CN107961806B - Perovskite type strontium niobium nitrogen oxide semiconductor photocatalyst activation method - Google Patents
Perovskite type strontium niobium nitrogen oxide semiconductor photocatalyst activation method Download PDFInfo
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- CN107961806B CN107961806B CN201610916238.8A CN201610916238A CN107961806B CN 107961806 B CN107961806 B CN 107961806B CN 201610916238 A CN201610916238 A CN 201610916238A CN 107961806 B CN107961806 B CN 107961806B
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 10
- XJUYKJGECPPPKR-UHFFFAOYSA-N [N]=O.[Nb].[Sr] Chemical compound [N]=O.[Nb].[Sr] XJUYKJGECPPPKR-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 230000004913 activation Effects 0.000 title claims description 9
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 2
- WFPQISQTIVPXNY-UHFFFAOYSA-N niobium strontium Chemical compound [Sr][Nb] WFPQISQTIVPXNY-UHFFFAOYSA-N 0.000 claims 2
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 description 20
- 239000010431 corundum Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002981 Mott–Schottky analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
Annealing perovskite type strontium niobium nitrogen oxide semiconductor SrNbO by adopting inert atmosphere2N, the photocatalytic activity of the photocatalyst is obviously improved. In the method, the SrNbO is annealed in inert atmosphere2The concentration of the semiconductor donor with very low N is improved to a certain extent, and the separation of photoproduction electrons and holes is promoted, so that the photocatalysis efficiency is improved, and the photocatalysis oxygen production activity can be improved by 10 times.
Description
Technical Field
The invention relates to an activation method of a perovskite type strontium niobium nitrogen oxide semiconductor used for a photocatalyst.
Background
SrNbO2N is a metal oxynitride semiconductor having a perovskite-type crystal structure. Its forbidden band width is about 1.8eV, absorption edge is about 690nm, and it has wide range visible light response (ChemSusChem,2011,4, 74-78). SrNbO2N is used as a light-absorbing active semiconductor material, is excited by light to generate electrons and holes, and can be used for chemical reactions such as oxidation oxygen generation and reduction hydrogen generation of driving water (ChemSusChem,2011,4, 74-78; Materials Letters,2015,152, 131-. The method has attractive potential application in the aspect of solar energy absorption and conversion in the modes of photocatalysis, photoelectrocatalysis and the like.
Intrinsic SrNbO2The N semiconductor carrier concentration is low and the photo-generated electrons and holes are not well separated. The invention provides a method for annealing SrNbO by adopting inert atmosphere2And an anion vacancy is formed in the N and is used as a semiconductor electron donor to improve the carrier concentration, so that the separation of the photo-generated electrons and the holes is promoted. No information was found about this SrNbO2The literature reports or patents of the activation method of the N photocatalyst.
Disclosure of Invention
The invention aims to provide an activation method of a perovskite type strontium niobium nitrogen oxide semiconductor photocatalyst.
The activation method comprises the following steps:
the inert gas used is N2Or Ar, the annealing activation temperature is 550-950 ℃, preferably 650-750 ℃; the heating rate is 1-1000 deg.C/min, preferably 5-10 deg.CPer minute; the heat preservation time is 1-120 minutes, preferably 15-60 minutes; the cooling rate is 1-1000 deg.C/min, preferably 5-50 deg.C/min, so that SrNbO2The N semiconductor is activated, and the photocatalytic activity is improved.
Obtained SrNbO2The wavelength of a forbidden band-conduction band transition absorption edge in an ultraviolet-visible spectrum of the N semiconductor photocatalyst is 650-700 nm; after the annealing treatment in the inert atmosphere, the absorption of the defects with the wavelength larger than the absorption edge is increased, the donor concentration is increased, and the photocatalytic activity is improved.
The invention has the advantages and beneficial effects that:
annealing in inert atmosphere to make SrNbO2The concentration of the semiconductor donor with very low N is improved to a certain extent, and the separation of photoproduction electrons and holes is promoted, so that the photocatalysis efficiency is improved, and the photocatalysis oxygen production activity can be improved by 10 times.
Drawings
FIG. 1 is SrNbO in example 52XRD patterns of N before and after annealing at 700 ℃ in Ar atmosphere.
FIG. 2 is SrNbO in example 52The ultraviolet-visible diffuse reflection spectrograms of N before and after annealing at 700 ℃ in Ar atmosphere show absorption edges of about 680 nm.
FIG. 3 is SrNbO in example 52Scanning electron micrographs of N before and after annealing at 700 ℃ in Ar atmosphere.
FIG. 4 shows SrNbO in example 52Mott-Schottky analysis chart before and after annealing of N at 700 ℃ in Ar atmosphere and slope chart thereof, wherein the slope of the Mott-Schottky analysis chart is inversely proportional to the semiconductor donor concentration, and shows that SrNbO2The concentration of annealing carriers of N at 700 ℃ in Ar atmosphere is 2 orders of magnitude higher than that before annealing.
Detailed Description
To further illustrate the invention, the following examples are listed.
Example 1
SrNbO2Placing N in a corundum boat, sealing in a horizontal tube furnace, exhausting air, replacing with Ar for 3 times, introducing Ar, heating to 550 ℃ at the speed of 1 ℃/min, keeping for 1 min, cooling to 100 ℃ at 1 ℃, and taking out.
Example 2
SrNbO2And (3) placing N in a corundum boat, sealing the corundum boat in a horizontal tube furnace, exhausting air, replacing Ar for 3 times, introducing Ar, heating to 625 ℃ at the speed of 5 ℃/min, keeping for 60 min, cooling to 100 ℃ at the speed of 5 ℃/min, and taking out.
Example 3
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 650 ℃ at the speed of 5 ℃/min, the temperature is kept for 60 min, and the temperature is lowered to 50 ℃ at the speed of 5 ℃/min and then taken out.
Example 4
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is exhausted, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 675 ℃ at the speed of 5 ℃/min, the temperature is kept for 60 min, and the temperature is reduced to 30 ℃ at the speed of 5 ℃/min and then taken out.
Example 5
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the temperature is kept for 15 min, and the temperature is reduced to 20 ℃ at the speed of 5 ℃/min and then the corundum boat is taken out.
Example 6
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is increased to 725 ℃ at the speed of 5 ℃/min, the temperature is kept for 60 min, and the corundum boat is taken out after being reduced to 100 ℃ at the speed of 5 ℃/min.
TABLE 1 SrNbO prepared by activation of examples 2-6 (corresponding in order from top to bottom) before activation2Photocatalytic oxygen production activity of N photocatalyst
Reaction conditions are as follows: 0.1g catalyst, 100mL water, 10mmol/L AgNO3，0.1g La2O3As a buffer, the reaction solution was subjected to light irradiation with a 300W xenon lamp light source at 10 ℃ and then to light filtering with a wavelength of 400nm cut offThe uv light is filtered off by the disc.
Example 7
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 750 ℃ at the speed of 10 ℃/min, the temperature is kept for 60 min, and the temperature is reduced to 100 ℃ at the speed of 10 ℃/min and then the corundum boat is taken out.
Example 8
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 800 ℃ at the speed of 10 ℃/min, the temperature is kept for 120 min, and the temperature is reduced to 80 ℃ at the speed of 10 ℃/min and then the corundum boat is taken out.
Example 9
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 850 ℃ at the speed of 10 ℃/min, the temperature is kept for 120 min, and the temperature is lowered to 80 ℃ at the speed of 10 ℃/min and then taken out.
Example 10
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is increased to 900 ℃ at the speed of 900 ℃/min, the temperature is kept for 120 min, and the temperature is reduced to 100 ℃ at the speed of 900 ℃/min and then the corundum boat is taken out.
Example 11
SrNbO2N is put in a corundum boat, sealed in a horizontal tube furnace, air is discharged, Ar is replaced for 3 times, Ar is introduced, the temperature is raised to 950 ℃ at the speed of 1000 ℃/min, the temperature is kept for 120 min, and the temperature is lowered to 100 ℃ at the speed of 1000 ℃/min and then the corundum boat is taken out.
Example 12
SrNbO2N is contained in a corundum boat and sealed in a horizontal tube furnace to discharge air, N2Replacing 3 times, introducing Ar, heating to 550 ℃ at the speed of 5 ℃/min, keeping for 60 min, and taking out after cooling to 100 ℃ at the speed of 5 ℃/min.
Example 13
SrNbO2N is contained in a corundum boat and sealed in a horizontal tube furnace to discharge air, N2Replacing 3 times, introducing Ar, raising the temperature to 950 ℃ at the speed of 1000 ℃/min, keeping the temperature for 120 min, and reducing the temperature to 100 ℃ at the speed of 1000 ℃/min and taking out.
The results of the product characterization (see the attached figure) prepared in the examples show that the SrNbO annealing method of the invention adopts inert gas2N, the concentration of semiconductor donor is increased, and the photocatalytic activity is high. The particular embodiments described in detail hereinabove are illustrative only and are not limiting as to the scope of the invention, which is to be given the full breadth of the appended claims.
Claims (6)
1. A perovskite type strontium niobium nitrogen oxide semiconductor photocatalyst activation method is characterized in that: annealing the perovskite type strontium niobium oxynitride semiconductor in an inert atmosphere at the temperature of 550-950 ℃ to improve the activity of the semiconductor photocatalyst; the heating rate is 1-1000 ℃/min; the heat preservation time is 1-120 minutes; the cooling rate is 1-1000 deg.C/min.
2. The method of claim 1, wherein: the inert gas used for the inert atmosphere annealing treatment is Ar or N2One or two of them.
3. The method of claim 1, wherein:
the annealing treatment temperature of the inert atmosphere is 650-750 ℃; the heating rate is 5-10 ℃/min; the heat preservation time is 15-60 minutes; the cooling rate is 5-50 ℃/min.
4. A method according to claim 1 or 3, characterized by: and in the inert atmosphere annealing treatment process, the temperature is programmed to rise from room temperature to the annealing treatment temperature, and the temperature is programmed to fall to 20-100 ℃ after the heat preservation annealing treatment.
5. The method of claim 1, wherein: the perovskite type strontium niobium oxynitride semiconductor is SrNbO2The wavelength of the forbidden band-conduction band transition absorption edge in the ultraviolet-visible spectrum is 650-700 nm.
6. The method of claim 1 or 5, wherein: after the annealing treatment in the inert atmosphere, the absorption of the defects with the wavelength larger than the absorption edge is increased, the concentration of the semiconductor donor is increased, and the photocatalytic activity is improved.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085925A (en) * | 2014-07-15 | 2014-10-08 | 渤海大学 | Preparation method of LATON perovskite-type oxynitride powder |
| CN104085924A (en) * | 2014-07-15 | 2014-10-08 | 渤海大学 | Method for preparing SLYTON perovskite type nitrogen oxide powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104085925A (en) * | 2014-07-15 | 2014-10-08 | 渤海大学 | Preparation method of LATON perovskite-type oxynitride powder |
| CN104085924A (en) * | 2014-07-15 | 2014-10-08 | 渤海大学 | Method for preparing SLYTON perovskite type nitrogen oxide powder |
Non-Patent Citations (1)
| Title |
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| Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites;Daixi Chen等;《Solid State Sciences》;20150831;第54卷;2-6 * |
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