CN111167434B - Photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And preparation method and application thereof - Google Patents

Photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And preparation method and application thereof Download PDF

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CN111167434B
CN111167434B CN202010093142.2A CN202010093142A CN111167434B CN 111167434 B CN111167434 B CN 111167434B CN 202010093142 A CN202010093142 A CN 202010093142A CN 111167434 B CN111167434 B CN 111167434B
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chromium
tin
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CN111167434A (en
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宋朋
马静怡
范晓星
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Liaoning University
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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
    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/26Chromium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/39Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group

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Abstract

The invention belongs to the technical field of photocatalytic materials, and particularly discloses a photocatalytic composite material Cr for degrading gaseous pollutants2O3‑SnO2The preparation method and the application thereof are as follows: mixing chromium salt and tin salt in a certain molar ratio in deionized water, continuously stirring for 0.5-3h, and drying to obtain a precursor of the catalyst. Placing the precursor in a crucible, calcining under the condition of inert gas or air at the temperature of 300-800 ℃ for 1-4h, naturally cooling to room temperature, and grinding to obtain the composite photocatalytic material Cr2O3‑SnO2. Cr prepared by the method of the invention2O3‑SnO2The composite photocatalyst can effectively separate electron hole pairs, reduce the recombination rate of the electron holes, further effectively improve the photocatalytic activity and achieve the purpose of efficiently degrading gaseous pollutants.

Description

Photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite material Cr for photocatalytic degradation of gaseous pollutants2O3-SnO2And a preparation method and application thereof.
Background
With the development of human society and the continuous progress of economy, the combustion of fuel causes a series of serious environmental problems, and gaseous pollution is always regarded as one of the most serious environmental problems threatening human survival, and so far, people have taken different methods to solve the problems. The photocatalysis technology is a sustainable development and environment-friendly technology, realizes the degradation of gaseous pollutants by utilizing sunlight, and has the characteristics of no secondary pollution, cyclic regeneration and the like.
Cr2O3The catalyst is a very promising catalytic material, has high chemical and thermal stability, and is mainly applied to industrial refractory materials, high-temperature oxidation-resistant substances and high-performance gas sensors. The publication of Ceramics International reports CuO/Cr2O3Research on the photocatalytic activity of the co-loaded multi-walled carbon nanotube; CoFe is reported in Journal of Molecular Catalysis A Chemical2O4-Cr2O3-SiO2Degrading methylene blue in water by the photocatalysis of the fluorescent magnetic nano composite material; journal of Materials Science reports Cr under visible light2O3-CNT/TiO2Synthesis and photocatalytic behavior of the composite material; the Journal of Environmental Sciences reported newly developed Fe3O4-Cr2O3The magnetic nano composite material is used for photocatalytic decomposition of 4-chlorophenol in water. Albeit Cr2O3The photocatalytic composite material Cr can be used for the experiment of catalytic degradation of pollutants, but can efficiently degrade gaseous pollutants2O3-SnO2There are no reports yet.
Cr2O3In the case of p-type semiconductors, the catalytic activity is low because electrons or holes are easily recombined. SnO2As an n-type semiconductor, Cr2O3With SnO2Recombination forms a heterojunction, recombination of electrons or holes can be overcome, catalytic activity can be improved, and therefore, Cr2O3-SnO2Composite photocatalysts are one of the most promising catalysts.
Disclosure of Invention
The invention aims to provide a composite photocatalyst Cr for degrading gaseous pollutants2O3-SnO2The preparation method and the application thereof. The method has the advantages of simplicity, convenience, easily controlled experiment conditions and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2The preparation method comprises the following steps:
1) dissolving chromium salt and tin salt in deionized water solution, stirring and maintaining for 0.5-3h to obtain mixed solution containing chromium and tin;
2) putting the mixed solution containing chromium and tin into an oven for drying to obtain a precursor;
3) calcining the precursor obtained in the step 2) under the condition of inert gas or air, cooling to room temperature, and grinding to obtain the composite photocatalyst Cr2O3-SnO2
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2In the step 1), the chromium salt is one of chromium nitrate nonahydrate, chromium chloride hexahydrate or chromium sulfate pentahydrate.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2In the step 1), the tin salt is tin chloride dihydrate or tin chloride.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And in the step 1), the molar ratio of the chromium salt to the tin salt is 1: 1.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And the drying process in the step 2) is drying for 1-15 hours at 50-150 ℃.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2In step 3)The inert gas is nitrogen or argon.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And in the step 3), the temperature rise speed is 1-10 ℃/min, and the calcination is carried out for 1-4h at the temperature of 300-800 ℃.
The photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2The application of the catalyst in the catalytic degradation of gaseous pollutants under visible light.
Preferably, for the above-mentioned application, the gaseous contaminant is isopropanol.
Preferably, the above application, method is as follows: the photocatalytic composite material Cr is added into a sealed reaction container containing gaseous pollutants2O3-SnO2And catalytically degrading gaseous pollutants under illumination.
The invention has the beneficial effects that:
1. the invention provides Cr2O3-SnO2The composite structure of the photocatalyst can more easily and effectively separate photoproduction electrons and holes, reduce the recombination rate and effectively improve the photocatalytic activity.
2. The invention provides Cr2O3-SnO2The preparation method of the composite photocatalyst has the advantages of cheap and easily-obtained raw materials, simple and convenient operation, greatly reduced cost and good development prospect.
3. The invention provides Cr2O3-SnO2The composite photocatalyst has the rate of degrading isopropanol to produce acetone under visible light, namely Cr2O3And SnO2About 6 and 6.7 times.
Drawings
FIG. 1(a) shows pure Cr prepared in example 12O3XRD pattern of photocatalyst.
FIG. 1(b) is pure SnO prepared in example 12XRD pattern of photocatalyst.
FIG. 2 shows the 500-SCr photocatalyst prepared in example 2 and pure Cr2O3Pure SnO2Comparison of photocatalystsXRD test of (1).
FIG. 3 is an SEM image of a 500-SCr photocatalyst prepared in example 2.
FIG. 4 is a mapping image of the 500-SCr photocatalyst prepared in example 2; wherein a is a graph of the oxygen element content, b is a graph of the chromium element content, c is a graph of the tin element content, and d is a mapping graph of the total element content of the 500-SCr photocatalyst.
FIG. 5 is a comparative UV-vis plot of 400-SCr photocatalyst, 500-SCr photocatalyst, and 600-SCr photocatalyst prepared in example 2.
FIG. 6 shows pure Cr prepared2O3Photocatalyst, pure SnO2The activities of the photocatalyst, 400-SCr photocatalyst, 500-SCr photocatalyst and 600-SCr photocatalyst for degrading isopropanol gas are compared.
Detailed Description
Example 1 photocatalyst Cr capable of degrading organic contaminants2O3、SnO2
(I) preparation method
Respectively dissolving 4.0g of chromium nitrate nonahydrate and 2.25g of stannic chloride dihydrate in 100mL of deionized water, fully stirring, putting into an oven for drying at 100 ℃ for 10h, and respectively obtaining Cr2O3Precursor, SnO2A precursor.
Respectively adding Cr2O3Precursor, SnO2The precursor is placed in a muffle furnace to be calcined for 2 hours at 500 ℃, and is ground after being cooled to room temperature to obtain the catalyst Cr capable of degrading gaseous pollutants2O3And SnO2
(II) detection
FIG. 1 shows a photocatalytic material Cr prepared in example 12O3、SnO2The XRD pattern of the sample is shown in figure 1(a), and the sample has seven diffraction peaks at 24.6 degrees, 33.73 degrees, 36.31 degrees, 41.69 degrees, 50.03 degrees, 55.0 degrees and 65.31 degrees, and is Cr2O3Characteristic peak of (1), pure Cr2O3The diffraction peak of the photocatalytic material sample is completely consistent with the peak spectrum of the chromium oxide standard card, which indicates that the prepared pure Cr2O3The photocatalytic material is actually chromium sesquioxide; from FIG. 1(b)) As can be seen, the sample has five diffraction peaks at 26.65 °, 33.88 °, 51.78 °, 54.78 ° and 65.98 °, and is SnO2Characteristic peak of (1), pure SnO2The diffraction peak of the photocatalytic material sample is completely consistent with the peak spectrum of the tin oxide standard card, which shows that the prepared pure SnO2The photocatalytic material is indeed tin oxide.
Example 2 photocatalyst Cr capable of degrading gaseous contaminants2O3/SnO2
(I) preparation method
4.0g of chromium nitrate nonahydrate and 2.25g of tin chloride dihydrate are dissolved in 100mL of deionized water, and the mixture is placed into an oven for drying at 100 ℃ for 10 hours after being fully stirred, so that a catalyst precursor is obtained.
And calcining the precursor in a muffle furnace at 400 ℃ for 2h, cooling to room temperature, and grinding to obtain the catalyst 400-SCr capable of degrading organic pollutants.
And calcining the precursor in a muffle furnace at 500 ℃ for 2h, cooling to room temperature, and grinding to obtain the catalyst 500-SCr capable of degrading organic pollutants.
And calcining the precursor in a muffle furnace at 600 ℃ for 2h, cooling to room temperature, and grinding to obtain the catalyst 600-SCr capable of degrading gaseous pollutants.
(II) detection
FIG. 2 shows 500-SCr prepared in example 2 and pure Cr prepared in example 12O3Pure SnO2As can be seen from FIG. 2, sample 500-SCr has diffraction peaks at 24.6 °, 26.65 °, 33.73 °, 33.88 °, 36.31 °, 41.69 °, 51.78 ° and 65.98 °, and pure Cr2O3Pure SnO2The characteristic peaks are similar, and the successful synthesis of 500-SCr is proved.
FIG. 3 is an SEM image of the 500-SCr photocatalyst prepared in example 2, and FIG. 4 is a corresponding mapping image, from which it can be clearly seen that the surface morphology of the composite catalyst is an irregular sheet structure and the distribution is very uniform and dense. Further, it can be seen that the alloy contains three elements of Cr, Sn and O.
FIG. 5 is a graph showing the comparison of UV-vs of 400-SCr photocatalyst and 500-SCr photocatalyst 600-SCr photocatalyst prepared in example 2, in which the light absorption range of 500-SCr photocatalyst is the largest, and then 600-SCr photocatalyst and 400-SCr photocatalyst, illustrating that the catalytic activity of 500-SCr photocatalyst is the best.
Example 3 application
The different photocatalysts prepared in the examples 1 and 2 were subjected to photocatalytic performance tests.
The test process is as follows: using a 300W xenon lamp as a light source, adjusting the photocurrent to be 20A, adjusting the light intensity center to irradiate the surface of the sample, fixing the position, and respectively preparing pure Cr2O3Pure SnO2400-SCr, 500-SCr, and 600-SCr placed at 4cm2In the glass tank, the glass tank carrying the photocatalyst is respectively placed into a 224mL reactor containing atmospheric air, finally 5ul of isopropanol liquid is injected into the reactor, timing is started after the reactor is placed for 1h, a needle is drawn out every 5 minutes for a sample to be tested, the peak area of acetone generated by isopropanol degradation is recorded, and the result is that the rate of acetone generated per minute is calculated after 6 times of recording (illumination for 30 minutes) as shown in FIG. 6.
As can be seen from FIG. 6, pure Cr was produced2O3Pure SnO2Degradation isopropanol rate activity plots per minute for 400-SCr, 500-SCr, and 600-SCr. It can be seen that Cr is produced2O3-SnO2The catalytic activity ratio of the photocatalyst Cr2O3、 SnO2The activity is much higher, and the rate of degrading isopropanol to generate acetone is about 6 times and 6.7 times of the rate of the isopropanol to generate acetone. Furthermore, the activity of the 500-SCr sample is higher than that of 400-SCr and 600-SCr, and 500 ℃ is proved to be the optimal calcination temperature of the catalyst. Thus, it can be said that the prepared Cr2O3-SnO2The photocatalyst is more beneficial to the separation of photogenerated electron holes, and can provide higher catalytic activity.

Claims (5)

1. Photocatalytic composite material Cr2O3-SnO2The application of catalytic degradation of isopropanol under visible light is characterized in that a photocatalytic composite material Cr is added into a sealed reaction container containing isopropanol2O3-SnO2Light ofCatalyzing and degrading isopropanol to generate acetone under the irradiation;
the photocatalytic composite material Cr2O3-SnO2The preparation method comprises the following steps:
1) dissolving chromium salt and tin salt in deionized water solution, stirring and maintaining for 0.5-3h to obtain mixed solution containing chromium and tin;
2) putting the mixed solution containing chromium and tin into an oven for drying to obtain a precursor;
3) calcining the precursor obtained in the step 2) under the air condition, cooling to room temperature, and grinding to obtain the composite photocatalyst Cr2O3-SnO2
In the step 1), the molar ratio of the chromium salt to the tin salt is 1: 1.
2. The use of claim 1, wherein in step 1), the chromium salt is one of chromium nitrate nonahydrate, chromium chloride hexahydrate, or chromium sulfate pentahydrate.
3. The use according to claim 1, wherein in step 1) the tin salt is tin chloride dihydrate or tin chloride.
4. The use of claim 1, wherein the drying process in step 2) is drying at 50-150 ℃ for 1-15 hours.
5. The method as claimed in claim 1, wherein in step 3), the calcination is carried out at a temperature of 300-800 ℃ for 1-4h at a temperature rising rate of 1-10 ℃/min.
CN202010093142.2A 2020-02-14 2020-02-14 Photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And preparation method and application thereof Active CN111167434B (en)

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CN111569859A (en) * 2020-06-24 2020-08-25 辽宁大学 Cerium dioxide and chromium dioxide composite oxygen-containing defect photo-thermal catalyst and preparation method and application thereof
CN112958101A (en) * 2021-02-05 2021-06-15 辽宁大学 Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And preparation method and application thereof

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