CN106830087A - A kind of preparation method of monoclinic system tungstic acid - Google Patents
A kind of preparation method of monoclinic system tungstic acid Download PDFInfo
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- CN106830087A CN106830087A CN201710109750.6A CN201710109750A CN106830087A CN 106830087 A CN106830087 A CN 106830087A CN 201710109750 A CN201710109750 A CN 201710109750A CN 106830087 A CN106830087 A CN 106830087A
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- monoclinic system
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- tungstic acid
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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 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910000474 mercury oxide Inorganic materials 0.000 claims abstract description 8
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims abstract description 5
- 229920000151 polyglycol Polymers 0.000 claims abstract description 3
- 239000010695 polyglycol Substances 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910016510 CuCrO2 Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 tungsten ion Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/39—
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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 present invention is a kind of preparation method of monoclinic system tungstic acid.The method is comprised the following steps：（1）Under stirring, nitric acid is added in sodium tungstate solution, centrifugation after stirring, collection obtains yellow mercury oxide；（2）Yellow mercury oxide is transferred in reactor, deionized water, organic acid soln and polyglycol solution is added；（3）Nitric acid is added to stir 0.5 2 hours；（4）Gained slurry is transferred in autoclave, it is closed after be warming up to 160 250 DEG C of 20h of successive reaction 8；Obtain monoclinic system tungsten trioxide powder.The present invention has obtained finely dispersed micro/nano level tungstic acid crystal grain.Gained tungstic acid crystal grain has excellent photocatalysis performance.
Description
Technical field：
The invention belongs to tungstic acid preparing technical field, specially a kind of preparation method of monoclinic system tungstic acid.
Technical background：
Tungstic acid is a kind of conductor oxidate with N-type conductive features, because of convenient energy gap and calibration
Valence band current potential, good performance is shown during photochemical catalyzing.As photochemical catalyzing catalyst, three oxygen
Crystalline phase composition, granularity and the dispersiveness for changing tungsten have a major impact to its performance.Abundant experimental results show, monoclinic system tungstic acid
There is more excellent photocatalysis performance compared with the tungstic acid of other crystalline phases.And granularity reduction, the crystalline perfection of tungstic acid
Raising is all conducive to the raising of its photocatalyst activity.Simultaneously as the energy gap of tungstic acid is narrower, during exclusive use,
The purpose of decomposition water can not be reached in the presence of without sacrifice agent, by itself and P-type semiconductor oxide, such as CuCrO2It is multiple
Photocatalysis Decomposition pure water produces hydrogen by after conjunction, reduces the granularity of tungstic acid, improves its dispersiveness and is also beneficial to itself and p-type
Conductor oxidate it is compound.In document, in many cases, obtained tungstic acid presoma need to be through 600 DEG C of high temperature above at
The purpose for managing to reach conversion crystal formation and improve sample crystallization integrality, but high-temperature process can change the pattern of crystal, and cause
The granularity increase of crystal grain, dispersiveness is deteriorated.Explore one kind and be directly synthesized crystalline perfection at a lower temperature preferably, granularity
Tiny and finely dispersed monoclinic system tungstic acid is significant.
The content of the invention：
The purpose of the present invention is directed to not enough present in current techniques, there is provided a kind of preparation side of monoclinic system tungstic acid
Method.With sodium tungstate as raw material, organic acid is crystal growth controlling agent to the method, and nitric acid is that acidulant hydro-thermal method prepares WO3, pass through
Adding polyethylene glycol makes product dispersed in the solution, and monoclinic system WO is just directly obtained in the case of less than 250 DEG C3.This
Invention obtains monoclinic system tungstic acid for micro/nano level, and granularity is tiny, is uniformly dispersed.
The technical scheme is that：
A kind of preparation method of monoclinic system tungstic acid, comprises the following steps：
(1) under stirring, nitric acid is added in sodium tungstate solution, is stirred 0.5-2 hours, centrifugation, collection obtains Huang
Color is precipitated；
Wherein, the mass concentration of sodium tungstate solution is 5%-20%, mol ratio NHO3：Tungsten atom=2~4：1；
(2) obtained yellow mercury oxide in step (1) is transferred in reactor, adds deionized water, stir pulp；Again
Under agitation to organic acid soln is added in slurry, mixed slurry is obtained；
Wherein, mol ratio organic acid：Tungsten atom=1~4：1；Quality compares deionized water：Precipitation=5~10：1, organic acid
The mass concentration of solution is 15-20%；
(3) by mass concentration for the polyglycol solution of 15-20% is added in (2) gained mixed slurry；
Wherein, quality compares polyethylene glycol：Tungsten atom=0.1~1：1；
(4) nitric acid is added in (3) gained mixed slurry again, continues to stir 0.5-2 hours；Wherein, mol ratio NHO3：
Tungsten atom=4~10：1；
(5) by (4) gained slurry be transferred in autoclave, it is closed after be warming up to 160-250 DEG C of successive reaction 8-20h；Instead
After should terminating, material in kettle is centrifuged, after scrubbed, drying, grinding, obtains monoclinic system tungsten trioxide powder.
Described polyethylene glycol be polyethylene glycol 2000, Macrogol 4000, Macrogol 6000, PEG 8000 or
PEG20000.
Described organic acid is citric acid, levotartaric acid, DL-malic acid, butanedioic acid or oxalic acid.
The mass percentage concentration of the nitric acid in described step (1) and step (3) is preferably 63%.
Beneficial effects of the present invention are：
The present invention promotes crystallographic system to monocline during hydro-thermal method synthesis tungstic acid by controlling suitable acid strength
Inversion of phases；Using organic acid and the complexing of tungsten atom, the crystallization of tungstic acid is controlled by adding appropriate, appropriate organic acid
The speed of growth, it is ensured that the integrality of crystallization；Ensure the dispersiveness and granularity of sample by adding appropriate polyethylene glycol, make most
Prepared crystallographic system is monoclinic system, regular shape, finely dispersed micro/nano level tungstic acid crystal grain eventually.Gained tungstic acid is brilliant
Body particle has excellent photocatalysis performance.Experimental result shows that addition polyethylene glycol is used as dispersant gained in preparation process
WO3The product hydrogen activity of activity more non-addition polymerization ethylene glycol dispersant gained sample improve 55.6%.
Brief description of the drawings：
Fig. 1 is obtained WO for embodiment 13XRD.
Fig. 2 is obtained WO for embodiment 13SEM figure.
Fig. 3 is obtained WO for embodiment 23XRD.
Fig. 4 is obtained WO for embodiment 23SEM figure.
Specific implementation method：
Embodiment 1
(1) 5gNa is weighed2WO4.2H2O, plus deionized water is configured to the aqueous solution that mass concentration is 10%, by NHO3With tungsten
Atomic molar ratio is 2:1 ratio adds the salpeter solution that mass concentration is 63%, obtains pale yellow precipitate, stirs 0.5 hour, sinks
Shallow lake is converted into glassy yellow.Centrifugation, collection obtains yellow mercury oxide.
(2) yellow mercury oxide obtained in (1) is transferred in beaker, it is 6 to add with precipitation mass ratio:1 deionized water stirring
Pulp.It is 2 to press simultaneously with tungsten atom mol ratio:1 ratio weighs citric acid, and add water the water for being configured to that mass concentration is 20%
Solution；It is 0.5 by with tungsten atom mass ratio:1 ratio weighs polyethylene glycol 2000, and it is 20% to add water and be configured to mass concentration
The aqueous solution, the two order is added in afore-mentioned slurry.
(3) by NHO3It is 6 with tungsten ion mol ratio:1 concentrated nitric acid for measuring mass percentage concentration 63%, is added to (2) institute
State in slurry, stirred 2 hours under normal temperature.
(4) (3) gained slurry is transferred in 0.5L autoclaves, 190 DEG C of successive reaction 12h is warming up to after closed kettle cover.
After reaction terminates, material in kettle is centrifuged, pure water and absolute ethyl alcohol are respectively washed three times, 120 DEG C of drying, after grinding
Tungstic acid crystal powder.
XRD analysis are carried out to the step of embodiment 1 (4) gained sample, accompanying drawing 1, the diffraction maximum and monoclinic system of sample is as a result seen
Tungstic acid standard card PDF43-1035 coincide；Sem analysis are carried out to the step of embodiment 1 (4) gained sample, accompanying drawing is as a result seen
2, sample is square block particle of the granularity in 100-150nm, and crystal growth is complete, crystal shape rule.
Embodiment 2
(1) 5gNa is weighed2WO4.2H2O, plus deionized water is configured to the aqueous solution that mass concentration is 10%, by HNO3With tungsten
Atomic molar ratio is 2:1 ratio adds the salpeter solution that mass concentration is 63%, obtains pale yellow precipitate, stirs 0.5 hour, sinks
Shallow lake is converted into glassy yellow.Centrifugation, collection obtains yellow mercury oxide.
(2) yellow mercury oxide obtained in (1) is transferred in beaker, it is 6 to add with precipitation mass ratio:1 deionized water stirring
Pulp.It is 1 to press simultaneously with tungsten atom mol ratio:1 ratio weighs levotartaric acid, and it is 20% to add water and be configured to mass concentration
The aqueous solution；It is 0.3 by with tungsten atom mass ratio:1 ratio weighs polyethylene glycol 2000, and adding water is configured to mass concentration and is
20% aqueous solution, the two order is added in afore-mentioned slurry.
(3) by HNO3It is 6 with tungsten atom mol ratio:1 ratio measures the concentrated nitric acid of mass percentage concentration 63%, is added to
(2) in the slurry, stirred 2 hours under normal temperature.
(4) (3) gained slurry is transferred in 0.5L autoclaves, 160 DEG C of successive reaction 18h is warming up to after closed kettle cover.
After reaction terminates, material in kettle is centrifuged, pure water and absolute ethyl alcohol are respectively washed three times, 120 DEG C of drying, after grinding
Tungstic acid crystal powder.
XRD analysis are carried out to the step of embodiment 2 (4) gained sample, accompanying drawing 3, the diffraction maximum and monoclinic system of sample is as a result seen
Tungstic acid standard card PDF43-1035 fits like a glove；Sem analysis are carried out to the step of embodiment 2 (4) gained sample, is as a result seen
Accompanying drawing 4, sample is square block particle of the granularity between 200-350nm, and crystal growth is complete, crystal shape rule.
Embodiment 3
Weigh 4g copper nitrates, the aqueous solution that mass concentration is 10% be configured to deionized water, by oxalic acid and copper mole
Than being 1.1:1 weighs oxalic acid, and the oxalic acid aqueous solution that mass concentration is 15% is configured to deionized water, and the latter is added into the former shape
Into cupric oxalate precipitation, filtered after deposition 20min.It is 1 by the mol ratio of chromium and copper:1 weighs chromic nitrate, is configured to deionized water
Mass concentration is 10% chromium nitrate aqueous solution, and cupric oxalate precipitation is added thereto, and mechanical agitation makes pulp thing, stirring
Simultaneously in being heated in 85 DEG C of water-bath, slurry is dehydrated, drying in baking oven is moved into after sticky.The powder of drying is ground with mortar
Carefully, CuCrO is obtained through 600 DEG C of roastings 5h, 800 DEG C of roastings 3h, 950 DEG C of roastings 3h, 1000 DEG C of roasting 3h in blanket of nitrogen2。
Embodiment 4
Weigh 0.1mol embodiments 1 and WO is obtained3With CuCrO obtained in 0.1mol embodiments 32Powder, is added to ball mill
In, while weigh the absolute ethyl alcohol that pH value is 8 being added thereto, the pH value mass concentration of absolute ethyl alcohol is 5% ammonia spirit
Regulation, absolute ethyl alcohol and WO3+CuCrO2Mass ratio be 0.05, grind 0.5h under 800 revs/min of rotating speed.After grinding
Sample drying, and after under air atmosphere, 350 DEG C of heat treatment 3h obtain WO3-CuCrO2Composite catalyst.
Weigh above-mentioned WO3-CuCrO2Composite catalyst 0.1g, is added in the quartz reactor that volume is 500mL, plus go
Ionized water 400mL.Then by reactor one closed system of access, replaced by carrying out secondary vacuum pumping, applying argon gas to system
Method remove oxygen therein and carbon dioxide；Then in argon atmospher, absolute pressure be -0.05MPa under, magnetic agitation,
1h is reacted in the case of 250W high-pressure sodium lamp external irradiations, distance of the light source away from reactor outer is 5cm.After reaction terminates, survey
The growing amount for obtaining hydrogen is 2.1mL, and the growing amount of oxygen is 0.9mL.
Embodiment 5
With WO obtained in embodiment 23With CuCrO obtained in embodiment 32Prepare composite catalyst, and test compound catalyst
Photocatalyzed Hydrogen Production activity, the proportioning of composite catalyst, preparation method and activity test method are with embodiment 4.Measure hydrogen
Growing amount is 2.8mL, and the growing amount of oxygen is 1.2mL.
Embodiment 6
Method same as Example 1 is taken to synthesize WO3, other Step By Conditions are to gather with embodiment 1, difference
Ethylene glycol 2000 is 0.8 with tungsten atom mass ratio:1.Then with obtained WO3With CuCrO obtained in embodiment 32Prepare compound urging
Agent, and the Photocatalyzed Hydrogen Production of test compound catalyst is active.The proportioning of composite catalyst, preparation method and activity test method
With embodiment 4.The growing amount of hydrogen is measured for 1.9mL, the growing amount of oxygen is 0.8mL.
Embodiment 7
Method same as Example 2 is taken to synthesize WO3, other Step By Conditions are to use with embodiment 2, difference
Macrogol 4000 substitutes polyethylene glycol 2000, and Macrogol 4000 is 0.5 with tungsten atom mass ratio:1.Then obtained in
WO3With CuCrO obtained in embodiment 32Composite catalyst is prepared, and the Photocatalyzed Hydrogen Production of test compound catalyst is active.It is compound to urge
The proportioning of agent, preparation method and activity test method are with embodiment 4.The growing amount of hydrogen is measured for 2.3mL, the generation of oxygen
It is 0.9mL to measure.
Comparative example 1
Method same as Example 1 is taken to synthesize WO3, polyethylene glycol 2000 is not added with preparation, remaining condition is constant.So
Afterwards with obtained WO3With CuCrO obtained in embodiment 32Prepare composite catalyst, and test compound catalyst Photocatalyzed Hydrogen Production
Activity.The proportioning of composite catalyst, preparation method and activity test method are with embodiment 4.The growing amount for measuring hydrogen is
1.6mL, the growing amount of oxygen is 0.4mL.
Comparative example 2
Method same as Example 2 is taken to synthesize WO3, polyethylene glycol 2000 is not added with preparation, remaining condition is constant.So
Afterwards with obtained WO3With CuCrO obtained in embodiment 32Prepare composite catalyst, and test compound catalyst Photocatalyzed Hydrogen Production
Activity.The proportioning of composite catalyst, preparation method and activity test method are with embodiment 4.The growing amount for measuring hydrogen is
1.8mL, the growing amount of oxygen is 0.8mL.
Embodiment 5 is obtained WO3Activity WO is obtained compared with comparative example 23It is active high by 55.6%.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. a kind of preparation method of monoclinic system tungstic acid, it is characterized by the method is comprised the following steps：
（1）Under stirring, nitric acid is added in sodium tungstate solution, stirred 0.5-2 hours, centrifugation, collection obtains yellow and sinks
Form sediment；
Wherein, the mass concentration of sodium tungstate solution is 5%-20%, mol ratio NHO3：Tungsten atom=2.0 ~ 4：1；
（2）By step（1）In obtained yellow mercury oxide be transferred in reactor, add deionized water, stir pulp；Exist again
To organic acid soln is added in slurry under stirring, mixed slurry is obtained；
Wherein, mol ratio organic acid：Tungsten atom=1 ~ 4：1；Quality compares deionized water：Precipitation=5 ~ 10：1, the matter of organic acid soln
Amount concentration is 15-20%；
（3）By mass concentration for the polyglycol solution of 15-20% is added to（2）In gained mixed slurry；
Wherein, quality compares polyethylene glycol：Tungsten atom=0.1 ~ 1：1；
（4）Nitric acid is added to again（3）In gained mixed slurry, continue to stir 0.5-2 hours；Wherein, mol ratio NHO3：Tungsten is former
Son=4 ~ 10：1；
（5）Will（4）Gained slurry is transferred in autoclave, it is closed after be warming up to 160-250 DEG C of successive reaction 8-20h；Reaction knot
Shu Hou, material in kettle is centrifuged, and after scrubbed, drying, grinding, obtains monoclinic system tungsten trioxide powder.
2. the preparation method of monoclinic system tungstic acid as claimed in claim 1, it is characterized by described organic acid be citric acid,
Levotartaric acid, DL-malic acid, butanedioic acid or oxalic acid.
3. the preparation method of monoclinic system tungstic acid as claimed in claim 1, it is characterized by described step（1）And step
（3）In the mass percentage concentration of nitric acid be preferably 63%.
4. the preparation method of monoclinic system tungstic acid as claimed in claim 1, it is characterized by, described polyethylene glycol is poly- second
Glycol 2000, Macrogol 4000, Macrogol 6000, PEG 8000 or PEG20000.
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| CN111974419A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Novel method for preparing molybdenum disulfide/tungsten trioxide composite photocatalyst |
| CN111974407A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Method for preparing magnetic tungsten trioxide composite photocatalyst |
| CN111974418A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Preparation of ternary composite magnetic photocatalytic material MoS2/WO3/SrFe12O19Method (2) |
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| CN103787418A (en) * | 2014-01-21 | 2014-05-14 | 中国科学院金属研究所 | Method for preparing WO3.H2O hollow sphere assembled by nanosheets |
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| CN111974419A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Novel method for preparing molybdenum disulfide/tungsten trioxide composite photocatalyst |
| CN111974407A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Method for preparing magnetic tungsten trioxide composite photocatalyst |
| CN111974418A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Preparation of ternary composite magnetic photocatalytic material MoS2/WO3/SrFe12O19Method (2) |
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