CN110465286A - A kind of bismuth tungstate photocatalyst and its preparation method and application of Surface Oxygen vacancy defect modification - Google Patents
A kind of bismuth tungstate photocatalyst and its preparation method and application of Surface Oxygen vacancy defect modification Download PDFInfo
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- CN110465286A CN110465286A CN201910543986.XA CN201910543986A CN110465286A CN 110465286 A CN110465286 A CN 110465286A CN 201910543986 A CN201910543986 A CN 201910543986A CN 110465286 A CN110465286 A CN 110465286A
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- bismuth
- precursor liquid
- bismuth tungstate
- oxygen vacancy
- tungstate
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 89
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 89
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000001301 oxygen Substances 0.000 title claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 54
- 230000007547 defect Effects 0.000 title claims abstract description 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 230000004048 modification Effects 0.000 title claims abstract description 39
- 238000012986 modification Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002604 ultrasonography Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000010408 film Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 10
- 238000003776 cleavage reaction Methods 0.000 description 5
- 230000007017 scission Effects 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- 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
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/39—
-
- B01J35/59—
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
Abstract
The invention belongs to photocatalysis technology field, bismuth tungstate photocatalyst and its preparation and the application of a kind of Surface Oxygen vacancy defect modification are disclosed.The bismuth tungstate photocatalyst of the Surface Oxygen vacancy defect modification is that sodium tungstate precursor liquid and bismuth nitrate precursor liquid are mixed into bismuth tungstate precursor liquid, ultrasound is simultaneously transferred in the pyroreaction kettle for being placed with conductive substrates, in 100~180 DEG C of progress hydro-thermal reactions, it is cleaned with deionized water, it is dry under nitrogen stream, then 450~600 DEG C be sintered, will be grown on the bismuth tungstate film in plate conductive substrates under reproducibility atmosphere 150~400 DEG C carry out heat treatment be made.Surface Oxygen vacancy defect bismuth tungstate film surface of the invention has more active sites, obtain better photoelectric conversion efficiency, simultaneously Lacking oxygen defect presence can the forbidden bandwidth Eg to bismuth tungstate photocatalyst be finely adjusted, so that Eg is narrowed, to obtain broader visible light-responded range.
Description
Technical field
The invention belongs to photocatalysis hydrogen production technical fields, more particularly, to a kind of tungsten of Surface Oxygen vacancy defect modification
Sour bismuth photochemical catalyst and its preparation method and application.
Background technique
With the rapid development of society with the excessive development and utilization of fossil energy, global fossil energy storage capacity is that have
Limit, if can not find the alternative energy source of cheap rich reserves, then energy shortage problem will be that every country will face
Social concern.Hydrogen Energy is the energy of clean and environmental protection the most known today, and the final product water that it burns does not form environment
Secondary pollution.Photocatalytic cleavage water is hydrogen and oxygen is the most ideal strategy of hydrogen manufacturing, is low energy consumption, photocatalytic cleavage water first
What is utilized is solar energy, can be able to be inexhaustible again very much；Followed by abundant raw materials, photocatalytic cleavage water
Raw material be water, water is the substance that content is most on the earth；Last Hydrogen Energy final product is also water, without secondary pollution, and can
It recycles.
The photocatalytic cleavage water most important condition is to find suitable photochemical catalyst, the catalysis material of suitable photocatalytic cleavage water
Prerequisite condition is: it can be responded with suitable bandwidth, with suitable valence band and conduction band positions, in visible region,
The features such as chemical stability is good.Bismuth tungstate is that a kind of more satisfactory typical semiconductor material light urges agent, its forbidden bandwidth is
2.7eV-2.8eV can respond most of visible light, simultaneously because it can be used for light and urge with suitable valence band and conduction band positions
Change water-splitting hydrogen production, while also there is the raw electron-hole rate of departure of high light.The bismuth tungstate of crystalline state is often in the form of big crystal grain
In the presence of with longer photo-generated carrier transfer distance, this also results in bismuth tungstate, and there are high photo-generate electron-holes to compound
Rate.In addition, the bismuth tungstate of bulky grain crystalline form often exists in the form of sheet stacks, there is small surface area and specific surface area,
Also result in that its exposure is few with the photocatalytic activity site on surface, this will be highly detrimental to the progress of light-catalyzed reaction simultaneously.
For properties of catalyst improve method have very much, including adulterate, formed heterogeneous section, noble metal granule modify,
Surface topography regulation etc..The light absorption of catalysis material, absorption, photo-generated carrier transmits and the physics such as transfer, photocatalytic activity
Chemical property has close contact with photocatalyst surface defect.In addition, light-catalyzed reaction takes place mostly in photochemical catalyst table
At the active site in face, a kind of common regulation method for forming defect in photocatalyst surface is doping.Used here as difference
It is deprived by force in a certain temperature conditions in traditional atom doped hydrogen heat treating process using the hydrogen with reproducibility
The oxygen atom on bismuth tungstate surface increases bismuth tungstate surface to reach to form Lacking oxygen defect on bismuth tungstate film surface
The purpose of active site.Its key reaction principle is Bi2WO6+H2→Bi2WO6-X+xH2O.With the increase of oxygen vacancy concentration, shape
Lacking oxygen doping is formed on bismuth tungstate film surface, while being deprived of due to oxygen atom at Lacking oxygen, it is electric around Lacking oxygen
Son redistribution, and an intermediate level is formed, the original energy level of bismuth tungstate is adjusted, while Lacking oxygen defect is in wolframic acid
More active sites that bismuth thin film surface is formed, the further photocatalysis performance for improving bismuth tungstate, to obtain higher light
Catalytic performance.This hydrogen heat-treating methods simple process is applicable to most of metal-oxide semiconductor (MOS) photochemical catalyst, is
A kind of ideal photocatalysis modification technology, application prospect are very extensive.
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 to provide a kind of Surface Oxygen
The bismuth tungstate photocatalyst of vacancy defect modification.
Another object of the present invention is to provide the preparations of the bismuth tungstate photocatalyst of above-mentioned Surface Oxygen vacancy defect modification
Method.
A further object of the present invention is to provide the applications of the bismuth tungstate photocatalyst of above-mentioned Surface Oxygen vacancy defect modification.
The purpose of the present invention is realized by following technical proposals:
A kind of bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification, the wolframic acid of the Surface Oxygen vacancy defect modification
Bismuth photochemical catalyst is that sodium tungstate precursor liquid and bismuth nitrate precursor liquid are mixed into bismuth tungstate precursor liquid, and ultrasound is simultaneously transferred to and is placed with
In the pyroreaction kettle of conductive substrates, in 100~180 DEG C of progress hydro-thermal reactions, cleaned with deionized water, it is dry under nitrogen stream,
Then it is sintered at 450~600 DEG C, the bismuth tungstate film in plate conductive substrates will be grown on 150~400 under reproducibility atmosphere
It DEG C carries out heat treatment to be made, wherein the atmosphere of the reproducibility is hydrogen, hydrogen-argon-mixed body, hydrogen-nitrogen mixture gas or an oxygen
Change carbon.
Preferably, the sodium tungstate precursor liquid is that sodium tungstate dihydrate is dissolved in deionized water preparation；Described
Bismuth nitrate precursor liquid is that bismuth nitrate pentahapto object is dissolved in dust technology, adjusts pH value=3~6, and ultrasound to clarification is prepared.
It is further preferable that the molar ratio of the sodium tungstate dihydrate and bismuth nitrate pentahydrate is (0.8~1.2): 1.
It is further preferable that the amount of the substance of the sodium tungstate dihydrate and the volume ratio of deionized water are (0.2~1)
Mmol:7.5ml；The amount of the substance of the bismuth nitrate pentahydrate and the volume ratio of dust technology are (0.2~1) mmol:7.5ml.
Preferably, the volume ratio (0.8~1.2) of the sodium tungstate precursor liquid and bismuth nitrate precursor liquid: 1.
Preferably, the time of the ultrasound is 30~60min.
Preferably, the conductive substrates are that FTO electro-conductive glass, fluorine-doped tin oxide, tin-doped indium oxide or flexibility are led
Electric band.
Preferably, the time of the hydro-thermal reaction is 1~8h；The time of the sintering be 2~6h, the heat treatment when
Between be 0.5~4h.
The preparation method of the bismuth tungstate photocatalyst of the Surface Oxygen vacancy defect modification, comprises the following specific steps that:
S1. sodium tungstate dihydrate is dissolved in deionized water and prepares sodium tungstate precursor liquid；Bismuth nitrate pentahapto object is dissolved
In dust technology, pH value=3~6 are adjusted, ultrasound to clarification prepares bismuth nitrate precursor liquid；
S2. sodium tungstate precursor liquid and bismuth nitrate precursor liquid are mixed into bismuth tungstate precursor liquid, ultrasound and being transferred to is placed with
In the pyroreaction kettle of conductive substrates, in 100~180 DEG C of progress hydro-thermal reactions, cleaned with deionized water, it is dry under nitrogen stream；
S3. it is then sintered at 450~600 DEG C, the bismuth tungstate film in plate conductive substrates will be grown in reproducibility atmosphere
It encloses lower 150~400 DEG C to be heat-treated, the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification is made.
The bismuth tungstate photocatalyst of the Surface Oxygen vacancy defect modification is in photocatalysis hydrogen production, the organic dirt of photochemical catalytic oxidation
Contaminate the application in object field.
The present invention is compared by the Surface Oxygen vacancy defect bismuth tungstate photocatalyst that hydrogen heat treatment obtains and is made under equal conditions
Standby pure bismuth tungstate photocatalyst, Surface Oxygen vacancy defect bismuth tungstate film surface have more active sites, obtain more preferable
Photoelectric conversion efficiency, while the presence of Lacking oxygen defect can the forbidden bandwidth Eg to bismuth tungstate photocatalyst be finely adjusted, make
Eg narrows, to obtain broader visible light-responded range.
Compared with prior art, the invention has the following advantages:
1. the preparation process that hydrogen heat treatment of the invention obtains Surface Oxygen vacancy defect is simple, while being suitable for other similar
Metal-oxide semiconductor (MOS) photochemical catalyst property modification research.
It is reproducibility hydrogen 2. the present invention is heat-treated the bismuth tungstate photocatalyst for obtaining the modification of Surface Oxygen vacancy defect by hydrogen
The oxygen atom on bismuth tungstate film surface is deprived by force, to form Lacking oxygen defect, certain density Lacking oxygen is to bismuth tungstate light
Catalyst surface is doped, the energy level of adjustable section section bismuth tungstate, and then enhances the visible absorption of bismuth tungstate light photochemical catalyst
Ability widens its visible light-responded range.
3. the present invention when Surface Oxygen vacancy defect reaches a certain concentration, can on the basis of ortho-tungstic acid bismuth energy level formative
Energy level, to reach the adjusting to ortho-tungstic acid bismuth energy level.Surface vacancy defect forms active site on bismuth tungstate film surface,
To increase the amount of the active site on the surface of bismuth tungstate photocatalyst, and then improve photocatalysis performance.
Detailed description of the invention
Fig. 1 is the bismuth tungstate photocatalyst and comparative example 1 that hydrogen heat treatment obtains the modification of Surface Oxygen vacancy defect in embodiment 1
In do not have under condition of equivalent carry out hydrogen heat treatment preparation pure bismuth tungstate photocatalyst photoelectric conversion performance comparison diagram.
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.
Hydrogen-argon-mixed body used in the embodiment of the present invention, standard stuffing pressure are 10.0Mpa, and density of hydrogen is
3.98%.
Embodiment 1
1. 1mmol sodium tungstate dihydrate is taken to be dissolved in the deionized water of 7.5ml；Take 1mmol bismuth nitrate pentahydrate
It dissolves in dilute nitric acid solution of the pH value equal to 5 of 7.5ml；Both ultrasound obtains sodium tungstate precursor liquid and nitre to clarifying respectively
Sour bismuth precursor liquid.
2. clean plate FTO electro-conductive glass tilts bismuth nitrate precursor liquid and tungsten in the pyroreaction kettle for being placed on 25ml
Sour sodium precursor liquid mixing obtains the bismuth tungstate precursor liquid of milky turbid state, and is transferred in pyroreaction kettle at once.In
Hydro-thermal reaction 3h under the conditions of 100 DEG C rinses sample using deionized water after reaction, removes extra reaction residue, In
It is dry under condition of nitrogen gas, it is then transferred to Muffle furnace and crystallization is dried, it is thin that bismuth tungstate is grown on plate FTO electro-conductive glass
Film.
3. bismuth tungstate film keeps the temperature 2h in Muffle furnace under the conditions of 500 DEG C, heating rate is 5 DEG C/min.After sintering
Sample be transferred in tube furnace, using hydrogen-argon-mixed body be reaction gas.First with air volume ventilation 20min, then with small
Throughput ventilation 30min, is rapidly heated to 200 DEG C, and keep the temperature 2h with the heating-up time of 10min, Surface Oxygen vacancy defect is made
The bismuth tungstate photocatalyst of modification.
The bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification obtained carries out photocatalysis under the conditions of simulated solar irradiation
Splitting water reaction, the metabisulfite solution that reaction electrolyte is 0.1M.
Comparative example 1
1. 1mmol sodium tungstate dihydrate is taken to be dissolved in the deionized water of 7.5ml；Take 1mmol bismuth nitrate pentahydrate
It dissolves in dilute nitric acid solution of the pH value equal to 5 of 7.5ml；Both ultrasound obtains sodium tungstate precursor liquid and nitre to clarifying respectively
Sour bismuth precursor liquid.
2. clean plate FTO electro-conductive glass tilts bismuth nitrate precursor liquid and tungsten in the pyroreaction kettle for being placed on 25ml
Sour sodium precursor liquid mixing obtains the bismuth tungstate precursor liquid of milky turbid state, and is transferred in pyroreaction kettle at once.In
Hydro-thermal reaction 3h under the conditions of 100 DEG C rinses sample using deionized water after reaction, removes extra reaction residue, In
It is dry under condition of nitrogen gas, it is then transferred to Muffle furnace and crystallization is dried, it is thin that bismuth tungstate is grown on plate FTO electro-conductive glass
Film.
3. bismuth tungstate film keeps the temperature 2h in Muffle furnace under the conditions of 500 DEG C, heating rate is 5 DEG C/min.After sintering
Sample be transferred in tube furnace, using air be reaction gas.It is rapidly heated with the heating-up time of 10min to 200 DEG C, and protected
The bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification is made in warm 2h.
The bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification obtained carries out photocatalysis under the conditions of simulated solar irradiation
Splitting water reaction, the metabisulfite solution that reaction electrolyte is 0.1M.
Fig. 1 is that hydrogen heat treatment obtains surface oxygen defect modification bismuth tungstate photocatalyst in embodiment 1 and comparative example 1 is waiting
Not by the bismuth tungstate photocatalyst (Bi of hydrogen heat treatment preparation under the conditions of2WO6@P-FTO, wherein P-FTO indicates plate
FTO electro-conductive glass) under dark (block curve in Fig. 1) and illumination condition (dashed curve in Fig. 1) photoelectric conversion performance pair
Than figure.Wherein, in Fig. 1 uppermost line curve be at 200 DEG C hydrogen heat treatment 2h sample (illumination), intermediate curve is that do not have
The sample (illumination) for having hydrogen to be heat-treated, most beneath curve are the samples (no light, i.e., dark) of no hydrogen heat treatment.From figure
In 1 it is found that compared to the pure bismuth tungstate photocatalyst prepared under condition of equivalent, hydrogen heat treatment obtains the modification of Surface Oxygen vacancy defect
Bismuth tungstate photocatalyst has higher density of photocurrent.
Embodiment 2
1. 0.5mmol sodium tungstate dihydrate is taken to be dissolved in the deionized water of 7.5ml；Take five water of 0.2mmol bismuth nitrate
In dilute nitric acid solution of the pH value equal to 6 for closing object dissolution 7.5ml；Both ultrasound obtains sodium tungstate precursor liquid to clarifying respectively
With bismuth nitrate precursor liquid.
2. clean plate fluorine-doped tin oxide tilts bismuth nitrate precursor liquid and tungsten in the pyroreaction kettle for being placed on 25ml
Sour sodium precursor liquid mixing obtains the bismuth tungstate precursor liquid of milky turbid state, and is transferred in pyroreaction kettle at once.In
Hydro-thermal reaction 3h under the conditions of 150 DEG C rinses sample using deionized water after reaction, removes extra reaction residue, In
It is dry under condition of nitrogen gas, it is then transferred to Muffle furnace and crystallization is dried, it is thin that bismuth tungstate is grown on plate FTO electro-conductive glass
Film.
3. bismuth tungstate film keeps the temperature 2h in Muffle furnace under the conditions of 600 DEG C, heating rate is 5 DEG C/min.After sintering
Sample be transferred in tube furnace, using hydrogen be reaction gas.Elder generation leads to air volume ventilation 20min, then with stingy flow
Gas 60min is rapidly heated to 300 DEG C with the heating-up time of 10min, and keeps the temperature 2h, and the tungsten of Surface Oxygen vacancy defect modification is made
Sour bismuth photochemical catalyst.
The bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification obtained carries out photocatalysis under the conditions of simulated solar irradiation
Splitting water reaction, the metabisulfite solution that reaction electrolyte is 0.1M.
Embodiment 3
1. 0.3mmol sodium tungstate dihydrate is taken to be dissolved in the deionized water of 7.5ml；Take five water of 0.2mmol bismuth nitrate
In dilute nitric acid solution of the pH value equal to 3 for closing object dissolution 7.5ml；Both ultrasound obtains sodium tungstate precursor liquid to clarifying respectively
With bismuth nitrate precursor liquid.
2. clean plate fluorine-doped tin oxide tilts bismuth nitrate precursor liquid and tungsten in the pyroreaction kettle for being placed on 25ml
Sour sodium precursor liquid mixing obtains the bismuth tungstate precursor liquid of milky turbid state, and is transferred in pyroreaction kettle at once.In
Hydro-thermal reaction 3h under the conditions of 180 DEG C rinses sample using deionized water after reaction, removes extra reaction residue, In
It is dry under condition of nitrogen gas, it is then transferred to Muffle furnace and crystallization is dried, it is thin that bismuth tungstate is grown on plate FTO electro-conductive glass
Film.
3. bismuth tungstate film keeps the temperature 2h in Muffle furnace under the conditions of 450 DEG C, heating rate is 5 DEG C/min.After sintering
Sample be transferred in tube furnace, using hydrogen-nitrogen mixture gas be reaction gas.First with air volume ventilation 20min, then with small
Throughput ventilation 60min, is rapidly heated to 400 DEG C, and keep the temperature 2h with the heating-up time of 10min, Surface Oxygen vacancy defect is made
The bismuth tungstate photocatalyst of modification.
The bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification obtained carries out photocatalysis under the conditions of simulated solar irradiation
Splitting water reaction, the metabisulfite solution that reaction electrolyte is 0.1M.
Embodiment 4
The present embodiment the difference from embodiment 1 is that, sodium tungstate dihydrate and bismuth nitrate pentahydrate 1:1 in molar ratio
Ratio, sodium tungstate precursor liquid and bismuth nitrate precursor liquid are respectively configured with the incremental gradient of 0.2mmol, initial taken amount is
0.2mmol。
Embodiment 5
The present embodiment the difference from embodiment 1 is that, hydrothermal temperature in the range of 100 DEG C -180 DEG C by 20 DEG C be incremented by
Gradient hydro-thermal, initial temperature are 100 DEG C.
Embodiment 6
The present embodiment the difference from embodiment 1 is that, sintering temperature in the range of 450 DEG C -600 DEG C by 50 DEG C be incremented by
Gradient sintering, initial temperature are 450 DEG C.
Embodiment 7
The present embodiment the difference from embodiment 1 is that, the sintered heat insulating time in the range of 2h-6h press 0.5h incremental ladder
Degree sintering, initial parameter 2h.
Embodiment 8
The present embodiment the difference from embodiment 1 is that, sample is heat-treated in hydrogen-argon-mixed body atmosphere, heat treatment temperature
It is heat-treated in the range of 150 DEG C -400 DEG C by 50 DEG C of incremental gradient, initial parameter is 150 DEG C.
Embodiment 9
The present embodiment the difference from embodiment 1 is that, hydrogen heat treatment time in the range of 30min-4h press 30min
Incremental gradient heat treatment, initial parameter 30min.
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 bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification, which is characterized in that the Surface Oxygen vacancy defect
The bismuth tungstate photocatalyst of modification is that sodium tungstate precursor liquid and bismuth nitrate precursor liquid are mixed into bismuth tungstate precursor liquid, and ultrasound simultaneously turns
It moves to and is placed in the pyroreaction kettle of conductive substrates, in 100~180 DEG C of progress hydro-thermal reactions, cleaned with deionized water, nitrogen
Drying is flowed down, is then sintered at 450~600 DEG C, the bismuth tungstate film in plate conductive substrates will be grown in reducibility gas
Under atmosphere 150~400 DEG C carry out heat treatment be made, wherein the gas of the reproducibility be hydrogen, hydrogen-argon-mixed body, hydrogen nitrogen
Mixed gas or carbon monoxide.
2. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1, which is characterized in that described
Sodium tungstate precursor liquid is that sodium tungstate dihydrate is dissolved in deionized water preparation；The bismuth nitrate precursor liquid is by bismuth nitrate
Pentahapto object is dissolved in dust technology, adjusts pH value=3~6, and ultrasound to clarification is prepared.
3. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 2, which is characterized in that the tungsten
The molar ratio of sour sodium dihydrate and bismuth nitrate pentahydrate is (0.8~1.2): 1.
4. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 2, which is characterized in that the tungsten
The amount of the substance of sour sodium dihydrate and the volume ratio of deionized water are (0.2~1) mmol:7.5ml；The bismuth nitrate five is hydrated
The amount of the substance of object and the volume ratio of dust technology are (0.2~1) mmol:7.5ml.
5. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1, which is characterized in that described
The volume ratio (0.8~1.2) of sodium tungstate precursor liquid and bismuth nitrate precursor liquid: 1.
6. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1, which is characterized in that described super
The time of sound is 30~60min.
7. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1, which is characterized in that described
Conductive substrates are FTO electro-conductive glass, fluorine-doped tin oxide, tin-doped indium oxide or flexible circuit.
8. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1, which is characterized in that the water
The time of thermal response is 1~8h；The time of the sintering is 2~6h, and the time of the heat treatment is 0.5~4h.
9. the preparation side of the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1-8
Method, which is characterized in that comprise the following specific steps that:
S1. sodium tungstate dihydrate is dissolved in deionized water and prepares sodium tungstate precursor liquid；Bismuth nitrate pentahapto object is dissolved in dilute
In nitric acid, pH value=3~6 are adjusted, ultrasound to clarification prepares bismuth nitrate precursor liquid；
S2. sodium tungstate precursor liquid and bismuth nitrate precursor liquid are mixed into bismuth tungstate precursor liquid, ultrasound is simultaneously transferred to and is placed with conduction
In the pyroreaction kettle of substrate, in 100~180 DEG C of progress hydro-thermal reactions, cleaned with deionized water, it is dry under nitrogen stream；
S3. it is then sintered at 450~600 DEG C, the bismuth tungstate film in plate conductive substrates will be grown under reproducibility atmosphere
150~400 DEG C are heat-treated, and the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification is made.
10. the bismuth tungstate photocatalyst of Surface Oxygen vacancy defect modification according to claim 1-8 is in photocatalysis
Application in hydrogen manufacturing, photochemical catalytic oxidation organic pollutant field.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252352A (en) * | 2019-05-23 | 2019-09-20 | 广东工业大学 | A kind of carbon quantum dot modification bismuth tungstate/ordered big hole fluorine-doped tin oxide composite photo-catalyst and its preparation method and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561979A (en) * | 2014-12-29 | 2015-04-29 | 中南大学 | Preparation method for bismuth tungstate film |
| JP2015199065A (en) * | 2014-03-31 | 2015-11-12 | 新日鉄住金化学株式会社 | Photocatalyst and production method therefor |
| CN106390992A (en) * | 2016-11-08 | 2017-02-15 | 广西大学 | Preparation method and photocatalytic performance of Bi2WO6-x micro-nano material |
| CN107262023A (en) * | 2017-08-17 | 2017-10-20 | 广东工业大学 | A kind of compound bismuth tungstate photocatalyst of aerosil, its preparation method and its application |
| CN108126689A (en) * | 2017-12-20 | 2018-06-08 | 江苏大学 | A kind of Bi rich in oxygen defect2WO6/In2O3The Preparation method and use of heterojunction composite photocatalyst |
-
2019
- 2019-06-21 CN CN201910543986.XA patent/CN110465286A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015199065A (en) * | 2014-03-31 | 2015-11-12 | 新日鉄住金化学株式会社 | Photocatalyst and production method therefor |
| CN104561979A (en) * | 2014-12-29 | 2015-04-29 | 中南大学 | Preparation method for bismuth tungstate film |
| CN106390992A (en) * | 2016-11-08 | 2017-02-15 | 广西大学 | Preparation method and photocatalytic performance of Bi2WO6-x micro-nano material |
| CN107262023A (en) * | 2017-08-17 | 2017-10-20 | 广东工业大学 | A kind of compound bismuth tungstate photocatalyst of aerosil, its preparation method and its application |
| CN108126689A (en) * | 2017-12-20 | 2018-06-08 | 江苏大学 | A kind of Bi rich in oxygen defect2WO6/In2O3The Preparation method and use of heterojunction composite photocatalyst |
Non-Patent Citations (3)
| Title |
|---|
| CHUAN ZHANG ET AL.: "Synthesis of Square Bi2WO6 Nanoplates as High-Activity Visible-Light-Driven Photocatalysts", 《CHEM. MATER.》 * |
| YANHUI LV ET AL.: "Fabrication of Wide–Range–Visible Photocatalyst Bi2WO6−x nanoplates via Surface Oxygen Vacancies", 《SCIENTIFIC REPORTS》 * |
| 周红君: "铋系光催化剂的制备及光电催化技术在去除气相氮氧化物中的应用", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
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