio AG)2Z: CN =80: 20) is abbreviated AGZ/CN 20.
The application of the AGZ/CN5, AGZ/CN10, AGZ/CN15 and AGZ/CN20 photocatalysts in degrading organic dyes in wastewater, such as methylene blue, has the same specific steps as the degradation reaction step in the example 1.
As shown in fig. 7, the result of visible light degradation of methylene blue for 1.5h shows that: the degradation efficiencies of AGZ/CN5, AGZ/CN10, AGZ/CN15 and AGZ/CN20 are respectively 78.2%, 90.5%, 94.0% and 93.7%, which means that the photocatalytic activity of the AGZ/CN15 photocatalyst is the highest. The photocatalytic activity of the AGZ/CN composite material can follow the g-C3N4Increase of the compounding amount, and the mass ratio AG of the two phases2CN =85: at 15, AGZ/CN15, the photocatalytic activity reached its highest. Continued increase in g-C3N4The composite amount and the photocatalytic activity of the composite material are not continuously increased but slightly reduced.
The present invention has been described in detail with reference to the specific embodiments, but the description should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The graphite phase carbon nitride modified aluminum gallium codoped zinc oxide composite material is characterized in that the aluminum gallium codoped zinc oxide is a nano powder material with the grain size of 20-25nm and is uniformly attached to the surface of graphite phase carbon nitride; in the aluminum-gallium co-doped zinc oxide, the doping amount of Al is 1-4at%, and the doping amount of Ga is 1-4 at%.
2. The graphite phase carbon nitride modified aluminum gallium co-doped zinc oxide composite material according to claim 1, wherein the Al doping amount is 1 at%, and the Ga doping amount is 2 at%.
3. The preparation method of the graphite phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 1 or 2, characterized by comprising the following steps:
(1) adding a precursor of zinc oxide into ethylene glycol monomethyl ether solution, stirring, then adding an aluminum precursor, a gallium precursor and ethanolamine, reacting in a water bath at 50-60 ℃ for 2-3h, and standing at room temperature to obtain a light yellow colloid;
(2) drying the yellow colloid by air blast to obtain a deep yellow viscous colloid, annealing the deep yellow viscous colloid at 350-550 ℃ for 2-3h, cooling along with the furnace, and grinding to obtain the aluminum-gallium co-doped zinc oxide;
(3) calcining any one or more of melamine, dicyandiamide, urea, cyanamide and thiourea at the temperature of 500-600 ℃ for 3-5h to obtain graphite-phase carbon nitride;
(4) and putting the graphite phase carbon nitride material into alcohol, performing ultrasonic homogenization, adding the aluminum-gallium co-doped zinc oxide into the solution, stirring at room temperature until the mixture is viscous, and performing forced air drying at the temperature of 100-110 ℃ to obtain a white powder product, namely the graphite phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material.
4. The method for preparing the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein the precursor of the zinc oxide comprises zinc acetate or zinc nitrate.
5. The method for preparing the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein the aluminum precursor comprises aluminum chloride or aluminum nitrate.
6. The method for preparing the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein the gallium precursor comprises gallium nitrate.
7. The preparation method of the graphite phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein the molar ratio of the added ethanolamine to the total metal ions of aluminum-gallium-zinc is 1: 0.8-1.5.
8. The preparation method of the graphite phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein in the step (2), the annealing temperature is 400 ℃, the heating rate is 8 ℃/min, and the heat preservation reaction is carried out for 2 hours.
9. The preparation method of the graphite phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material according to claim 3, wherein in the step (3), the annealing temperature is 560 ℃, the heating rate is 5 ℃/min, and the heat preservation reaction is carried out for 4 hours.
10. The application of the graphite-phase carbon nitride modified aluminum-gallium co-doped zinc oxide composite material prepared according to any one of claims 3 to 9 in photocatalytic degradation of methylene blue in wastewater.
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| Title |
|---|
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| 孙佳欣: ""新型光催化剂的设计、合成及其光催化性能研究"", 《中国优秀硕士论文全文数据库》 * |
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