CN110354863A - A kind of tungstic acid/di-iron trioxide composite photo-catalyst and its preparation method and application - Google Patents
A kind of tungstic acid/di-iron trioxide composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN110354863A CN110354863A CN201910577165.8A CN201910577165A CN110354863A CN 110354863 A CN110354863 A CN 110354863A CN 201910577165 A CN201910577165 A CN 201910577165A CN 110354863 A CN110354863 A CN 110354863A
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- iron trioxide
- tungstic acid
- composite photo
- precursor liquid
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 238000005245 sintering Methods 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002604 ultrasonography Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000004687 hexahydrates Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- 229910001887 tin oxide Inorganic materials 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 239000012692 Fe precursor Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 7
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- -1 di-iron trioxide compound Chemical class 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BLGJOEGUMNZGEX-UHFFFAOYSA-N methanol;tungsten Chemical compound [W].OC BLGJOEGUMNZGEX-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/888—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
- 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
- B01J35/33—Electric or magnetic properties
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to photocatalysis oxidation technique field, a kind of tungstic acid/di-iron trioxide composite photo-catalyst and its preparation method and application is disclosed.The tungstic acid/di-iron trioxide composite photo-catalyst is that ferric trichloride (III) hexahydrate and deionized water ultrasound are prepared ferric trichloride precursor liquid to being completely dissolved, plate conductive substrates, which lean to, to be placed in pyroreaction kettle, ferric trichloride precursor liquid is added and did not had plate conductive substrates top, in 90~140 DEG C of progress hydro-thermal reactions, after washing and drying, it is calcined at 500~700 DEG C, ferric oxide film is made in plate conductive substrates conducting surface；Di-iron trioxide substrate is leaned to and is placed in reaction kettle, tungsten chloride precursor liquid is added, it is washed and dry in 100~180 DEG C of progress hydro-thermal reactions, it is made in 450~550 DEG C of sintering.The photochemical catalyst has preferable photocatalysis performance, and preparation process is simple, can be used for photocatalysis hydrogen production, can also be applied to light and urges oxidation technology field.
Description
Technical field
The invention belongs to photocatalysis oxidation technique fields, compound more particularly, to a kind of tungstic acid/di-iron trioxide
Photochemical catalyst and its preparation method and application.
Background technique
Fossil fuel belongs to non-renewable energy resources resource, and the storage capacity of fossil fuel is limited on the earth, but with work
The fast development of industry technology, the rapidly increase of energy consuming equipment, fossil fuel are rapidly depleted, and energy shortage will be future
The significant problem that human society faces.To solve this problem, scientific research person throw oneself into searching and research it is cheap, storage
Standby alternative energy source abundant.Hydrogen Energy is the known energy the most clean now because in its reaction process with the oxygen in air
Depressed symphysis Cheng Shui, does not generate the gases such as carbon dioxide, carbon monoxide, oxynitrides, and generation environment does not pollute.In addition, hydrogen
The final product of reaction -- water, but also as the original material for preparing hydrogen, water is that the earth is the most substance of storage level, so hydrogen
It can be the optimal energy for substituting fossil energy.
The main means for preparing hydrogen at present have electrolysis water technology, photocatalysis hydrogen production technology, chemical reaction hydrogen producing technology.Always
For body, photocatalysis hydrogen production technology be it is ideal, using solar energy as energy source, pass through photochemical catalyst splitting water
Hydrogen is obtained, entire photocatalytic process does not need the additional energy and supports, but due to the factors such as technology, material, at present photocatalysis
Hydrogen manufacturing is also unable to reach practical stage.In the receivable sunlight in ground, energy be distributed mainly on visible light region and
Infrared light region, ultraviolet light only accounts for overall 4% or so, and infrared light region wavelength width range is larger, and energy is not concentrated,
The visible light land occupation table of 380nm-780nm wavelength region range can receive solar energy close to half, and energy is concentrated.Traditional light
Catalyst such as titanium dioxide, forbidden bandwidth 3.0eV, only response accounts for the ultraviolet light of sunshine gross energy about 4%, this is to the sun
Light energy is unable to fully utilize, thus photochemical catalyst selection premise first is that can be responded in visible light region.Furthermore photocatalysis
Hydrogen manufacturing requires photochemical catalyst to have suitable forbidden bandwidth and conduction band valence band location, H of the photochemical catalyst conduction band bottom than water decomposition+/H2's
Oxidation-reduction potential (0V vs.NHE) is more negative or photochemical catalyst semiconductor top of valence band than water decomposition O2/H2The redox electricity of O
Position (1.23V) corrigendum, the photochemical catalyst with such conduction band valence band location just can be carried out photodestruciton water evolving hydrogen reaction.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art, primary and foremost purpose of the present invention is that providing one kind three aoxidizes
Tungsten/di-iron trioxide composite photo-catalyst.
Another object of the present invention is to provide above-mentioned tungstic acid/di-iron trioxide composite photo-catalyst preparation sides
Method.Simple hydro-thermal-the sintering process of this method, preparation process are simple
A further object of the present invention is to provide the applications of above-mentioned tungstic acid/di-iron trioxide composite photo-catalyst.
The purpose of the present invention is realized by following technical proposals:
A kind of tungstic acid/di-iron trioxide composite photo-catalyst, the tungstic acid/di-iron trioxide complex light are urged
Agent is that ferric trichloride (III) hexahydrate and deionized water ultrasound are prepared ferric trichloride precursor liquid, plate to being completely dissolved
Conductive substrates are placed in pyroreaction kettle and lean to inner wall with 30~60 °, and ferric trichloride precursor liquid is added and did not had plate conductive substrates top,
In 90~140 DEG C of progress hydro-thermal reactions, after washing and nitrogen stream drying, calcines at 500~700 DEG C, led in plate conductive substrates
Electric wheat flour obtains ferric oxide film；It is oblique with 30~60 ° that the di-iron trioxide substrate of above-mentioned acquisition is placed on pyroreaction kettle
By inner wall, tungsten chloride precursor liquid is added, is dried under 100~180 DEG C of progresss hydro-thermal reactions, washed and nitrogen stream, 450~
550 DEG C of sintering are made.Slant setting is in order to avoid forming blocked up photocatalyst film.
Preferably, the concentration of the ferric trichloride precursor liquid is 1~5mmol/L.
Preferably, the tungsten chloride precursor liquid is that tungsten chloride ultrasonic dissolution is made in alcoholic solution.
Preferably, the quality of the tungsten chloride and the volume ratio of alcoholic solution are (0.05~0.3) g:4ml；The alcoholic solution
For methanol, ethyl alcohol or propyl alcohol.
Preferably, the time that hydro-thermal reaction is carried out at 90~140 DEG C is 1-3h.
Preferably, the time that hydro-thermal reaction is carried out at 100~180 DEG C is 8~15h.
Preferably, the time of the calcining is 2~4h；The time of the sintering is 2~4h.
Preferably, the plate conductive substrates are fluorine-doped tin oxide, indium doping tin oxide or tin mixed with zinc oxide.
The tungstic acid/di-iron trioxide composite photo-catalyst preparation method, comprises the following specific steps that:
S1. ferric trichloride (III) hexahydrate and deionized water ultrasound are prepared into ferric trichloride precursor liquid to being completely dissolved；
S2. plate conductive substrates inclination is placed in pyroreaction kettle, and ferric trichloride precursor liquid is added and did not had plate conductive
It after washing and nitrogen stream drying, is calcined at 500~700 DEG C, in 90~140 DEG C of progress hydro-thermal reactions in plate conduction on substrate top
Base conductive wheat flour obtains ferric oxide film；
S3., tungsten chloride ultrasonic dissolution is made to tungsten chloride precursor liquid in methanol solution；
S4. the di-iron trioxide substrate that step S2 is obtained is leaned to and is placed in pyroreaction kettle, tungsten chloride forerunner is added
Liquid, it is dry under 100~180 DEG C of progress hydro-thermal reactions, washed and nitrogen stream, three oxidations are made in 450~550 DEG C of sintering
Tungsten/di-iron trioxide composite photo-catalyst.
The tungstic acid/application of the di-iron trioxide composite photo-catalyst in photocatalysis hydrogen production field.
Tungstic acid of the present invention is a kind of extraordinary metal-oxide semiconductor (MOS) photochemical catalyst of chemical stability, forbidden band
Width is 2.8eV, H of the conduction band positions than water+/H2Oxidation-reduction potential is just, slightly more negative than the conduction band positions of di-iron trioxide, valence
Valence band location with position than di-iron trioxide is corrected.After tungstic acid and di-iron trioxide are compound, on the compound boundary of the two
Heterogeneous section is formed at face, the intrinsic level of di-iron trioxide and the intrinsic level of tungstic acid interact, specifically, interface
Light induced electron be easily transferred to di-iron trioxide conduction band positions from tungstic acid conduction band positions, and photohole is easily from three oxidations two
The valence band location of iron is transferred to the valence band location of tungstic acid, it is suppressed that photo-generated carrier it is compound, while improve photoproduction load
The separation and transfer for flowing son allow more photo-generated carriers to participate in the reaction of photocatalytic cleavage water, further improve compound
The photocatalysis performance of photochemical catalyst.Di-iron trioxide is classical metal-oxide semiconductor (MOS) photochemical catalyst, and forbidden bandwidth is
2.3eV, conduction band positions are higher than the H of water decomposition+/H2Oxidation-reduction potential, valence band location be higher than water decomposition O2/H2The oxygen of O
Change reduction potential, is good optical anode material, di-iron trioxide can respond the visible light of 539nm-380nm wave-length coverage.But
Actual experiment is the results show that its theoretical photoelectric conversion threshold values is much not achieved in di-iron trioxide, because of its high photoproduction current-carrying
Sub- recombination rate, low light induced electron transfer rate, seriously inhibits the photocatalysis performance of di-iron trioxide.It is asked to solve this
Topic, it is compound with tungstic acid to propose di-iron trioxide here, formation hetero-junctions, and then improves its photocatalysis performance.
The present invention is grown one layer of ferric oxide film in plate conductive substrates by the method for simple hydro-thermal-sintering and made
For the supporting substrate of tungsten trioxide photocatalyst.Tungstic acid and di-iron trioxide interface form hetero-junctions, thus three oxidations
The intrinsic level band gap of tungsten and the intrinsic level band gap of di-iron trioxide interact, and the conduction band and valence band location of the two are mutually handed over
Mistake further improves the transmission of photo-generated carrier, inhibits the compound of photo-generate electron-hole pair, widens composite photo-catalyst
Optical response range improves tungstic acid/di-iron trioxide composite photo-catalyst photocatalysis performance.
Compared with prior art, the invention has the following advantages:
1. tungstic acid of the invention/di-iron trioxide composite photo-catalyst is by hydro-thermal-sintering twice in tungstic acid
Hetero-junctions is formed with di-iron trioxide compound interface.
2. tungstic acid and di-iron trioxide of the invention make the intrinsic energy of tungstic acid in the formation of interface hetero-junctions
The intrinsic level of grade and di-iron trioxide interacts, and is conducive to light induced electron from the conduction band positions of tungstic acid and is transferred to three oxygen
The conduction band positions for changing two iron are conducive to the valence band position that photohole is transferred to tungstic acid from the valence band location of di-iron trioxide
It sets, promotes the separation of photo-generated carrier, accelerate the transfer of photo-generated carrier, inhibit the compound of photo-generate electron-hole pair.
3. of the invention go out to form mutual doping at interface, change the lattice arrangement of original photochemical catalyst, generates doping energy
Grade, is further adjusted the forbidden bandwidth of composite photo-catalyst, improves the photocatalysis performance of composite photo-catalyst.
Detailed description of the invention
Fig. 1 is the photoelectric properties I-V diagram that tungstic acid/di-iron trioxide composite photo-catalyst is in embodiment 1.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. ferric chloride hexahydrate is taken to be placed in deionized water, ultrasound is 1mmol/L's to obtained concentration is completely dissolved
Ferric trichloride (III) precursor liquid；
2. clean plate fluorine-doped tin oxide electro-conductive glass inclination is added three by being placed on clean pyroreaction kettle inner wall
Iron chloride (III) precursor liquid, precursor liquid did not had at the top of electro-conductive glass, and was transferred to air dry oven, and hydro-thermal is carried out at 100 DEG C
React 1h.
3. after reaction, repeatedly washing using deionized water, extra hydro-thermal reaction residue is removed, in nitrogen stream phase
Like drying, the sample after drying, which is transferred in Muffle furnace, to be sintered, and sintering temperature is 600 DEG C, sintering time 3h, and heating rate is
5 DEG C/min, rate of temperature fall is 10 DEG C/min, obtains after sintering and is grown in plate fluorine-doped tin oxide electro-conductive glass conducting surface
On ferric oxide film, and the supporting substrate as loaded tungsten trioxide metal-oxide semiconductor (MOS) photochemical catalyst.
4. 0.1g tungsten chloride is taken to be dissolved in the methanol solution of 20ml, ultrasound prepares tungsten chloride precursor liquid to being completely dissolved.
5. by the di-iron trioxide supporting substrate inclination of acquisition by being placed in pyroreaction kettle, addition tungsten chloride precursor liquid,
And be transferred to air dry oven and carry out hydro-thermal reaction, hydrothermal temperature is 100 DEG C, and the hydro-thermal time is 12h, after hydro-thermal, is used
Methanol solution is washed, and extra hydro-thermal reaction residue is removed, and Muffle furnace sintering is transferred to after drying under nitrogen flowing, is burnt
Junction temperature is 470 DEG C, sintering time 3h, and heating rate is 5 DEG C/min, is air-cooled to room temperature, and three oxidations are obtained after sintering
Tungsten/di-iron trioxide composite photo-catalyst is labeled as WO3/Fe2O3@p-FTO。
Comparative example 1
1. ferric chloride hexahydrate is taken to be placed in deionized water, ultrasound is 1mmol/L's to obtained concentration is completely dissolved
Ferric trichloride (III) precursor liquid；
2. clean plate fluorine-doped tin oxide electro-conductive glass inclination is added three by being placed on clean pyroreaction kettle inner wall
Iron chloride (III) precursor liquid, precursor liquid did not had at the top of electro-conductive glass, and was transferred to air dry oven, and hydro-thermal is carried out at 100 DEG C
React 1h.
3. after reaction, repeatedly washing using deionized water, extra hydro-thermal reaction residue is removed, in nitrogen stream phase
Like drying, the sample after drying, which is transferred in Muffle furnace, to be sintered, and sintering temperature is 600 DEG C, sintering time 3h, and heating rate is
5 DEG C/min, rate of temperature fall is 10 DEG C/min, obtains after sintering and is grown in plate fluorine-doped tin oxide electro-conductive glass conducting surface
On ferric oxide film, be labeled as and as Fe2O3@p-FTO。
Comparative example 2
1. 0.1g tungsten chloride is taken to be dissolved in the methanol solution of 20ml, ultrasound prepares tungsten chloride precursor liquid to being completely dissolved.
2. tungsten chloride forerunner is added by being placed in pyroreaction kettle in clean fluorine-doped tin oxide conductive substrates inclination
Liquid, and be transferred to air dry oven and carry out hydro-thermal reaction, hydrothermal temperature is 100 DEG C, and the hydro-thermal time is 12h, after hydro-thermal, is made
It is washed with methanol solution, removes extra hydro-thermal reaction residue, Muffle furnace sintering is transferred to after drying under nitrogen flowing,
Sintering temperature is 470 DEG C, sintering time 3h, and heating rate is 5 DEG C/min, is air-cooled to room temperature, three oxygen are obtained after sintering
Change tungsten photochemical catalyst, is labeled as WO3@p-FTO。
Three oxygen in tungstic acid/di-iron trioxide composite photo-catalyst, comparative example 1 in the embodiment 1 of above-mentioned preparation
The tungsten trioxide photocatalyst changed in two iron photochemical catalysts and comparative example 2 carries out evolving hydrogen reaction under the conditions of simulated solar irradiation, instead
Answering electrolyte is the metabisulfite solution of 0.1M.
Fig. 1 is tungstic acid/di-iron trioxide composite photo-catalyst of the preparation of embodiment 1 in simulated solar illumination condition
Under, the I-V diagram tested using standard three electrode electrochemical workstation, wherein electrolyte is the metabisulfite solution of 0.1M, from Fig. 1
It can be seen that tungstic acid/di-iron trioxide composite photo-catalyst (WO3/Fe2O3@p-FTO) than three oxidation made from comparative example 1
Two iron photochemical catalyst (Fe2O3@p-FTO) and comparative example 2 made from tungsten trioxide photocatalyst (WO3@p-FTO) with higher
Photocatalysis performance, its density of photocurrent is equal to 0.15mA/cm under conditions of not being biased (0V)2., it is 1V's in bias
When, density of photocurrent 1.2mA/cm2。
Embodiment 2
1. ferric chloride hexahydrate is taken to be placed in deionized water, ultrasound is 5mmol/L's to obtained concentration is completely dissolved
Ferric trichloride (III) precursor liquid；
2. clean plate fluorine-doped tin oxide electro-conductive glass inclination is added three by being placed on clean pyroreaction kettle inner wall
Iron chloride (III) precursor liquid, precursor liquid did not had at the top of electro-conductive glass, and was transferred to air dry oven, and hydro-thermal is carried out at 140 DEG C
React 2h.
3. after reaction, repeatedly washing using deionized water, extra hydro-thermal reaction residue is removed, in nitrogen stream phase
Like drying, the sample after drying, which is transferred in Muffle furnace, to be sintered, and sintering temperature is 700 DEG C, sintering time 2h, and heating rate is
5 DEG C/min, rate of temperature fall is 10 DEG C/min, obtains after sintering and is grown in plate fluorine-doped tin oxide electro-conductive glass conducting surface
On ferric oxide film, and the supporting substrate as loaded tungsten trioxide metal-oxide semiconductor (MOS) photochemical catalyst.
4. 1.5g tungsten chloride is taken to be dissolved in the ethanol solution of 20ml, ultrasound prepares tungsten chloride precursor liquid to being completely dissolved.
5. by the di-iron trioxide supporting substrate inclination of acquisition by being placed in pyroreaction kettle, addition tungsten chloride precursor liquid,
And be transferred to air dry oven and carry out hydro-thermal reaction, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 8h, after hydro-thermal, uses first
Alcoholic solution is washed, and extra hydro-thermal reaction residue is removed, and Muffle furnace sintering, sintering are transferred to after drying under nitrogen flowing
550 DEG C of temperature, sintering time 2h, heating rate is 5 DEG C/min, is air-cooled to room temperature, and tungstic acid/tri- are obtained after sintering
Two iron composite photo-catalysts are aoxidized, WO is labeled as3/Fe2O3@p-FTO2。
Embodiment 3
1. ferric chloride hexahydrate is taken to be placed in deionized water, ultrasound is 2mmol/L's to obtained concentration is completely dissolved
Ferric trichloride (III) precursor liquid；
2. trichlorine is added by being placed on clean pyroreaction kettle inner wall in net plate fluorine-doped tin oxide electro-conductive glass inclination
Change iron (III) precursor liquid, precursor liquid did not had at the top of electro-conductive glass, and was transferred to air dry oven, and it is anti-that hydro-thermal is carried out at 90 DEG C
Answer 3h.
3. after reaction, repeatedly washing using deionized water, extra hydro-thermal reaction residue is removed, in nitrogen stream phase
Like drying, the sample after drying, which is transferred in Muffle furnace, to be sintered, and sintering temperature is 600 DEG C, sintering time 3h, and heating rate is
5 DEG C/min, rate of temperature fall is 10 DEG C/min, obtains after sintering and is grown in plate fluorine-doped tin oxide electro-conductive glass conducting surface
On ferric oxide film, and the supporting substrate as loaded tungsten trioxide metal-oxide semiconductor (MOS) photochemical catalyst.
4. 0.5g tungsten chloride is taken to be dissolved in the propanol solution of 20ml, ultrasound prepares tungsten chloride precursor liquid to being completely dissolved.
5. by the di-iron trioxide supporting substrate inclination of acquisition by being placed in pyroreaction kettle, addition tungsten chloride precursor liquid,
And be transferred to air dry oven and carry out hydro-thermal reaction, hydrothermal temperature is 100 DEG C, and the hydro-thermal time is 12h, after hydro-thermal, is used
Methanol solution is washed, and extra hydro-thermal reaction residue is removed, and Muffle furnace sintering is transferred to after drying under nitrogen flowing, is burnt
Junction temperature is 450 DEG C, sintering time 4h, and heating rate is 5 DEG C/min, is air-cooled to room temperature, and three oxidations are obtained after sintering
Tungsten/di-iron trioxide composite photo-catalyst is labeled as WO3/Fe2O3@p-FTO3。
Embodiment 4
The present embodiment the difference from embodiment 1 is that, take 0.1g methanol tungsten salt to be dissolved in 20ml methanol, ultrasound is to completely molten
Methanol tungsten precursor liquid is made in solution, replaces the tungsten chloride precursor liquid in embodiment 1, carries out hydro-thermal reaction.
Embodiment 5
The present embodiment the difference from embodiment 1 is that, ferric trichloride (III) Concentration of precursor solution of preparation is in 1mmol/L-
In the range of 5mmol/L, by the progressive concentration of 1mmol/L, ferric trichloride (III) precursor liquid of various concentration is prepared.
Embodiment 6
The present embodiment the difference from embodiment 1 is that, grow three on plate fluorine-doped tin oxide electro-conductive glass conducting surface
Two iron thin film processes are aoxidized, hydrothermal temperature, with 10 DEG C of temperature increment amount, prepares different hydro-thermals within the scope of 90 DEG C -140 DEG C
At a temperature of sample.
Embodiment 7
The present embodiment the difference from embodiment 1 is that, prepare in the water-heat process of ferric oxide film, the hydro-thermal time exists
In the time range of 1h-3h, with the time incremental change of 1h, the sample of different hydro-thermal times is prepared.
Embodiment 8
The present embodiment the difference from embodiment 1 is that, prepare the sintering process of ferric oxide film, sintering temperature exists
In 500 DEG C of -700 DEG C of temperature ranges, with 50 DEG C of temperature increment amount, the sample under different sintering temperatures is prepared.
Embodiment 9
The present embodiment the difference from embodiment 1 is that, prepare tungsten chloride precursor liquid, wherein the quality of tungsten chloride and methanol are molten
The ratio between volume of liquid is (0.05-1.5) g:20ml, and ultrasound is to being completely dissolved.
Embodiment 10
The present embodiment the difference from embodiment 1 is that, in tungstic acid water-heat process, hydrothermal temperature is at 100 DEG C -180 DEG C
In temperature range, with 20 DEG C for incremental change, the tungstic acid sample under different hydrothermal temperatures is prepared.
Embodiment 11
The present embodiment the difference from embodiment 1 is that, sintering time is incremental with 30min in the range of 1.5h-4h
Amount, obtains the sample of different soaking times.
Embodiment 12
The present embodiment the difference from embodiment 1 is that, in tungstic acid water-heat process, the hydro-thermal reaction time is 8h-15h's
In time range, with the incremental change of 1h, the tungstic acid sample of different hydro-thermal times is obtained.
Embodiment 13
The present embodiment the difference from embodiment 1 is that, in tungstic acid sintering process, sintering temperature is at 450 DEG C -550 DEG C
In temperature range, with 50 DEG C for incremental change, tungstic acid/di-iron trioxide composite photocatalyst under different sintering temperatures is obtained
Agent.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of tungstic acid/di-iron trioxide composite photo-catalyst, which is characterized in that the tungstic acid/tri- oxidations two
Iron composite photo-catalyst be by ferric trichloride (III) hexahydrate and deionized water ultrasound to before being completely dissolved and prepare ferric trichloride
Liquid is driven, plate conductive substrates are placed in pyroreaction kettle and lean to inner wall with 30~60 °, ferric trichloride precursor liquid is added and there was not plate to lead
It after washing and nitrogen stream drying, calcines at 500~700 DEG C, is led in plate in 90~140 DEG C of progress hydro-thermal reactions in electric substrate top
Electric base conductive wheat flour obtains ferric oxide film；The di-iron trioxide substrate of above-mentioned acquisition is placed on pyroreaction kettle with 30
~60 ° lean to inner wall, and tungsten chloride precursor liquid is added, dry under 100~180 DEG C of progress hydro-thermal reactions, washed and nitrogen stream,
It is made in 450~550 DEG C of sintering.
2. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that the trichlorine
The concentration for changing iron precursor liquid is 1~5mmol/L.
3. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that the chlorination
Tungsten precursor liquid is that tungsten chloride ultrasonic dissolution is made in alcoholic solution.
4. tungstic acid according to claim 3/di-iron trioxide composite photo-catalyst, which is characterized in that the chlorination
The quality of tungsten and the volume ratio of alcoholic solution are (0.05~0.3) g:4ml；The alcoholic solution is methanol, ethyl alcohol or propyl alcohol.
5. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that it is described
The time of 90~140 DEG C of progress hydro-thermal reactions is 1-3h.
6. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that it is described
The time of 100~180 DEG C of progress hydro-thermal reactions is 8~15h.
7. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that the calcining
Time be 2~4h；The time of the sintering is 2~4h.
8. tungstic acid according to claim 1/di-iron trioxide composite photo-catalyst, which is characterized in that the plate
Conductive substrates are fluorine-doped tin oxide, indium doping tin oxide or tin mixed with zinc oxide.
9. tungstic acid according to claim 1-8/di-iron trioxide composite photo-catalyst preparation method,
It is characterized in that, comprises the following specific steps that:
S1. ferric trichloride (III) hexahydrate and deionized water ultrasound are prepared into ferric trichloride precursor liquid to being completely dissolved；
S2. plate conductive substrates inclination is placed in pyroreaction kettle, and ferric trichloride precursor liquid is added and did not had plate conductive substrates
It after washing and nitrogen stream drying, is calcined at 500~700 DEG C, in plate conductive substrates in 90~140 DEG C of progress hydro-thermal reactions on top
Ferric oxide film is made in conducting surface；
S3., tungsten chloride ultrasonic dissolution is made to tungsten chloride precursor liquid in methanol solution；
S4. the di-iron trioxide substrate that step S2 is obtained is leaned to and is placed in pyroreaction kettle, tungsten chloride precursor liquid is added,
100~180 DEG C of progress hydro-thermal reactions, it is washed to be dried under nitrogen stream, it is sintered at 450~550 DEG C and tungstic acid/tri- oxygen is made
Change two iron composite photo-catalysts.
10. the described in any item tungstic acids of claim 1-8/di-iron trioxide composite photo-catalyst is in photocatalysis hydrogen production field
In application.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981213A (en) * | 2019-12-18 | 2020-04-10 | 济南大学 | Preparation method of crossed plate-shaped tungsten trioxide-ferric oxide composite material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2647430A1 (en) * | 2012-04-05 | 2013-10-09 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof |
| US20140054442A1 (en) * | 2012-07-20 | 2014-02-27 | Board Of Regents Of The University Of Nebraska | Nanocomposite Photodetector |
| WO2017019146A1 (en) * | 2015-07-29 | 2017-02-02 | Regents Of The University Of California The | Z-scheme microbial photoelectrochemical system (mps) for wastewater-to-chemical fuel conversion |
| CN106512985A (en) * | 2016-09-20 | 2017-03-22 | 河南师范大学 | Synthetic method of ZnO/WO3 heterojunction arrays |
| CN106881078A (en) * | 2017-01-22 | 2017-06-23 | 天津大学 | Z-type junction ZnO-WO3Electrode, preparation method thereof and application thereof in photoelectrocatalysis |
| CN108465465A (en) * | 2018-04-04 | 2018-08-31 | 广东工业大学 | A kind of semiconductive thin film and preparation method thereof |
| CN109746001A (en) * | 2018-12-13 | 2019-05-14 | 广东工业大学 | A kind of tin oxide photonic crystal load tungsten oxide and vulcanization silver composite membrane and its preparation method and application |
-
2019
- 2019-06-28 CN CN201910577165.8A patent/CN110354863A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2647430A1 (en) * | 2012-04-05 | 2013-10-09 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof |
| US20140054442A1 (en) * | 2012-07-20 | 2014-02-27 | Board Of Regents Of The University Of Nebraska | Nanocomposite Photodetector |
| WO2017019146A1 (en) * | 2015-07-29 | 2017-02-02 | Regents Of The University Of California The | Z-scheme microbial photoelectrochemical system (mps) for wastewater-to-chemical fuel conversion |
| CN106512985A (en) * | 2016-09-20 | 2017-03-22 | 河南师范大学 | Synthetic method of ZnO/WO3 heterojunction arrays |
| CN106881078A (en) * | 2017-01-22 | 2017-06-23 | 天津大学 | Z-type junction ZnO-WO3Electrode, preparation method thereof and application thereof in photoelectrocatalysis |
| CN108465465A (en) * | 2018-04-04 | 2018-08-31 | 广东工业大学 | A kind of semiconductive thin film and preparation method thereof |
| CN109746001A (en) * | 2018-12-13 | 2019-05-14 | 广东工业大学 | A kind of tin oxide photonic crystal load tungsten oxide and vulcanization silver composite membrane and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| SHOULI BAI ET AL.: "An Integrating Photoanode of WO3/Fe2O3 Heterojunction Decorated with NiFe-LDH to Improve PEC Water Splitting Efficiency", 《ACS SUSTAINABLE CHEMISTRY ENGINEERING》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981213A (en) * | 2019-12-18 | 2020-04-10 | 济南大学 | Preparation method of crossed plate-shaped tungsten trioxide-ferric oxide composite material |
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