CN113413899A - Preparation method and application of all-weather photocatalytic composite material - Google Patents

Preparation method and application of all-weather photocatalytic composite material Download PDF

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CN113413899A
CN113413899A CN202110354023.2A CN202110354023A CN113413899A CN 113413899 A CN113413899 A CN 113413899A CN 202110354023 A CN202110354023 A CN 202110354023A CN 113413899 A CN113413899 A CN 113413899A
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photocatalytic
composite material
weather
sral
set forth
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杨纯
张锋
刘晓
张喆
陈芳
刘军
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Hunan University of Technology
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Hunan University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/40Organic compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The invention relates to a preparation method and application of an all-weather photocatalytic composite material, wherein the preparation method comprises the following steps: weighing prepared long afterglow SrAl material2O4:Eu2+,Dy3+Grinding and mixing with urea, calcining at high temperature in muffle furnace to obtain solid powder, cooling, grinding to obtain loose and superfine SrAl2O4:Eu2+,Dy3+(x)/g‑C3N4The obtained photocatalyst is used for degrading methyl orange in aqueous solution efficiently for a whole dayWhen the visible light is degraded in a photocatalytic manner, the degradation rate can reach 97.9%, and the photocatalyst has excellent photocatalytic degradation capability and is expected to be practically applied to dye wastewater treatment. Meanwhile, the composite material can still play a photocatalysis role by depending on the afterglow performance of the long afterglow material under the condition of no light irradiation, and the problem that the traditional photocatalytic material depends on light energy is solved, so that the composite photocatalytic material prepared by the method has good application prospect.

Description

Preparation method and application of all-weather photocatalytic composite material
Technical Field
The invention relates to an all-weather visible light response type SrAl2O4:Eu2+,Dy3+(x)/g-C3N4A preparation method and an application method of a composite photocatalyst, belongs to the technical field of nano materials, and particularly relates to a photocatalyst SrAl capable of degrading azo dyes and other pollutants in water2O4:Eu2+,Dy3+(x)/g-C3N4The preparation and application methods thereof.
Background
With the worsening of the current environmental problems and the shortage of renewable energy, semiconductor photocatalysis technology comes into play, and the research on TiO is mainly conducted in the early stage due to the convenience in operation, the availability of materials, the rapid and thorough reaction and the use of renewable energy2The combination with aluminate fluorescent powder, but the photocatalysis technology depends on a light source, the use of the technology in a dark environment is limited, and the combination with the silicate-based long afterglow material ensures that the catalysis activity can be maintained at night, but the light emitted by the long afterglow material is usually positioned in a visible light wave band and cannot be widely diffused by TiO with a wide band gap of 3.2eV2In response, the graphite phase carbon nitride (g-C) at this time3N4) The appearance of (a) solves such a problem, g-C3N4The band gap of the catalyst is narrow (2.7eV), the catalyst has good photochemical stability and outstanding photocatalytic performance under the irradiation of visible light, is convenient and easy to obtain, can be polymerized by using raw materials such as urea, melamine, cyanamide and the like in one step, and is much cheaper in raw material price compared with some traditional noble metal catalysts.
So that one can enhance g-C3N4Method for utilizing visible light and photocatalytic activity in catalyzing antibiosis and degrading organic mattersHas wide application prospect.
In the process of photocatalytic reaction, a semiconductor photocatalyst is excited by light to generate photo-generated electrons, the photo-generated electrons jump from a valence band of the catalyst to a conduction band, and photo-generated holes are generated on the valence band, so that high-energy electron-hole pairs are formed in the catalyst. Wherein g-C3N4Easily combined with azo dyes or with H adsorbed on the surface of the catalyst2O or OH-The active species hydroxyl radical (HO) with strong oxidizing ability is generated by reaction, and then the organic matter is converted into harmless CO2And H2O; the electrons on the conduction band have the reducing capacity and can be matched with dissolved oxygen (O) in the solution2) Reaction to generate superoxide radical (O)2-) Then directly reacting with organic pollutants or firstly generating hydroxyl free radicals (HO) through a series of reactions, and then carrying out degradation reaction with organic matters. While dissolving oxygen (O) in the process2) Can capture photoproduction electrons, prevent electron hole recombination and improve the photocatalytic activity.
At present by modifying g-C3N4The photocatalyst can play a role under the condition of illumination, and the long-afterglow luminescent material can store light energy during light irradiation and slowly release the light energy in a dark state, so that the long-afterglow luminescent material and the traditional photocatalyst are compounded to play double roles, and a novel material which can play high-efficiency photocatalytic and antibacterial functions in the dark state is formed. Therefore, the long-afterglow material and the modified photocatalyst are combined to form the all-weather composite photocatalytic material, and the all-weather composite photocatalytic material has great scientific research significance and social and economic values.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of an all-weather photocatalytic composite material, wherein the composite material is a SrAl2O4: Eu2+, Dy3+ (x)/g-C3N4 composite material, and the SrAl2O4: Eu2+, Dy3+ (x)/g-C3N4 composite material can degrade methyl orange after illumination and illumination stop, so that a new way is provided for degrading organic matters in all weather.
The present invention achieves the above-described object by the following technical means.
A preparation method of an all-weather photocatalytic composite material comprises the following steps:
a. SrAl with different mass fraction ratios2O4:Eu2+,Dy3+(x)/g-C3N4Preparing a composite material: weighing a proper amount of long afterglow SrAl according to the proportion (x is 32.4-48.9 percent)2O4:Eu2+,Dy3+Mixing with appropriate amount of urea, grinding to obtain uniform powder, and placing in 50ml corundum crucible (with cover);
b. heating to 550 deg.C at a rate of 5 deg.C/min in a muffle furnace by high temperature solid phase method, maintaining for 2 hr, cooling to room temperature, taking out to obtain yellowish powder, and grinding to obtain SrAl2O4:Eu2+,Dy3+(x)/g-C3N4A composite photocatalytic material.
The SrAl2O4:Eu2+,Dy3+(x)/g-C3N4SrAl prepared by preparation method of composite material2O4:Eu2+,Dy3+(37.5%)/g-C3N4A composite material.
Further, the SrAl2O4:Eu2+,Dy3+(x)/g-C3N4SrAl in composite material2O4:Eu2+,Dy3+Is long afterglow powder.
SrAl2O4:Eu2+,Dy3+(x)/g-C3N4The composite light material is used for degrading methyl orange and is characterized in that SrAl2O4:Eu2+,Dy3+(x)/g-C3N4The methyl orange solution is degraded under both illumination and no light.
Further, the light source is visible light (300W xenon lamp).
SrAl2O4:Eu2+,Dy3+(x)/g-C3N4The composite light material is used for photocatalytic degradation of organic matters all day long.
Further, all mode contaminants were methyl orange solutions.
The invention has the beneficial effects that:
the preparation method is simple and easy to implement, and SrAl is enabled to be prepared by a high-temperature solid phase method2O4:Eu2+,Dy3+And g-C3N4The method is simple and easy to operate, the raw materials are cheap and easy to obtain, and the equipment and the process are simple and easy to operate; the method has the advantages of small reagent pollution, good reaction repeatability, mild preparation conditions and the like. Obtained SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4The composite material shows a good degradation effect in the process of degrading methyl orange by photocatalysis, and the photocatalysis performance is stable.
Drawings
FIG. 1 shows SrAl2O4:Eu2+,Dy3+(x)/g-C3N4Screening the optimal proportion of the composite material;
FIG. 2 shows SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4A degradation effect graph for methyl orange solutions with different concentrations;
FIG. 3 shows SrAl2O4:Eu2+,Dy3+(x)/g-C3N4A degradation efficiency graph of the methyl orange solution with the optimal degradation concentration under light and dark alternation;
FIG. 4 shows SrAl prepared by the present invention2O4:Eu2+,Dy3+(37.5%)/g-C3N4SEM images of the composite;
FIG. 5 shows SrAl prepared by the present invention2O4:Eu2+,Dy3+(x)/g-C3N4An XRD pattern of the composite material;
FIG. 6 shows SrAl prepared by the present invention2O4:Eu2+,Dy3+(x)/g-C3N4(ii) an infrared spectrum of the composite;
FIG. 7 shows SrAl prepared by the present invention2O4:Eu2+,Dy3+(37.5%)/g-C3N4Composite material in the sunAnd (4) a graph of degradation efficiency of organic matters in an actual water sample (Xiangjiang water) under light.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
A preparation method of an all-weather photocatalytic composite material comprises the following steps:
(1)SrAl2O4:Eu2+,Dy3+(x)/g-C3N4preparation of mixed powder: weighing a proper amount of long afterglow SrAl according to the proportion (x is 32.4-48.9 percent)2O4:Eu2+,Dy3+And 10g of urea, grinding the mixture after uniform mixing to obtain uniform powder, and placing the powder in a 50ml corundum crucible (with a cover);
(2)SrAl2O4:Eu2+,Dy3+(x)/g-C3N4preparing a composite material:
heating to 550 ℃ at a heating rate of 5 ℃/min in a muffle furnace by a high-temperature solid phase method, preserving heat for 2h, cooling to room temperature, taking out, and grinding to obtain a light yellow product SrAl2O4:Eu2+,Dy3+(x)/g-C3N4A composite photocatalyst powder.
SrAl is proved by degrading methyl orange solution2O4:Eu2+,Dy3+(x)/g-C3N4The composite photocatalyst has photocatalytic degradation capability.
SrAl was characterized by SEM2O4:Eu2+,Dy3+(37.5%)/g-C3N4Surface topography of the composite.
SrAl was characterized by XRD, FTIR2O4:Eu2+,Dy3+(x)/g-C3N4A composite material.
Example 1: degradation of organic molecule methyl orange
We measured SrAl in different proportions2O4:Eu2+,Dy3+(x)/g-C3N4The degradation capability and the degradation effect of methyl orange under the irradiation of visible light are shown in figure 1, and finally the sample with the optimal proportion is determined to be SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4
Note: the methyl orange concentration used in the experiment of FIG. 1 was 3X 10-5mol/L-1The photocatalyst concentration was 1.5 g/L.
By carrying out SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4In the visible light irradiation, the degradation effect of the material on the methyl orange solution is shown in figure 2, and finally, when the concentration of the photocatalyst is 1.25g/L, SrAl is found2O4:Eu2+,Dy3+(37.5%)/g-C3N4Has the best degradation effect. Note: in the experiment of FIG. 2, methyl orange was used at a concentration of 3X 10-5mol/L-1
FIG. 3 shows the measurement of SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4Whether the composite material still has the photocatalytic performance after the illumination is stopped or not is finally found, and the photocatalyst still can play a catalytic effect in a dark environment.
Note: in the experiment of FIG. 3, methyl orange was used at a concentration of 3X 10-5mol/L-1The photocatalyst concentration was 1.25 g/L.
Example 2: test of degradation of Xiangjiang water methyl orange solution under sunlight
The practical performance test of the photocatalytic degradation of the sample is carried out according to the following steps: firstly, a proper amount of the catalyst material in the embodiment 1 is weighed and added into the filtered Xiangjiang water sample and the deionized water. Under sunlight (9/2019, 29/16: 00 start, intensity 45.10cd/m2) Continuous light was applied (9 months and 30 days in 2019, 6: 30 end).
The degradation effect is shown in FIG. 7, SrAl2O4:Eu2+,Dy3+(37.5%)/g-C3N4The composite material still has good degradation effect on pollutants in the actual water body under the irradiation of sunlight, and also plays a role at night.
Note: in the experiment of FIG. 7, methyl orange was used at a concentration of 3X 10-5mol/L-1The photocatalyst concentration was 1.25 g/L.
Example 3: testing sample stability
The stability performance of the sample is tested according to the following steps: firstly, adding a proper amount of the catalyst material in the embodiment 1 in urban areas into a methyl orange solution, measuring the degradation effect after 90min under the irradiation of a xenon lamp (300W), then recovering a sample, washing and drying, then carrying out a second experiment, circulating for 5 times, observing the degradation effect, and determining the stability and repeatability of the catalyst material.
Note: the methyl orange concentration used in the experiment was 3 x 10-5mol/L-1The photocatalyst concentration was 1.25 g/L.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of the invention is to be accorded the full scope of the claims.

Claims (8)

1. An all-weather photocatalytic composite material is characterized in that: the general formula of the composite material is SrAl2O4:Eu2+,Dy3+(x)/g-C3N4The composite catalyst with the best effect is obtained by doping in different proportions, wherein x is a long afterglow material SrAl2O4:Eu2+,Dy3+The composite material has the specific gravity of x being 32.4-48.9%, belongs to light flocculent nanometer materials, and exists in a heterojunction.
2. A method of making an all-weather photocatalytic composite as claimed in claim 1, comprising the steps of:
a. in proportion (x ═32.4% -48.9%) of SrAl, weighing proper amount of long afterglow material2O4:Eu2+,Dy3+Simultaneously in accordance with g-C3N4Weighing a proper amount of urea, grinding and uniformly mixing the urea by using an agate mortar, and placing the mixture in a 50ml corundum crucible (with a cover);
b. placing the corundum crucible with the mixed material in a muffle furnace, preparing a sample by a high-temperature calcination method, taking out the sample after the temperature in the furnace is reduced to room temperature to obtain a light yellow product, and placing the light yellow product in an agate mortar for secondary grinding to obtain SrAl2O4:Eu2+,Dy3 +(x)/g-C3N4A composite material.
3. The all-weather photocatalytic composite material according to claim 2, characterized in that: the g to C3N4According to the theoretical yield of 1g-C per 20g of urea3N4To calculate.
4. The all-weather photocatalytic composite material as set forth in claim 2, characterized in that: the SrAl2O4:Eu2+,Dy3 +Is long afterglow material powder.
5. The all-weather photocatalytic composite material as set forth in claim 2, characterized in that: is used for the all-weather photocatalytic degradation.
6. The all-weather photocatalytic composite material as set forth in claim 2, characterized in that: is used for degrading methyl orange.
7. The all-weather photocatalytic composite material as set forth in claim 2, characterized in that: is used for photocatalytic degradation of organic matters in all weather.
8. The all-weather photocatalytic composite material as set forth in claim 2, characterized in that: the method is used for photocatalytic degradation of pollutants in actual water bodies by sunlight.
CN202110354023.2A 2021-04-01 2021-04-01 Preparation method and application of all-weather photocatalytic composite material Pending CN113413899A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555003A (en) * 2022-09-20 2023-01-03 江西联锴科技有限公司 Silicon dioxide-rare earth composite photocatalytic material and preparation method and application thereof
CN115646551A (en) * 2022-11-08 2023-01-31 喀什大学 Preparation method and application of all-weather composite nano photocatalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QIANG ZHOU等: "Long afterglow phosphor driven round-the-clock g-C3N4 photocatalyst", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 *
SHIELAH MAVENGERE等: "Photocatalytic Properties of g-C3N4–Supported on the SrAl2O4:Eu,Dy/SiO2", 《COATINGS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555003A (en) * 2022-09-20 2023-01-03 江西联锴科技有限公司 Silicon dioxide-rare earth composite photocatalytic material and preparation method and application thereof
CN115646551A (en) * 2022-11-08 2023-01-31 喀什大学 Preparation method and application of all-weather composite nano photocatalyst
CN115646551B (en) * 2022-11-08 2023-12-08 喀什大学 Preparation method and application of all-weather composite nano photocatalyst

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