CN112958101A - Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And preparation method and application thereof - Google Patents
Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And preparation method and application thereof Download PDFInfo
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- CN112958101A CN112958101A CN202110161841.0A CN202110161841A CN112958101A CN 112958101 A CN112958101 A CN 112958101A CN 202110161841 A CN202110161841 A CN 202110161841A CN 112958101 A CN112958101 A CN 112958101A
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 230000000593 degrading effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011651 chromium Substances 0.000 claims abstract description 44
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 35
- 231100000719 pollutant Toxicity 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000001844 chromium Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 6
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 2
- ZSPCEEBYANPQIX-UHFFFAOYSA-H chromium(3+) trisulfate pentahydrate Chemical compound O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cr+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Cr+3] ZSPCEEBYANPQIX-UHFFFAOYSA-H 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 10
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a photocatalytic composite material Cr for degrading gaseous pollutants2O3‑Fe2O3And a preparation method and application thereof. Dissolving chromium salt and ferric salt in deionized water, stirring for 0.5-3h, and putting the obtained mixed solution into an oven for drying to obtain a precursor; calcining the precursor in inert gas or air environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr2O3‑Fe2O3. Cr prepared by the method of the invention2O3‑Fe2O3A composite photocatalyst capable of makingThe obtained electron hole pairs are effectively separated, the recombination rate of the electron holes is reduced, and then the photocatalytic activity can be effectively improved, and the purpose of efficiently degrading gaseous pollutants is achieved.
Description
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-Fe2O3And 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.
Cr2O3In the case of p-type semiconductors, the catalytic activity is low because electrons or holes are easily recombined. Fe2O3As an n-type semiconductor, Cr2O3With Fe2O3The heterojunction is formed by compounding, recombination of electrons or holes can be overcome, catalytic activity can be improved, and the magnetic material is magnetic and convenient to recycle. Thus, Cr2O3-Fe2O3Composite photocatalysts are one of the most promising catalysts.
Disclosure of Invention
The invention aims to provide a composite photocatalyst Cr for degrading gaseous pollutants2O3-Fe2O3The 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 technical scheme that: photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3The preparation method comprises the following steps:
1) dissolving chromium salt and ferric salt in deionized water, stirring for 0.5-3h, and putting the obtained mixed solution into an oven for drying to obtain a precursor;
2)calcining the precursor in inert gas or air environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr2O3-Fe2O3。
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3The chromium salt is chromium nitrate nonahydrate, chromium chloride hexahydrate or chromium sulfate pentahydrate.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And the iron salt is ferric nitrate nonahydrate or ferric chloride.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3The molar ratio of chromium salt to iron salt is 1: 0.5-2.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And in the step 1), drying for 1-15 hours at the temperature of 50-150 ℃.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And in the step 2), the inert gas is nitrogen or argon.
Preferably, the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3In the step 2), the calcination is carried out at the temperature rise speed of 1-10 ℃/min and the temperature of 300-800 ℃ for 1-4 h.
The invention provides a photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3The application of the catalyst in the catalytic degradation of gaseous pollutants under visible light.
Preferably, the gaseous contaminant is isopropanol.
Preferably, the method is as follows: adding a photocatalytic composite material Cr for degrading gaseous pollutants into a sealed reaction container containing the gaseous pollutants2O3-Fe2O3And catalytically degrading gaseous pollutants under illumination.
The invention has the beneficial effects that:
1. the invention provides Cr2O3-Fe2O3The photocatalyst and the composite structure 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-Fe2O3The preparation method of the photocatalyst has the advantages of cheap and easily-obtained raw materials, simple and convenient operation, greatly reduced cost and good development prospect.
Drawings
FIG. 1 shows the photocatalytic composite Cr prepared in examples 1-3 of the present invention2O3-Fe2O3XRD pattern of (a).
FIG. 2 shows the photocatalytic composite Cr prepared in examples 1-3 of the present invention2O3-Fe2O3Graph comparing the activity of degrading isopropanol gas.
Detailed Description
Example 1 photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3
The preparation method comprises the following steps
Dissolving 4.0g of chromium nitrate nonahydrate and 4.04g of ferric nitrate nonahydrate in 100mL of deionized water, stirring for 1h, putting the obtained mixed solution into an oven, and drying for 10h at 100 ℃ to obtain a precursor.
Placing the obtained precursor in a muffle furnace, calcining for 2h at 400 ℃ in a nitrogen atmosphere environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3Labeled as a.
Example 2 photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3
Dissolving 4.0g of chromium nitrate nonahydrate and 2.02g of ferric nitrate nonahydrate in 100mL of deionized water, stirring for 1h, putting the obtained mixed solution into an oven, and drying for 10h at 100 ℃ to obtain a precursor.
Placing the obtained precursor in a muffle furnace, calcining for 2h at 400 ℃ in a nitrogen atmosphere environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And labeled B.
Example 3 photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3
Dissolving 4.0g of chromium nitrate nonahydrate and 8.08g of ferric nitrate nonahydrate in 100mL of deionized water, stirring for 1h, putting the obtained mixed solution into an oven, and drying for 10h at 100 ℃ to obtain a precursor.
Placing the obtained precursor in a muffle furnace, calcining for 2h at 400 ℃ in a nitrogen atmosphere environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And labeled as C.
FIG. 1 shows the photocatalytic composite Cr prepared in examples 1-3 of the present invention2O3-Fe2O3XRD pattern of (a). As can be seen from FIG. 1, comparison with the standard card proves the successful synthesis of Cr2O3-Fe2O3A photocatalytic composite material.
Example 4 application
The method comprises the following steps: the photocatalytic composite material Cr prepared in the examples 1 to 3 was respectively applied to a 300W xenon lamp as a light source, a photocurrent was adjusted to 20A, the light intensity center was adjusted to irradiate the sample surface, and the position was fixed2O3-Fe2O3Placing in a 4cm container2In the glass tank, the glass tank carrying the photocatalyst is respectively placed into 224mL reactors containing atmospheric air, 5ul of isopropanol liquid is finally injected into the reactors, timing is started after the reaction is placed for 1h, a needle is drawn out every 5 minutes for the sample to be tested, the peak area of acetone generated by isopropanol degradation is recorded, and the result is shown in FIG. 2. FIG. 2 shows the rate of acetone production per minute calculated after 6 recordings (30 minutes of light exposure).
As can be seen from FIG. 2, Cr produced in example 32O3-Fe2O3Catalytic activity of composite photocatalyst C is higher than that of Cr prepared in example 12O3-Fe2O3Composite photocatalyst A and Cr prepared in example 22O3-Fe2O3The activity of the composite photocatalyst B is much higher. Thus, it can be said that the prepared Cr2O3-Fe2O3The photocatalyst is more beneficial to the separation of photogenerated electron holes, and can provide higher catalytic activity.
Claims (10)
1. Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3The preparation method is characterized by comprising the following steps:
1) dissolving chromium salt and ferric salt in deionized water, stirring for 0.5-3h, and putting the obtained mixed solution into an oven for drying to obtain a precursor;
2) calcining the precursor in inert gas or air environment, cooling to room temperature, and grinding to obtain the photocatalytic composite material Cr2O3-Fe2O3。
2. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3The chromium salt is chromium nitrate nonahydrate, chromium chloride hexahydrate or chromium sulfate pentahydrate.
3. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3Wherein the iron salt is ferric nitrate nonahydrate or ferric chloride.
4. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3The preparation method is characterized in that the molar ratio of chromium salt to iron salt is 1: 0.5-2.
5. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3The method is characterized in that in the step 1), the drying is carried out for 1-15 hours at the temperature of 50-150 ℃.
6. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3And the method is characterized in that in the step 2), the inert gas is nitrogen or argon.
7. The photocatalytic composite material Cr for degrading gaseous pollutants as claimed in claim 12O3-Fe2O3The method is characterized in that in the step 2), the calcination is carried out at the temperature rise speed of 1-10 ℃/min and the calcination temperature of 300-800 ℃ for 1-4 h.
8. Photocatalytic composite material Cr for degrading gaseous pollutants as set forth in any one of claims 1 to 72O3-Fe2O3The application of the catalyst in the catalytic degradation of gaseous pollutants under visible light.
9. The use of claim 8, wherein the gaseous contaminant is isopropanol.
10. Use according to claim 9, characterized in that the method is as follows: adding the photocatalytic composite material Cr for degrading gaseous pollutants, which is disclosed by any one of claims 1 to 7, into a sealed reaction vessel containing gaseous pollutants2O3-Fe2O3And catalytically degrading gaseous pollutants under illumination.
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| CN202110161841.0A CN112958101A (en) | 2021-02-05 | 2021-02-05 | Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116515320A (en) * | 2023-04-30 | 2023-08-01 | 烟台大学 | Sol process of preparing Fe 2 O 3 -Cr 2 O 3 Method for preparing high near infrared reflective pigment |
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| CN101502792A (en) * | 2009-02-19 | 2009-08-12 | 北京化工大学 | Inorganic sensitized visible-light responsive photocatalyst and preparation method thereof |
| CN111167434A (en) * | 2020-02-14 | 2020-05-19 | 辽宁大学 | Photocatalytic composite material Cr for degrading gaseous pollutants2O3-SnO2And preparation method and application thereof |
| 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 |
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2021
- 2021-02-05 CN CN202110161841.0A patent/CN112958101A/en active Pending
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