CN109663584A - The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst - Google Patents
The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst Download PDFInfo
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- CN109663584A CN109663584A CN201811558781.0A CN201811558781A CN109663584A CN 109663584 A CN109663584 A CN 109663584A CN 201811558781 A CN201811558781 A CN 201811558781A CN 109663584 A CN109663584 A CN 109663584A
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- lacking oxygen
- photochemical catalyst
- oxide semiconductor
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000001301 oxygen Substances 0.000 title claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 73
- 239000004065 semiconductor Substances 0.000 title claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 13
- 229910001930 tungsten oxide Inorganic materials 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910003081 TiO2−x Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000003823 mortar mixing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/39—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
-
- 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
- B01J37/16—Reducing
Abstract
The present invention provides the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst, step includes first mixing metal oxide powder metal simple-substance particle corresponding with the metal oxide, and resulting mixture is sintered under inert atmosphere.The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst provided by the invention, solve the problems, such as exist when high temperature and pressure pure hydrogen reduction method and replacement method prepare Lacking oxygen type metal oxide semiconductor photochemical catalyst in the prior art, preparation method of the invention will not introduce impurity element, preparation process is simple and convenient, high safety and reliability, the prior art is higher than using the Lacking oxygen type semiconductor material optical electro-chemistry activity that the method for the present invention is prepared, preparation method of the invention, there is quantitative controllability when preparing Lacking oxygen, the semiconductor catalyst of different content Lacking oxygen can be obtained in mass fraction by controlling metal simple-substance.
Description
Technical field
The invention belongs to be catalyzed field of engineering technology, and in particular to Lacking oxygen type metal oxide semiconductor photochemical catalyst
Preparation method.
Background technique
Metal-oxide semiconductor (MOS) because it has many advantages, such as nontoxic, easy preparation, cheap and good stability,
It has a wide range of applications in terms of photocatalytic water, light degradation, photochromic and solar battery.
The defects of semiconductor structure plays very important effect in photocatalysis field.On the one hand, suitable defect knot
Structure provides active site for light-catalyzed reaction；On the other hand, Lacking oxygen caused by the metal ion of lower valency can be in semiconductor
Band structure in form new impurity energy level, further widen light abstraction width.
In the prior art, the method for preparing Lacking oxygen type semiconductor material is high temperature and pressure pure hydrogen reduction method.
CN106890653A discloses a kind of preparation method and application of Lacking oxygen auto-dope BiOI visible light catalyst, which uses
A kind of novel narrow gap semiconductor BiOI is handled to obtain Lacking oxygen auto-dope BiOI visible by hydrogen reduction method by high temperature hydrogenation
Photochemical catalyst, invention gained Lacking oxygen auto-dope BiOI visible light catalyst will not be introduced compared to traditional element doping
Impurity element, to protect the stability of BiOI catalyst crystal lattice.Excessive Lacking oxygen can be in the valence band and conduction band of BiOI
Centre forms an Intermediate Gray, to greatly improve the visible absorption of BiOI.Spectral response range can be effectively widened, significantly
The recombination probability of carrier is reduced, photocatalysis efficiency is improved.The photochemical catalyst is under visible light conditions, to Microcystin
The toxic organic pollutant of representative has good degradation effect, the preparation method simple process of the invention.CN107999110A
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application is disclosed, the invention is with Lacking oxygen
WO2.72Processing is doped to carbonitride as doped semiconductor, the Lacking oxygen structure of tungsten oxide can be in light-catalyzed reaction
More active sites, while Lacking oxygen tungsten oxide/carbonitride (WO are provided2.72/C3N4) composite material have smaller forbidden band it is wide
Degree, has broader response range to sunlight.
However, above method the high requirements on the equipment, preparation process is at high cost, and there are some potential safety problemss.In addition to
Other than high temperature and pressure pure hydrogen reduction method, the displacement reaction (such as thermit reaction) of active metal also be used to prepare Lacking oxygen type
Semiconductor material, this method can introduce the impurity element for being difficult to eliminate.Therefore it still needs to develop a kind of new Lacking oxygen type partly to lead
Preparation.
Summary of the invention
Exist to solve the problem of to prepare Lacking oxygen type semiconductor in the prior art, the purpose of the present invention is to provide oxygen
The preparation method of vacancy type metal oxide semiconductor photochemical catalyst.
To achieve the above object, the invention adopts the following technical scheme:
The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst, step include:
(1) metal oxide powder metal simple-substance particle corresponding with the metal oxide is mixed；
(2) sintering step (1) resulting mixture under inert atmosphere.
Preferably, the metal oxide is tungstic acid (WO3), titanium dioxide (TiO2), iron oxide (Fe2O3) and oxygen
Change at least one of zinc (ZnO).
Preferably, the metal oxide is 100:(0.1~10 with the mass ratio of corresponding metal simple-substance).
Preferably, the partial size of the metal oxide powder is less than 200nm.
Preferably, the partial size of the metal simple-substance particle is less than 200nm.
Preferably, the temperature of step (2) described sintering is 300~800 DEG C, and the time of the sintering is 0.5~12h.
It is further preferred that the temperature of step (2) described sintering is 500~700 DEG C, the time of the sintering is 4~8h.
Preferably, step (2) inert atmosphere is argon gas.
(metal simple-substance and highest oxides) are utilized between eigenelement different valence state in preparation method of the invention
Valence state comproportionation reaction, under suitable condition carry out identity element itself redox reaction, generate the metal of lower valency
Ion, to form Lacking oxygen.
Preparation method of the invention, using the autoreduction method of element, compared with prior art securely and reliably, simply just
Just, it is not introduced into that impurity element, environmentally protective, universality is strong, and Lacking oxygen type semiconductor material obtained is with higher
Optical electro-chemistry activity.
Beneficial effects of the present invention
1, the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst provided by the invention, solves existing skill
Art high temperature high pressure pure hydrogen reduction method and replacement method are deposited when preparing Lacking oxygen type metal oxide semiconductor photochemical catalyst
The problem of, preparation process is simple and convenient, will not introduce impurity element, high safety and reliability；
2, the Lacking oxygen type semiconductor material prepared using the method for the present invention, optical electro-chemistry activity are higher than the prior art
The same material of preparation；
3, preparation method of the invention has quantitative controllability when preparing Lacking oxygen, by the matter for controlling metal simple-substance
The semiconductor catalyst of different content Lacking oxygen can be obtained in amount score.
Detailed description of the invention
Fig. 1 is tungsten oxide powder (WO of the embodiment 1 containing oxygen vacancy3-x, 0 < x < 0.5) transmission electron microscope picture.
Fig. 2 is tungsten oxide powder (WO of the embodiment 1 containing oxygen vacancy3-x, 0 < x < 0.5) Raman map.
Fig. 3 is tungsten oxide powder (WO of the embodiment 1 containing oxygen vacancy3-x, 0 < x < 0.5) EPR figure.
Fig. 4 is tungsten oxide powder (WO of the embodiment 1 containing oxygen vacancy3-x, 0 < x < 0.5) absorbing properties map.
Fig. 5 is tungsten oxide powder (WO of the embodiment 1 containing oxygen vacancy3-x, 0 < x < 0.5) photoelectrochemical behaviour map.
Fig. 6 is titanium dioxide powder (TiO of the embodiment 2 containing oxygen vacancy2-x, 0 < x < 0.5) transmission electron microscope picture.
Fig. 7 is titanium dioxide powder (TiO of the embodiment 2 containing oxygen vacancy2-x, 0 < x < 0.5) Raman map.
Fig. 8 is titanium dioxide powder (TiO of the embodiment 2 containing oxygen vacancy2-x, 0 < x < 0.5) EPR figure.
Fig. 9 is titanium dioxide powder (TiO of the embodiment 2 containing oxygen vacancy2-x, 0 < x < 0.5) absorbing properties map.
Titanium dioxide powder (TiO of Figure 10 embodiment 2 containing oxygen vacancy2-x, 0 < x < 0.5) photoelectrochemical behaviour map.
Figure 11 is ferric oxide powder (Fe of the embodiment 3 containing oxygen vacancy2O3-x, 0 < x < 0.5) transmission electron microscope picture.
Figure 12 is ferric oxide powder (Fe of the embodiment 3 containing oxygen vacancy2O3-x, 0 < x < 0.5) Raman map.
Figure 13 is ferric oxide powder (Fe of the embodiment 3 containing oxygen vacancy2O3-x, 0 < x < 0.5) EPR figure.
Figure 14 is ferric oxide powder (Fe of the embodiment 3 containing oxygen vacancy2O3-x, 0 < x < 0.5) absorbing properties map.
Figure 15 is ferric oxide powder (Fe of the embodiment 3 containing oxygen vacancy2O3-x, 0 < x < 0.5) photoelectrochemical behaviour figure
Spectrum.
Figure 16 is WO3-xThe W4f map of XPS detection.
Figure 17 is WO3-xThe O1s map of XPS detection.
Specific embodiment
The following is specific embodiments of the present invention, and further retouches to technical solution of the present invention work in conjunction with the embodiments
It states, however, the present invention is not limited to these examples.
Embodiment 1
This example is prepared for Lacking oxygen type metal oxide semiconductor photochemical catalyst WO3-x(0 < x < 0.5), specifically:
Weigh 2.0g commercialization WO3Powder and 0.05g (2.5wt%) metal tungsten powder, are fully ground mixed in the agate mortar
It closes.Said mixture is put into porcelain boat, in tube furnace under Ar protective atmosphere, 600 DEG C of heat treatment 4h naturally cool to room temperature,
Obtain the tungsten oxide powder (WO of oxygen-containing omission3-x, 0 < x < 0.5).
Since after introducing Lacking oxygen, the lattice of semiconductor can be by partial destruction, therefore will appear partial folds and be crushed,
Tungsten oxide powder (the WO that will be prepared3-x, 0 < x < 0.5) and it is characterized with transmission electron microscope, as shown in Figure 1, lattice fringe
Fold suggests the formation of Lacking oxygen.
Fig. 2 is the tungsten oxide powder (WO being prepared3-x, 0 < x < 0.5) Raman characterization map, the missing of O will cause
The vibration frequency of Me-O key reduces, so that Raman curve be made red shift (Δ s=3cm occur-1).For tungsten oxide, it is in
680cm-1Raman characteristic peak correspond to tungsten oxide surface W-O key, characteristic peak of the tungsten oxide powder at this after heat treatment
Weaken, shows the presence of Lacking oxygen.
Fig. 3 is the EPR figure of material, wherein it can be observed that characteristic peak (O corresponding to Lacking oxygenv)。
Fig. 4 is the absorbing properties map of material, which illustrates that the formation of Lacking oxygen enhances semiconductor material to the sun
The absorption of light.
Fig. 5 is the photoelectrochemical behaviour map of Lacking oxygen type semiconductor material, it can be seen that the defect knot of Lacking oxygen
Structure significantly improves the PhotoelectrocatalytiPerformance Performance of material.
Embodiment 2
This example is prepared for Lacking oxygen type metal oxide semiconductor photochemical catalyst TiO2-x(0 < x < 0.5), specifically:
2.0g commercialization TiO2 powder (P25) and 0.05g (2.5wt%) metallic titanium powder is weighed, in the agate mortar sufficiently
Ground and mixed.Said mixture is put into porcelain boat, in tube furnace under Ar protective atmosphere, 600 DEG C of heat treatment 4h are naturally cooled to
Room temperature to get arrive the titanium dioxide powder (TiO containing oxygen vacancy2-x, 0 < x < 0.5).
To TiO2-xIt is tested with transmission electron microscope, as a result the fold of lattice fringe as shown in Figure 6 suggests the formation of oxygen sky
Position.
Test results are shown in figure 7 for Raman；EPR testing result is as shown in Figure 8；Absorbing properties and photoelectrochemical behaviour point
Not not as shown in Figure 9 and Figure 10.
Embodiment 3
This example is prepared for Lacking oxygen type metal oxide semiconductor photochemical catalyst Fe2O3-x(0 < x < 0.5), specifically:
2.0g commercialization ferric oxide powder and 0.05g (2.5wt%) metal iron powder are weighed, is fully ground in the agate mortar
Mixing.Said mixture is put into porcelain boat, in tube furnace under Ar protective atmosphere, 600 DEG C of heat treatment 4h naturally cool to room
Temperature to get arrive the ferric oxide powder (Fe containing oxygen vacancy2O3-x, 0 < x < 0.5).
To Fe2O3-xIt is tested with transmission electron microscope, as a result as shown in figure 11；Raman map is as shown in figure 12；EPR detection
As a result as shown in figure 13；Absorbing properties and photoelectrochemical behaviour difference are as shown in Figure 14 and Figure 15.
Embodiment 4
This example is prepared for Lacking oxygen type metal oxide semiconductor light-catalyst ZnO1-x(0 < x < 0.5), specifically:
2.0g commercialization Zinc oxide powder and 0.05g (2.5wt%) metal zinc are weighed, is fully ground in the agate mortar
Mixing.Said mixture is put into porcelain boat, in tube furnace under Ar protective atmosphere, 600 DEG C of heat treatment 4h naturally cool to room
Temperature to get arrive the Zinc oxide powder (ZnO containing oxygen vacancy1-x, 0 < x < 0.5).
Comparative example 1
Lacking oxygen type metal oxide semiconductor photocatalysis has been prepared by high temperature and pressure pure hydrogen reduction method in this example
Agent WO3-x, show that oxygen index (OI) is 2.95 by XPS detection.
In addition the semiconductor light-catalyst of same oxygen index (OI), specific method have been prepared using preparation method of the invention
And condition are as follows: weigh 2.0g commercialization WO3Powder and 0.01g (0.5wt%) metal tungsten powder, are fully ground mixed in the agate mortar
It closes.Said mixture is put into porcelain boat, in tube furnace under Ar protective atmosphere, 600 DEG C of heat treatment 4h naturally cool to room temperature,
The tungsten oxide powder for obtaining oxygen-containing omission detects through XPS and confirms, the oxygen index (OI) of material is 2.95.
WO3-xMiddle oxygen index (OI) 3-x is obtained by element area O/W in xps map (Figure 16 and Figure 17), and data are as shown in table 1.
The oxygen index (OI) of 1 difference W metal simple-substance content of table
Figure 16 is WO3-xThe W4f map of XPS detection, Figure 17 WO3-xThe O1s map of XPS detection.
The absorbing properties and photoelectrochemical behaviour of two kinds of materials are tested respectively, and discovery uses preparation method system of the present invention
Standby semiconductor light-catalyst is compared with the semiconductor light-catalyst that high temperature and pressure pure hydrogen reduction method is prepared, light absorption
Performance is suitable, and photoelectrochemical behaviour improves 15 times, illustrates the Lacking oxygen type semiconductor material prepared using the method for the present invention,
Optical electro-chemistry activity is higher than the same material of prior art preparation.
Claims (7)
1. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst, which is characterized in that step includes:
(1) metal oxide powder metal simple-substance particle corresponding with the metal oxide is mixed；
(2) sintering step (1) resulting mixture under inert atmosphere.
2. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
The metal oxide is tungstic acid (WO3), titanium dioxide (TiO2), iron oxide (Fe2O3) and zinc oxide (ZnO) in extremely
Few one kind.
3. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
The metal oxide is 100:(0.1~10 with the mass ratio of corresponding metal simple-substance).
4. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
The partial size of the metal oxide powder is less than 200nm.
5. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
The partial size of the metal simple-substance particle is less than 200nm.
6. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
The temperature of step (2) described sintering is 300~800 DEG C, and the time of the sintering is 0.5~12h.
7. the preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst according to claim 1, which is characterized in that
Step (2) inert atmosphere is argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811558781.0A CN109663584B (en) | 2018-12-19 | 2018-12-19 | Preparation method of oxygen vacancy type metal oxide semiconductor photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811558781.0A CN109663584B (en) | 2018-12-19 | 2018-12-19 | Preparation method of oxygen vacancy type metal oxide semiconductor photocatalyst |
Publications (2)
| Publication Number | Publication Date |
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| CN111792700A (en) * | 2020-07-07 | 2020-10-20 | 桂林理工大学 | Application of BiOBr or oxygen vacancy BiOBr in removing algae organic matters and removing method |
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| CN111634956A (en) * | 2020-05-28 | 2020-09-08 | 上海大学 | Method for synthesizing oxygen vacancy of oxygen-containing metal compound |
| CN111634956B (en) * | 2020-05-28 | 2022-07-05 | 上海大学 | Method for synthesizing oxygen vacancy of oxygen-containing metal compound |
| CN111792700A (en) * | 2020-07-07 | 2020-10-20 | 桂林理工大学 | Application of BiOBr or oxygen vacancy BiOBr in removing algae organic matters and removing method |
| CN113003602A (en) * | 2021-02-24 | 2021-06-22 | 山东大学 | Aluminothermic reduction cerium dioxide octahedral material and preparation method and application thereof |
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