CN105836807A - Tungsten oxide with two-dimensional slice self-assembly multilevel structure and preparation method thereof and application - Google Patents
Tungsten oxide with two-dimensional slice self-assembly multilevel structure and preparation method thereof and application Download PDFInfo
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- CN105836807A CN105836807A CN201610382040.6A CN201610382040A CN105836807A CN 105836807 A CN105836807 A CN 105836807A CN 201610382040 A CN201610382040 A CN 201610382040A CN 105836807 A CN105836807 A CN 105836807A
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- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- 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
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- B01J23/30—Tungsten
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses tungsten oxide with a multilevel structure and a preparation method thereof and application. The tungsten oxide is of a multilevel structure formed by (002) crystal plane exposed two-dimensional slice self-assembly. The preparation method comprises the steps of using ammonium fluoride aqueous solution as a reaction system, using sodium tungstate as a tungsten source; after the reaction under hydrothermal conditions, causing an obtained product to undergo centrifugation, washing, drying and calcination to obtain the tungsten oxide with the two-dimensional slice self-assembly multilevel structure. According to the method, the shape and size of the tungsten oxide can be regulated by changing the concentration of the ammonium fluoride aqueous solution, a conventional surfactant and a template agent are replaced, and the synthetic process is green and environmentally friendly. The synthesized tungsten oxide with the multilevel structure is uniform in size and can be used as a water decomposition and oxygen generation photocatalyst.
Description
Technical field
The invention belongs to nano-functional material preparing technical field, be specifically related to a kind of multilevel hierarchy tungsten oxide preparation method and
Decompose the application of Aquatic product oxygen.
Background technology
Since the industrial revolution, the consumption of Fossil fuel is grown with each passing day by the mankind with demand, and result in a series of global
Environmental problem.Therefore, find a kind of new continuable clean energy resource and become the key solving these problems.Concurrent having been found that
In the emerging energy technology of exhibition, utilize solar energy to become world community scientific research and industrial quarters is tried to be the first the emphasis of development.Tungsten oxide is one
Kind of multi-functional n-type semiconductor oxide, its band gap width between 2.5eV to 2.9eV, the higher (3.0eV of valence band location electromotive force
Vs NHE), using the teaching of the invention it is possible to provide sufficiently large electromotive force carries out oxidation reaction, thus becomes a kind of important metal oxide semiconductor and answered
For a lot of fields, such as solaode, gas sensor, pollutant removal and decomposition Aquatic product oxygen etc..Miyauchi et al.
Utilize urea molecule as end-capping reagent, control formation and the growth of wolframic acid nucleus, thus obtained the oxidation of a series of different-shape
The micro-nano multilevel hierarchy of tungsten, such as (J.Phys.Chem.C, 2009,113,6539.) such as hollow ball, nanotube, Hemicentrotus seu Strongylocentrotus shapes.Zheng
Et al. with polyvinyl alcohol as surfactant, be prepared for tungsten oxide nanometer flower electrode, and study its surface characteristic and light thereof further
Electrochemical properties (ACS Nano, 2014,8,11770.).But, due to WO3The surface activity site of monocrystalline is not enough, photoproduction electricity
Lotus separation efficiency is low, causes its photocatalytic activity the most relatively low, especially in terms of photolysis Aquatic product oxygen, therefore, and its photocatalysis
Activity needs to be improved further.
Summary 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 this tungsten oxide has two-dimensional slice list
Unit is self-assembly of multilevel hierarchy, it is achieved that high exposure crystal face and the coupling of multilevel hierarchy characteristic, makes the photocatalysis performance of tungsten oxide
It is significantly improved；And the preparation method related to has technique advantage simple, non-toxic and environmentally friendly, it is suitable for popularization and application.
It is a further object of the present invention to provide the application in terms of photocatalysis Decomposition Aquatic product oxygen of the described multilevel hierarchy tungsten oxide, show
Good photocatalysis performance.
For achieving the above object, the technical solution used in the present invention is:
A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, it has what the two-dimensional slice exposed by (002) crystal face was self-assembly of
Multilevel hierarchy, its a size of 1～3 μm, and pattern is homogeneous, specific surface area is 40～60m2/g。
The preparation method of above-mentioned a kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the steps: sodium tungstate and fluorination
Ammonium is soluble in water, is uniformly mixed, and obtains mixed liquor I；Drip certain density hydrochloric acid solution the most wherein, until Huang occurs
The suspended thing of color occurs, adds a certain amount of oxalic acid solution, stirring and dissolving, gained mixed liquor I I is transferred to stainless steel cauldron
In carry out hydro-thermal reaction, after products therefrom is cooled to room temperature, be centrifuged, wash and be dried, finally calcine, obtain two
Dimension thin slice self assembly multilevel hierarchy tungsten oxide.
In such scheme, described sodium tungstate is tungstate dihydrate acid sodium.
In such scheme, in described mixed liquor I I, the concentration of ammonium fluoride is 12.24～122.4mmol/L.
In such scheme, described sodium tungstate aqueous solution introduces the mol ratio of the ammonium fluoride that sodium tungstate introduces with ammonium fluoride aqueous solution and is
(1～10): 1.
In such scheme, the hydrochloric acid that described hydrochloric acid solution introduces is (2～5) with the mol ratio of the sodium tungstate that sodium tungstate aqueous solution introduces: 1.
In such scheme, the oxalic acid that described oxalic acid solution introduces is 1 with the mol ratio of the sodium tungstate that sodium tungstate aqueous solution introduces:
(3～5).
In such scheme, described hydrothermal reaction condition is to react 2～6h at 70～100 DEG C.
In such scheme, described calcining step is to calcine 1～2h at 400～550 DEG C.
The application in photocatalysis Decomposition Aquatic product oxygen field of the two-dimensional slice self assembly multilevel hierarchy tungsten oxide described in such scheme.
The principle of the present invention is:
The formation of two-dimensional slice self assembly multilevel hierarchy tungsten oxide of the present invention is largely divided into core stage and growth stage: in nucleation
In the stage, mainly affected by concentration of hydrochloric acid；Owing to forming H2WO4Hydrionic participation is needed during nucleus, and ammonium fluoride
Together decide on hydrionic concentration in solution with the concentration of hydrochloric acid, thus control the growth of its nucleus；Liter along with concentration of hydrochloric acid
Height, gained tungsten oxide particles is from large to small；In growth stage, the ammonium root cation that ammonium fluoride the introduces effect by Electrostatic Absorption,
It is preferentially adsorbed on H2WO4On (002) crystal face of nucleus so that crystal grows along [002] crystalline axis direction, thus it is raw to play regulation and control
The effect of growth process, ultimately results in (002) crystal face and exposes, and forms tungsten oxide nanometer thin slice, and then is self-assembly of special multistage
Structure；Finally, the tungsten oxide nanometer flower multilevel hierarchy that (002) crystal face exposes by calcining manners, is obtained；Along with ammonium fluoride concentration
Rising, gained tungsten oxide particles is become multilevel hierarchy by single lamellar；Two kinds of factor synergism, and then obtain different chi
Very little multilevel hierarchy tungsten oxide.
The beneficial outcomes of the present invention is:
1) it is prepared for the multilevel hierarchy tungsten oxide of a kind of two-dimensional slice self assembly, is successfully realized particular crystal plane and exposes and multilevel hierarchy
The coupling of characteristic.
2) use exposure crystal face and the appearance structure of nontoxic, cheap ammonium fluoride regulation tungsten oxide, instead of traditional surface activity
The Morphological control agent such as agent template alive, building-up process environmental protection.
3) in reaction system, utilize the hydrion in environment and ammonium radical ion to play the advantage of its regulation and control nucleus growth.
4) the two-dimensional slice self assembly multilevel hierarchy tungsten oxide pattern that prepared by the present invention is homogeneous, size modification scope is wide.
5) the multilevel hierarchy tungsten oxide that prepared by the inventive method has good photocatalysis Decomposition Aquatic product oxygen performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 products therefrom.
Fig. 2 is the SEM figure of the embodiment of the present invention 2 products therefrom.
Fig. 3 is the SEM figure that the embodiment of the present invention 4 prepares multilevel hierarchy tungsten oxide.
Fig. 4 is the embodiment of the present invention 1 products therefrom and commodity WO3Photochemical catalyzing produce oxygen performance comparison figure.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office
It is limited to the following examples.
Following example as no specific instructions, the commercially available chemical reagent of reagent of employing or industrial products.
Embodiment 1
A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, its preparation method comprises the steps:
6.12mmol sodium tungstate and 6.12mmol ammonium fluoride are dissolved in 12.5mL deionized water, are slowly added to 12.5mL salt
Acid solution (2mol/L), stirring is until there is the suspended thing of yellow；Then 25mL oxalic acid solution (1.53mmol) it is added dropwise over,
Stirring 30min；Gained mixed liquor is transferred in teflon-lined stainless steel cauldron, is heated to 90 DEG C and carries out water
Thermal response 3h；Carry out centrifuge washing after products therefrom is cooled to room temperature and be dried, being finally placed in Muffle furnace at 500 DEG C
Calcining 1h i.e. obtains end product.
The present embodiment products therefrom is carried out X-ray diffraction analysis, and result is shown in Fig. 1, the characteristic peak of products therefrom and oxidation in figure
Tungsten standard diagram JCPDS 43-1035 is consistent, and does not has impurity peaks to occur, illustrates that products obtained therefrom is the tungsten oxide that purity is higher.
Embodiment 2
The preparation method of a kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the steps:
6.12mmol sodium tungstate and 0.612mmol ammonium fluoride are dissolved in 12.5mL concentration deionized water, are slowly added to 12.5mL
Dilute hydrochloric acid (1mol/L), there is the suspended thing of yellow in stirring；Then it is added dropwise over 25mL oxalic acid solution (1.75mmol), stirs
Mix 30min；Gained mixed liquor is transferred in teflon-lined stainless steel cauldron, is heated to 90 DEG C and carries out hydro-thermal
Reaction 3h；Carry out centrifuge washing after products therefrom is cooled to room temperature and be dried, being finally placed in 500 DEG C of calcining 1h in Muffle furnace
Obtain end product.
Fig. 2 is the present embodiment gained tungsten oxide SEM figure, and as can be seen from the figure products therefrom pattern is thin slice self assembly stacking
Design of scattered small flowers and plants flap granule, a size of 1 μm.
Embodiment 3
The preparation method of a kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the steps:
6.12mmol sodium tungstate and 2.448mmol ammonium fluoride are dissolved in 12.5mL concentration deionized water, are slowly added to 12.5mL
Hydrochloric acid (2mol/L), there is the suspended thing of yellow in stirring；Then 25mL oxalic acid solution (1.91mmol) it is added dropwise over, stirring
30min；Being transferred in teflon-lined stainless steel cauldron by gained mixed liquor, being heated to 100 DEG C, to carry out hydro-thermal anti-
Answer 3h；Carrying out centrifuge washing after products therefrom is cooled to room temperature and be dried, being finally placed in 500 DEG C of calcining 1h in Muffle furnace is
Obtain two-dimensional slice self assembly multilevel hierarchy tungsten oxide.
Embodiment 4
The preparation method of a kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide, comprises the steps:
6.12mmol sodium tungstate and 2.448mmol ammonium fluoride are dissolved in 12.5mL concentration deionized water, are slowly added to 12.5mL
Hydrochloric acid (2mol/L), there is the suspended thing of yellow in stirring；Then 25mL oxalic acid solution (2.04mmol oxalic acid) it is added dropwise over,
Stirring 30min；Gained mixed liquor is transferred in teflon-lined stainless steel cauldron, is heated to 90 DEG C and carries out water
Thermal response 3h；Carry out centrifuge washing after products therefrom is cooled to room temperature and be dried, being finally placed in 550 DEG C of calcinings 1 in Muffle furnace
H i.e. obtains 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 steps:
6.12mmol sodium tungstate and 0.224mmol ammonium fluoride are dissolved in 12.5mL deionized water, are slowly added to 12.5mL
Dilute hydrochloric acid (2mol/L), stirs；Then it is added dropwise over 25mL oxalic acid solution (61.2mmol/L), stirs 30min；
Gained mixed liquor is transferred in teflon-lined stainless steel cauldron, is heated to 90 DEG C and carries out hydro-thermal reaction 3h；Will
Products therefrom carries out centrifuge washing and is dried after being cooled to room temperature, be finally placed in Muffle furnace at 500 DEG C and calcine 1h and i.e. obtain
End-product.
Fig. 3 is the SEM figure of this comparative example gained tungsten oxide, and as can be seen from the figure products therefrom pattern is nanometer sheet, a size of
300nm。
Comparative example 2
A kind of simple two-dimensional slice tungsten oxide, its preparation method comprises the steps:
6.12mmol sodium tungstate and 0.224mmol ammonium fluoride are dissolved in 12.5mL concentration deionized water, are slowly added to 12.5mL
Dilute hydrochloric acid (2mol/L), stirs；Then it is added dropwise over 25mL oxalic acid solution (61.2mmol/L), stirs 30min；
Gained mixed liquor is transferred in teflon-lined stainless steel cauldron, is heated to 90 DEG C and carries out hydro-thermal reaction 6h；Will
Products therefrom carries out centrifuge washing and is dried after being cooled to room temperature, be finally placed in Muffle furnace at 500 DEG C and calcine 1h and i.e. obtain
End-product.
Application examples
It is applied to embodiment 1 gained two-dimensional slice self assembly multilevel hierarchy tungsten oxide carry out the experiment of photolysis Aquatic product oxygen, specifically wraps
Include following steps:
Weigh 50mg the present embodiment gained two-dimensional slice self assembly multilevel hierarchy tungsten oxide and be scattered in the nitre of 200mL 0.03mol/L
In acid silver solution, it is subsequently adding 0.2g lanthana, is placed in product oxygen reactor and lucifuge carries out magnetic agitation.Simultaneously, right
Response system evacuation processes, and removes oxygen in reactor.Under the conditions of the irradiation of 500W xenon lamp, use commodity WO3Make
For contrast experiment, read oxygen sensor data at regular intervals, it is thus achieved that in reactor, oxygen concentration changes over curve,
Thus evaluate photocatalyst decomposition water efficiency.
Fig. 4 is two-dimensional slice self assembly multilevel hierarchy tungsten oxide and the commodity WO of embodiment 1 preparation3Oxidation water produce oxygen
Performance comparison figure, it can be seen that gained two-dimensional slice self assembly multilevel hierarchy tungsten oxide photolysis water produces oxygen performance higher than business
Change WO3, produce oxygen concentration when 180min and reach about 70 μm ol/L, compare commercialization tungsten oxide and improve 3.3 times,
Photocatalysis efficiency is substantially strengthened.
The above results shows, preparation technology of the present invention is simple and environmentally-friendly, and the multilevel hierarchy tungsten oxide of preparation is at simulated solar irradiation
Lower decomposition water produces the efficiency of oxygen and is substantially better than commercialization WO3。
The foregoing is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, making some modifications and variations, these broadly fall into protection scope of the present invention.
Claims (10)
1. a two-dimensional slice self assembly multilevel hierarchy tungsten oxide, it is characterised in that this tungsten oxide has by the exposure of (002) crystal face
The multilevel hierarchy that two-dimensional slice is self-assembly of, its size is in 1～3 μm, and pattern is homogeneous, and 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 include as follows
Step: by soluble in water to sodium tungstate and ammonium fluoride, be uniformly mixed, obtain mixed liquor I；Drip hydrochloric acid solution the most wherein,
Until the suspended thing of yellow occurs, add oxalic acid solution, stirring and dissolving, gained mixed liquor I I is transferred in stainless steel cauldron
Carry out hydro-thermal reaction, after products therefrom is cooled to room temperature, be centrifuged, wash and be dried, finally calcine, obtain two-dimentional
Thin slice self assembly multilevel hierarchy tungsten oxide.
Preparation method the most according to claim 2, it is characterised in that in described mixed liquor I I, the concentration of ammonium fluoride is
12.24～122.4mmol/L.
Preparation method the most according to claim 2, it is characterised in that described sodium tungstate with the mol ratio of ammonium fluoride is
(1～10): 1.
Preparation method the most according to claim 2, it is characterised in that described hydrochloric acid is (2～5) with the mol ratio of sodium tungstate: 1.
Preparation method the most according to claim 2, it is characterised in that described oxalic acid is 1:(3～5 with the mol ratio of sodium tungstate).
Preparation method the most according to claim 2, it is characterised in that described hydrothermal reaction condition is anti-at 70～100 DEG C
Answer 2～6h.
Preparation method the most according to claim 2, it is characterised in that described calcining step is to calcine at 400～550 DEG C
1～2h.
9. the application in photocatalysis Decomposition Aquatic product oxygen field of the two-dimensional slice self assembly multilevel hierarchy tungsten oxide described in claim 1.
10. the two-dimensional slice self assembly multilevel hierarchy tungsten oxide that prepared by preparation method described in any one of claim 2～8 is in photocatalysis
Decompose the application in Aquatic product oxygen field.
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| CN106830087A (en) * | 2017-02-28 | 2017-06-13 | 河北工业大学 | A kind of preparation method of monoclinic system tungstic acid |
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| CN109647378A (en) * | 2018-12-17 | 2019-04-19 | 福州大学 | It is a kind of for removing odors the preparation method of the nanometer sheet self assembly micron ball catalysis material of hydrogen sulfide |
| CN110090638A (en) * | 2019-03-26 | 2019-08-06 | 北京工业大学 | A kind of solid-carrying type tungstic acid hollow sphere and its preparation method and application |
| 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 |
| CN111333129A (en) * | 2020-02-28 | 2020-06-26 | 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 |
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| CN106830087A (en) * | 2017-02-28 | 2017-06-13 | 河北工业大学 | A kind of preparation method of monoclinic system tungstic acid |
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| 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 |
| CN109647378A (en) * | 2018-12-17 | 2019-04-19 | 福州大学 | It is a kind of for removing odors the preparation method of the nanometer sheet self assembly micron ball catalysis material of hydrogen sulfide |
| 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 |
| CN110090638A (en) * | 2019-03-26 | 2019-08-06 | 北京工业大学 | A kind of solid-carrying type tungstic acid hollow sphere and its preparation method and application |
| 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 |
| CN111333129A (en) * | 2020-02-28 | 2020-06-26 | 上海应用技术大学 | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor |
| 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 |
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