CN105836807B - A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application - Google Patents
A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application Download PDFInfo
- Publication number
- CN105836807B CN105836807B CN201610382040.6A CN201610382040A CN105836807B CN 105836807 B CN105836807 B CN 105836807B CN 201610382040 A CN201610382040 A CN 201610382040A CN 105836807 B CN105836807 B CN 105836807B
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- preparation
- multilevel hierarchy
- dimensional slice
- self assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
- B01J23/16—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
-
- 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
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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 discloses a kind of multilevel hierarchy tungsten oxide and its preparation method and application, the tungsten oxide has the multilevel hierarchy that the two-dimensional slice exposed by (002) crystal face is self-assembly of, and its preparation is concretely comprised the following steps：Using ammonium fluoride aqueous solution as reaction system, using sodium tungstate as tungsten source, after being reacted under hydrothermal condition, products therefrom can obtain many structure tungsten oxides of two-dimensional slice self assembly after centrifugation, washing, dry, calcining.The inventive method can regulate and control the pattern and size of tungsten oxide by changing the concentration of ammonium fluoride aqueous solution, instead of traditional surfactant and template, building-up process environmental protection；Synthesized multilevel hierarchy tungsten oxide size uniformity, can be used as decomposing aquatic products oxygen photochemical catalyst.
Description
Technical field
The invention belongs to nano-functional material preparing technical field, and in particular to a kind of preparation side of multilevel hierarchy tungsten oxide
Method and its decomposition aquatic products oxygen application.
Background technology
Since the industrial revolution, consumption and demand of the mankind to fossil fuel are growing day by day, and result in a series of complete
The environmental problem of ball.Therefore, finding a kind of new sustainable clean energy resource turns into the key for solving these problems.Sending out
Now and in the emerging energy technology of development, the emphasis for development of being tried to be the first using solar energy as world community scientific research and industrial quarters.Oxygen
It is a kind of multi-functional n-type semiconductor oxide to change tungsten, and its band gap width is between 2.5eV to 2.9eV, and valence band location potential is higher
(3.0eV vs NHE), using the teaching of the invention it is possible to provide sufficiently large potential carries out oxidation reaction, so that as a kind of important semiconductor alloy
Oxide is applied to many fields, such as solar cell, gas sensor, pollutant removal and decomposition aquatic products oxygen.
Miyauchi et al. controls the formation and growth of wolframic acid nucleus, so as to obtain a series of by the use of urea molecule as end-capping reagent
The micro-nano multilevel hierarchy of tungsten oxide of different-shape, such as hollow ball, nanotube, sea urchin shape (J.Phys.Chem.C, 2009,
113,6539.).Zheng et al. is prepared for tungsten oxide nanometer flower electrode, and further grind using polyvinyl alcohol as surfactant
Study carefully its surface characteristic and its PhotoelectrochemicalProperties Properties (ACS Nano, 2014,8,11770.).However, due to WO3Live on the surface of monocrystalline
Property site it is not enough, photogenerated charge low separation efficiency causes its photocatalytic activity generally relatively low, especially decomposes aquatic products oxygen side in light
Face, therefore, its photocatalytic activity need further raising.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of multilevel hierarchy tungsten oxide and preparation method thereof, and the tungsten oxide has two dimension
Wafer blocks are self-assembly of multilevel hierarchy, realize the coupling of high exposure crystal face and multilevel hierarchy characteristic, make the light of tungsten oxide
Catalytic performance is significantly improved；And the preparation method being related to has that technique is simple, non-toxic and environmentally friendly advantage, it is adapted to push away
Wide application.
It is a further object of the present invention to provide application of the multilevel hierarchy tungsten oxide in terms of photocatalysis Decomposition aquatic products oxygen,
Show good photocatalysis performance.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, it has the two-dimensional slice exposed by (002) crystal face from group
The multilevel hierarchy formed is filled, its size is 1~3 μm, and pattern is homogeneous, specific surface area is 40~60m2/g。
A kind of preparation method of above-mentioned two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the following steps：By sodium tungstate
It is soluble in water with ammonium fluoride, it is uniformly mixed, obtains mixed liquor I；Then certain density hydrochloric acid solution is added dropwise thereto, until
There are yellow suspended things to occur, add a certain amount of oxalic acid solution, gained mixed liquor I I is transferred to stainless steel by stirring and dissolving
Hydro-thermal reaction is carried out in reactor, products therefrom is cooled to after room temperature, centrifuged, washed and dried, finally calcined, i.e.,
Obtain two-dimensional slice self assembly multilevel hierarchy tungsten oxide.
In such scheme, the sodium tungstate is the sour sodium of tungstate dihydrate.
In such scheme, the concentration of ammonium fluoride is 12.24~122.4mmol/L in the mixed liquor I I.
In such scheme, the wolframic acid sodium water solution introduces mole for the ammonium fluoride that sodium tungstate is introduced with ammonium fluoride aqueous solution
Than for (1~10):1.
In such scheme, the mol ratio for the sodium tungstate that the hydrochloric acid that the hydrochloric acid solution is introduced is introduced with wolframic acid sodium water solution is
(2~5):1.
In such scheme, the mol ratio for the sodium tungstate that the oxalic acid that the oxalic acid solution is introduced is introduced with wolframic acid sodium water solution is
1:(3~5).
In such scheme, the hydrothermal reaction condition is that 2~6h is reacted at 70~100 DEG C.
In such scheme, the calcining step is that 1~2h is calcined at 400~550 DEG C.
The answering in photocatalysis Decomposition aquatic products oxygen field of two-dimensional slice self assembly multilevel hierarchy tungsten oxide described in such scheme
With.
The present invention principle be：
The formation of two-dimensional slice self assembly multilevel hierarchy tungsten oxide of the present invention is largely divided into core stage and growth phase：
In nucleation stage, mainly influenceed by concentration of hydrochloric acid；Due to forming H2WO4Need hydrionic participation during nucleus, and fluorine
The concentration for changing ammonium and hydrochloric acid has together decided on hydrionic concentration in solution, so as to control the growth of its nucleus；As hydrochloric acid is dense
The rise of degree, gained tungsten oxide particles are from large to small；In growth phase, the ammonium root cation that ammonium fluoride is introduced passes through Electrostatic Absorption
Effect, be preferentially adsorbed on H2WO4On (002) crystal face of nucleus so that crystal grows along [002] crystalline axis direction, so as to play
Regulate and control the effect of growth course, ultimately result in the exposure of (002) crystal face, form tungsten oxide nanometer thin slice, and then be self-assembly of spy
Different multilevel hierarchy；Finally, by calcining manners, the tungsten oxide nanometer flower multilevel hierarchy of (002) crystal face exposure is obtained；With fluorine
Change the rise of ammonium concentration, gained tungsten oxide particles become multilevel hierarchy by single sheet；Two kinds of factor synergies, and then
To various sizes of multilevel hierarchy tungsten oxide.
The present invention beneficial outcomes be：
1) a kind of multilevel hierarchy tungsten oxide of two-dimensional slice self assembly is prepared for, particular crystal plane exposure is successfully realized and many
The coupling of level structure characteristic.
2) using the exposure crystal face and appearance structure of nontoxic, cheap ammonium fluoride regulation tungsten oxide, it instead of traditional table
The Morphological control agent, building-up process environmental protection such as face activating agent work template.
3) in reaction system, it is played using the hydrogen ion and ammonium ion in environment and regulates and controls the excellent of nucleus growth
Gesture.
4) the two-dimensional slice self assembly multilevel hierarchy tungsten oxide pattern for preparing of the present invention is homogeneous, size modification scope is wide.
5) multilevel hierarchy tungsten oxide prepared by the inventive method has good photocatalysis Decomposition aquatic products oxygen performance.
Brief description of the drawings
Fig. 1 is the XRD of the products therefrom of the embodiment of the present invention 1.
Fig. 2 schemes for the SEM of the products therefrom of the embodiment of the present invention 2.
Fig. 3 is the SEM figures that multilevel hierarchy tungsten oxide is made in the embodiment of the present invention 4.
Fig. 4 is the products therefrom of the embodiment of the present invention 1 and commodity WO3Photochemical catalyzing produce oxygen performance comparison
Figure.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Following examples unless specific instructions, the commercially available chemical reagent of reagent or industrial products of use.
Embodiment 1
A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, its preparation method comprises the following steps：
6.12mmol sodium tungstates and 6.12mmol ammonium fluorides are dissolved in 12.5mL deionized waters, 12.5mL salt is slowly added to
Acid solution (2mol/L), stirring is until there are yellow suspended things；Then 25mL oxalic acid solutions (1.53mmol) are added dropwise, stir
30min；Gained mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, 90 DEG C of progress hydro-thermal reactions are heated to
3h；Products therefrom is cooled to after room temperature and carries out centrifuge washing and drying, is finally placed in Muffle furnace and calcines 1h i.e. at 500 DEG C
Obtain final product.
The present embodiment products therefrom is subjected to X-ray diffraction analysis, as a result see in Fig. 1, figure the characteristic peak of products therefrom with
Tungsten oxide standard diagram JCPDS 43-1035 are consistent, and occur without impurity peaks, and it is the higher oxidation of purity to illustrate products obtained therefrom
Tungsten.
Embodiment 2
A kind of preparation method of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the following steps：
6.12mmol sodium tungstates and 0.612mmol ammonium fluorides are dissolved in 12.5mL concentration deionized waters, are slowly added to
There are yellow suspended things in 12.5mL watery hydrochloric acid (1mol/L), stirring；Then 25mL oxalic acid solutions (1.75mmol) are added dropwise, stir
Mix 30min；Gained mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, 90 DEG C of progress hydro-thermals are heated to anti-
Answer 3h；Products therefrom is cooled to after room temperature and carries out centrifuge washing and drying, 500 DEG C of calcining 1h in Muffle furnace is finally placed in and produces
Final product.
Fig. 2 is tungsten oxide SEM figures obtained by the present embodiment, and as can be seen from the figure products therefrom pattern is thin slice self assembly heap
Folded design of scattered small flowers and plants flap particle, size is 1 μm.
Embodiment 3
A kind of preparation method of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the following steps：
6.12mmol sodium tungstates and 2.448mmol ammonium fluorides are dissolved in 12.5mL concentration deionized waters, are slowly added to
There are yellow suspended things in 12.5mL hydrochloric acid (2mol/L), stirring；Then 25mL oxalic acid solutions (1.91mmol) are added dropwise, stir
30min；Gained mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, 100 DEG C of progress hydro-thermals are heated to anti-
Answer 3h；Products therefrom is cooled to after room temperature and carries out centrifuge washing and drying, 500 DEG C of calcining 1h in Muffle furnace is finally placed in and produces
Two-dimensional slice self assembly multilevel hierarchy tungsten oxide.
Embodiment 4
A kind of preparation method of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the following steps：
6.12mmol sodium tungstates and 2.448mmol ammonium fluorides are dissolved in 12.5mL concentration deionized waters, are slowly added to
There are yellow suspended things in 12.5mL hydrochloric acid (2mol/L), stirring；Then 25mL oxalic acid solutions (2.04mmol oxalic acid) are added dropwise,
Stir 30min；Gained mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, 90 DEG C of progress hydro-thermals are heated to
React 3h；Products therefrom is cooled to after room temperature and carries out centrifuge washing and drying, 550 DEG C of calcining 1h are finally placed in Muffle furnace i.e.
Obtain two-dimensional slice self assembly multilevel hierarchy tungsten oxide.
Comparative example 1
A kind of simple two-dimensional slice tungsten oxide, its preparation method comprises the following steps：
6.12mmol sodium tungstates and 0.224mmol ammonium fluorides are dissolved in 12.5mL deionized waters, 12.5mL is slowly added to
Watery hydrochloric acid (2mol/L), stirs；Then 25mL oxalic acid solutions (61.2mmol/L) are added dropwise, 30min is stirred；By gained
Mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is heated to 90 DEG C and is carried out hydro-thermal reaction 3h；Gained is produced
Thing, which is cooled to after room temperature, carries out centrifuge washing and drying, is finally placed in Muffle furnace the calcining 1h at 500 DEG C and produces final product.
Fig. 3 is the SEM figures of tungsten oxide obtained by this comparative example, and as can be seen from the figure products therefrom pattern is nanometer sheet, chi
Very little is 300nm.
Comparative example 2
A kind of simple two-dimensional slice tungsten oxide, its preparation method comprises the following steps：
6.12mmol sodium tungstates and 0.224mmol ammonium fluorides are dissolved in 12.5mL concentration deionized waters, are slowly added to
12.5mL watery hydrochloric acid (2mol/L), stirs；Then 25mL oxalic acid solutions (61.2mmol/L) are added dropwise, 30min is stirred；
Gained mixed liquor is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, 90 DEG C is heated to and carries out hydro-thermal reaction 6h；Will
Products therefrom, which is cooled to after room temperature, carries out centrifuge washing and drying, is finally placed in Muffle furnace the calcining 1h at 500 DEG C and produces most
End-product.
Application examples
The gained two-dimensional slice self assembly multilevel hierarchy tungsten oxide of embodiment 1 is applied to carry out light decomposition aquatic products oxygen experiment,
Specifically include following steps：
Two-dimensional slice self assembly multilevel hierarchy tungsten oxide obtained by weighing 50mg the present embodiment is scattered in 200mL 0.03mol/L
Silver nitrate solution in, then add 0.2g lanthanas, be placed in production oxygen reactor and lucifuge carry out magnetic agitation.Simultaneously,
To reaction system vacuumize process, oxygen in reactor is removed.Under the conditions of the irradiation of 500W xenon lamps, using commodity WO3As
Contrast experiment, reads oxygen sensor data at regular intervals, obtains oxygen concentration in reactor and changes over time curve, from
And evaluate photochemical catalyst decomposition water efficiency.
Fig. 4 is two-dimensional slice self assembly multilevel hierarchy tungsten oxide and commodity WO prepared by embodiment 13Oxidation water produce oxygen
The performance comparison figure of gas, it can be seen that it is high that gained two-dimensional slice self assembly multilevel hierarchy tungsten oxide light decomposition water produces oxygen performance
In commercialization WO3, in 180min, generation oxygen concentration reaches 70 μm of ol/L or so, and 3.3 are improved compared to commercialization tungsten oxide
Times, photocatalysis efficiency is substantially strengthened.
The above results show that preparation technology of the present invention is simple and environmentally-friendly, and the multilevel hierarchy tungsten oxide prepared is in simulation
The efficiency of decomposition water generation oxygen is substantially better than commercialization WO under sunshine3。
It the foregoing is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, make some modifications and variations, these belong to the protection model of the present invention
Enclose.
Claims (10)
1. a kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, it is characterised in that the tungsten oxide has to be exposed by (002) crystal face
The nano flower multilevel hierarchy that is self-assembly of of two-dimensional slice, its size is at 1~3 μm, and pattern is homogeneous, specific surface area is 40~
60m2/g。
2. the preparation method of two-dimensional slice self assembly multilevel hierarchy tungsten oxide described in claim 1, it is characterised in that including as follows
Step：Sodium tungstate and ammonium fluoride is soluble in water, it is uniformly mixed, obtains mixed liquor I；Then hydrochloric acid solution is added dropwise thereto,
Until there are yellow suspended things, oxalic acid solution is added, gained mixed liquor I I is transferred in stainless steel cauldron by stirring and dissolving
Hydro-thermal reaction is carried out, products therefrom is cooled to after room temperature, is centrifuged, washed and dried, finally calcined, produce two dimension thin
Piece self assembly multilevel hierarchy tungsten oxide.
3. preparation method according to claim 2, it is characterised in that the concentration of ammonium fluoride is in the mixed liquor I I
12.24~122.4mmol/L.
4. preparation method according to claim 2, it is characterised in that the mol ratio of the sodium tungstate and ammonium fluoride for (1~
10):1。
5. preparation method according to claim 2, it is characterised in that the mol ratio of the hydrochloric acid and sodium tungstate for (2~
5):1。
6. preparation method according to claim 2, it is characterised in that the mol ratio of the oxalic acid and sodium tungstate is 1:(3~
5)。
7. preparation method according to claim 2, it is characterised in that the hydrothermal reaction condition is at 70~100 DEG C
React 2~6h.
8. preparation method according to claim 2, it is characterised in that the calcining step is to be calcined at 400~550 DEG C
1~2h.
9. the answering in photocatalysis Decomposition aquatic products oxygen field of two-dimensional slice self assembly multilevel hierarchy tungsten oxide described in claim 1
With.
10. two-dimensional slice self assembly multilevel hierarchy tungsten oxide prepared by any one of claim 2~8 preparation method is urged in light
Change the application decomposed in aquatic products oxygen field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610382040.6A CN105836807B (en) | 2016-06-01 | 2016-06-01 | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610382040.6A CN105836807B (en) | 2016-06-01 | 2016-06-01 | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105836807A CN105836807A (en) | 2016-08-10 |
| CN105836807B true CN105836807B (en) | 2017-08-18 |
Family
ID=56595537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610382040.6A Expired - Fee Related CN105836807B (en) | 2016-06-01 | 2016-06-01 | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105836807B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597100A (en) * | 2017-10-23 | 2018-01-19 | 郑州轻工业学院 | The preparation method of two-dimentional sodium tungstate/tungsten oxide catalysis material of carbon point modification |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830087B (en) * | 2017-02-28 | 2018-06-15 | 河北工业大学 | A kind of preparation method of monoclinic system tungstic acid |
| CN109647378B (en) * | 2018-12-17 | 2021-08-31 | 福州大学 | Preparation method of nanosheet self-assembled microsphere photocatalytic material for removing peculiar smell hydrogen sulfide |
| CN110090638B (en) * | 2019-03-26 | 2022-04-22 | 北京工业大学 | Immobilized tungsten trioxide hollow sphere and preparation method and application thereof |
| CN110252381A (en) * | 2019-07-31 | 2019-09-20 | 泉州师范学院 | A kind of preparation and application of 2D-2D tungstic acid/class graphite phase carbon nitride heterojunction structure photochemical catalyst |
| CN111333129B (en) * | 2020-02-28 | 2022-08-23 | 上海应用技术大学 | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor |
| CN115007136A (en) * | 2022-06-29 | 2022-09-06 | 河南大学 | Tungsten oxide photocatalyst with hollow structure and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318703A (en) * | 2008-07-08 | 2008-12-10 | 清华大学 | Tungstic oxide nano-wire and method for preparing tungstic oxide nano-wire ammonia sensitive sensor |
| CN102976403B (en) * | 2012-12-06 | 2015-08-26 | 南京大学 | A kind of controlled difference exposes the TiO of crystal face 2nanocrystalline preparation method |
| CN104724758B (en) * | 2015-03-06 | 2017-07-07 | 华北电力大学 | A kind of WO3The preparation method of nanoscale twins material |
-
2016
- 2016-06-01 CN CN201610382040.6A patent/CN105836807B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597100A (en) * | 2017-10-23 | 2018-01-19 | 郑州轻工业学院 | The preparation method of two-dimentional sodium tungstate/tungsten oxide catalysis material of carbon point modification |
| CN107597100B (en) * | 2017-10-23 | 2020-03-10 | 郑州轻工业学院 | Preparation method of carbon-point-modified two-dimensional sodium tungstate/tungsten oxide photocatalytic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105836807A (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105836807B (en) | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application | |
| CN105600828B (en) | A kind of porous nano CuFe2O4Preparation method | |
| CN105664950B (en) | A kind of porous nano ZnFe2O4Preparation method | |
| CN104772158A (en) | Preparation method of WO3/C3N4 mixed photocatalyst | |
| CN104148054B (en) | A kind of preparation method of pucherite nano rod bundle | |
| CN105521789B (en) | A kind of porous nano BiFeO3Preparation method | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN102974373A (en) | Visible-light photocatalytic material and preparation method thereof | |
| CN104056620A (en) | Visible-light catalyst and preparation method and application thereof | |
| CN109225194A (en) | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application | |
| CN103395822B (en) | A kind of Red copper oxide micrometre hollow sphere and synthetic method, application method | |
| CN112875755A (en) | Preparation method of bismuth tungstate nano powder | |
| TW202037586A (en) | Method for reducing carbon dioxide to manufacture carbon compound | |
| CN106215967A (en) | A kind of g C3n4the quantum dot sensitized Bi of quantum dot, Ag2moO6the preparation method of nanometer sheet | |
| CN106809871B (en) | A kind of preparation method of indium oxide nano powder | |
| CN106517311B (en) | A kind of preparation method of gallic acid zinc bivalve layer nano-hollow ball | |
| CN105084409B (en) | It is a kind of（200）Crystal face exposes the synthetic method of single dispersing CuO nanometer sheet | |
| CN103933957A (en) | Porous monocrystal nano-titanium dioxide photo-catalyst with high crystallization, controllable size and exposed high-energy surface, preparation method and application of photo-catalyst | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN103418394B (en) | Method for synthesizing nickel-doped indium vanadate nanocrystalline photocatalyst by adopting microwave heating method and application thereof for water decomposition under visible light | |
| CN105056965A (en) | Biological carbon sphere supported FeMoO4 Fenton catalyst, preparation method and application | |
| CN102616840A (en) | Method for preparing transition metal oxide nano single crystal with specific exposed crystal faces through stripping nanosheets | |
| CN109761261B (en) | Green preparation method of cerium dioxide powder with controllable particle size and morphology and large specific surface area | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN105198004B (en) | A kind of Fe3O4‑SnO2Nano composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170818 Termination date: 20200601 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |