CN105788870A - Application of mesoporous hollow spherical titanium dioxide/tungsten trioxide composite material in film electrode preparation - Google Patents
Application of mesoporous hollow spherical titanium dioxide/tungsten trioxide composite material in film electrode preparation Download PDFInfo
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- CN105788870A CN105788870A CN201610204309.1A CN201610204309A CN105788870A CN 105788870 A CN105788870 A CN 105788870A CN 201610204309 A CN201610204309 A CN 201610204309A CN 105788870 A CN105788870 A CN 105788870A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention provides an application of a mesoporous hollow spherical titanium dioxide/tungsten trioxide composite material in film electrode preparation. By compositing tungsten trioxide and titanium dioxide, the forbidden bandwidth of titanium dioxide can be narrowed effectively, titanium dioxide can be excited by visible light, and the utilization rate of sunlight is improved. Titanium dioxide can increase the acidity on the surface of the titanium dioxide and promote the adsorption of contaminants on the surface. By making the composite material into film electrodes, the problem that the traditional powder catalyst is hard to separate and recycle and even causes secondary pollution is solved, and a step further is taken for industrial application of the titanium dioxide catalyst. Under the synergistic effect of electrocatalysis and photocatalysis, photo-produced electrons can directionally move to the cathode under the action of an external electric field, and therefore, spatial separation of carriers is promoted, compositing of h<+>-e<-> pairs is reduced, the utilization rate of h<+>-e<-> is improved, and the efficiency of photoelectric catalysis is improved.
Description
(1) technical field
The invention belongs to the photoelectrocatalysis field of Inorganic Non-metallic Materials, be specifically related to a kind of mesic hole hollow ball-shape titania/tri-
The application in prepared by membrane electrode of the tungsten oxide composite.
(2) background technology
Energy problem and environmental problem are 21 century two significant problems urgently to be resolved hurrily.Conductor photocatalysis material is permissible because of it
Sunlight is effectively utilized to be referred to as a most promising class material.Titanium dioxide has peace as a kind of semiconductor light-catalyst
Entirely, nontoxic, cheap, superior photoelectricity, dielectric effect and good Photoelectrochemical stabilization, in contaminant degradation, photocatalysis
The fields such as hydrogen production by water decomposition have wide practical use.
Titanium dioxide has bigger energy gap, and Anatase is 3.2eV, Rutile Type is 3.0eV, only with the sun
Light accounts for the ultraviolet light of 5%, seriously limits the utilization rate to sunlight.Simultaneously as photo-generated carrier major part occurs
Compound, efficiently separate effect the lowest, thus the quantum yield of catalyst is generally less than in the light-catalyzed reaction system of aqueous phase
1%, and then cause photocatalysis efficiency low.And major part research concentrates on powder TiO2Catalyst, inevitably deposits
In the problem reclaiming difficulty, catalyst loss is serious, be difficult to secondary uses.So how improve this system to visible light-responded,
More make full use of the central issue that sunlight is the research of titanium dioxide semiconductor photocatalysis technology, be also in titanium dioxide practical process
The key issue that must solve.
In recent years, electrochemistry auxiliary TiO2Photocatalysis technology is by extensive concern.Its advantage is that applied voltage makes light excite generation
Light induced electron be driven on electrode by external circuit, prevent the compound of light induced electron and photohole, thus improve
Light-catalysed efficiency；By TiO2Immobilization, it is to avoid suspended state reaction system nano-catalyst particles separates with solution, with
Time remain TiO2Nanometer size effect.Optoelectronic pole is the critical component of photo electrocatalysis reactor, therefore prepares and has well
Photocatalysis performance, especially there is the TiO of visible light catalysis activity2Membrane electrode becomes the focus of current photocatalysis technology research
One of.
In order to strengthen TiO2The visible light-responded ability of membrane electrode, improves utilization rate to sunlight, people take doping,
The means such as noble metal surface modification, semiconductors coupling, applied voltage are to TiO2Membrane electrode is modified.(Lei H., the Yan such as Lei
Jun X., Hui ling L., Etal.J.Hazard.Mater.2010,175:524 1) by Plasma based ion implantation method
It is prepared for the TiO of N doping2/ Ti nano-array is also applied to the photoelectric catalysis degrading of excited by visible light.Kunpeng etc.
(Kunpeng X., Lan5., ChenglinW., etal.Electrochimica ACta2010,55:7211 1) uses pulse current
Sedimentation is prepared for the TiO of loaded Ag2Array film electrode, it is shown that higher PhotoelectrocatalytiPerformance Performance.But, by coating
Method is by the TiO of mesic hole hollow ball-shape semiconductors coupling2Cover preparation in conductive substrates and be used for the membrane electrode of photocatalytic degradation
Method have not been reported.
(3) summary of the invention
The invention provides a kind of visible light-responded mesic hole hollow ball-shape titania/Tungstic anhydride. composite at membrane electrode
Application in preparation.The mesoporous size of described composite is 1～50nm, and a diameter of 0.6～1.4 μm of ball, specific surface area is
60～150m2/g.Application process of the present invention is simple, controllability and reproducible, and prepared membrane electrode is suitableeer
Conjunction is applied to the field such as photocatalysis, DSSC.
The present invention adopts the following technical scheme that
The application in prepared by membrane electrode of a kind of mesic hole hollow ball-shape titania/Tungstic anhydride. composite, described application
Method is: described mesic hole hollow ball-shape titania/Tungstic anhydride. composite is modulated into slurry, then by equal for this slurry
It is coated in the conductive substrates of cleaning evenly, treats that slurry carries out calcination processing after drying, obtain described membrane electrode.
Described mesic hole hollow ball-shape titania/Tungstic anhydride. composite uses and is spray-dried high-temperature calcination two-step method system
Standby, concrete operation method is as follows: titanyl sulfate (titanium source), ammonium metatungstate (tungsten source), citric acid (chelating agent) are dissolved in
In ionized water, room temperature (20～30 DEG C) stirring 8～24h, then regulate pH to 7.0～8.0 with 2.5wt%～2.8wt% ammonia,
Obtain precursor solution, carry out gained precursor solution successively being spray-dried, high-temperature calcination, prepare described medium hole hollow ball
Shape titanium dioxide/Tungstic anhydride. composite；
Wherein,
Described titanyl sulfate in terms of titanium with ammonium metatungstate in terms of tungsten, the ratio of the amount of the material of citric acid, deionized water be 1:
0.01～0.2:0.1～0.5:1000～3000；
The condition of described spray drying is: inlet temperature 140～240 DEG C, material flow 400～1200mL/h, air pressure
0.2～0.6MPa；
The temperature of described high-temperature calcination is 200～600 DEG C, and heating rate is 1～5 DEG C/min, and calcination time is 1～5h.
Further, application of the present invention is carried out as follows: by mesic hole hollow ball-shape titania/Tungstic anhydride. composite wood
Material mixes with Kynoar (PVDF) and grinds uniformly, adds 1-methyl-2-pyrrolidone (NMP) furnishing slurry, uses
This slurry is homogeneously applied in the conductive substrates of cleaning by scraper, and is dried at room temperature for, and afterwards this conductive substrates is placed in horse
Stove not carries out calcination processing, obtains described membrane electrode；
Wherein,
Described mesic hole hollow ball-shape titania/Tungstic anhydride. composite and Kynoar, the matter of 1-methyl-2-pyrrolidone
Amount ratio is 1:0.15～0.4:1～3；
The conductive substrates of described cleaning is: by conductive substrates respectively in toluene, acetone, dehydrated alcohol, deionized water ultrasonic clearly
Cold drying after washing 15min and obtain；Described conductive substrates is selected from FTO electro-conductive glass, ITO electro-conductive glass, flexibility are led
Electricity substrate, platinized platinum, aluminium flake or iron plate etc.；
Described slurry coating thickness in conductive substrates is 5～30 μm；
The temperature of described calcination processing is 400～700 DEG C, and heating rate is 1～5 DEG C/min, and calcination time is 1～5h.
The invention have the advantage that
(1) Tungstic anhydride. is used to be combined with titanium dioxide, it is possible to the energy gap of the titanium dioxide that effectively narrows so that it is can
By excited by visible light, improving the utilization rate to sunlight, Tungstic anhydride. can increase the acidity of titanium dioxide surface simultaneously, promotes dirt
The dye thing absorption on surface；
(2) composite is made membrane electrode, solve conventional powder catalyst difficulty and separate, be unfavorable for recycling, very
To causing secondary pollution problems, make titanium deoxide catalyst realize industrial applications and more go a step further；
(3) electro-catalysis and light-catalysed cooperative effect are utilized, it is possible to make light induced electron displacement under the effect of extra electric field
On negative electrode, thus promote that carrier is spatially separated, reduce h+-e-To compound, improve h+-e-Utilization rate, Jin Erti
High photoelectrocatalysis efficiency.
(4) accompanying drawing explanation
Fig. 1 is the SEM image of embodiment 1 intermediary hole hollow ball-shape titania/Tungstic anhydride. laminated film；
Fig. 2 is the XED collection of illustrative plates of embodiment 1 intermediary hole hollow ball-shape titania/Tungstic anhydride. laminated film；
Fig. 3 is that the UV, visible light of mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode that embodiment 1 prepares is unrestrained anti-
Penetrate collection of illustrative plates；
Fig. 4 is the energy gap collection of illustrative plates of mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode that embodiment 1 prepares；
Fig. 5 is that the prepared mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode of embodiment 1 is at illumination and dark bar
Ac impedance spectroscopy under part；
Fig. 6 be mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode of preparing of embodiment 1 simulated visible light with
Transient state photoelectric current collection of illustrative plates under sunlight.
(5) detailed description of the invention
Below by specific embodiment, the invention will be further described.Following example are only used for clearly illustrating the present invention
Technical scheme, and can not limit the scope of the invention with this.
Embodiment 1
(1) precise 10.000g titanyl sulfate, 2.800g ammonium metatungstate (titanyl sulfate in terms of titanium with ammonium metatungstate with tungsten
The ratio of the amount of the material of meter is 1:0.03), 2.160g citric acid, in 2L beaker, adds 1600mL deionized water, room temperature
Magnetic agitation 16h, until material is dissolved completely in water becomes colourless transparent solution.Then with the weak ammonia regulation of 2.7wt%
The pH of solution to 7.5, obtains precursor solution.
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 200 DEG C,
Material flow is 800mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) step (2) gained white powder samples is put in Muffle furnace and calcine, be raised to 300 DEG C from 30 DEG C, heating rate
Being 5 DEG C/min, temperature retention time is 2h, obtains titanium dioxide/Tungstic anhydride. composite 3.877g.
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-Methyl-2-Pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 450 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
The Analysis of Surface Topography of gained membrane electrode uses HitachiS-4700II type field emission scanning electron microscope to observe, its result
As shown in Figure 1.Thin film does not has big slight crack, is firmly combined with substrate, and thin film intermediary hole hollow ball is evenly distributed, and does not has big
Clustering phenomena.
Embodiment 2
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 3
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 550 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 4
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 600 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 5
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mixing is the most uniform, is subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by uniform for this slurry
Be coated on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will conduction
Glass is put in Muffle furnace, is raised to 650 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h, i.e. can be situated between
Hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 6
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 700 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 7
(1) precise 10.000g titanyl sulfate, 0.327g ammonium metatungstate (titanyl sulfate in terms of titanium with ammonium metatungstate with tungsten
The ratio of the amount of the material of meter is 1:0.01), 2.160g citric acid, in 2L beaker, adds 1600mL deionized water, room temperature
Magnetic agitation 16h, until material is dissolved completely in water becomes colourless transparent solution.Then with the weak ammonia regulation of 2.7wt%
The pH of solution to 7.5, obtains precursor solution.
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 8
(1) precise 10.000g titanyl sulfate, 4.765g ammonium metatungstate (titanyl sulfate in terms of titanium with ammonium metatungstate with tungsten
The ratio of the amount of the material of meter is 1:0.05), 2.160g citric acid, in 2L beaker, adds 1600mL deionized water, room temperature
Magnetic agitation 16h, until material is dissolved completely in water becomes colourless transparent solution.Then with the weak ammonia regulation of 2.7wt%
The pH of solution to 7.5, obtains precursor solution.
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 9
(1) precise 10.000g titanyl sulfate, 6.533g ammonium metatungstate (titanyl sulfate in terms of titanium with ammonium metatungstate with tungsten
The ratio of the amount of the material of meter is 1:0.07), 2.160g citric acid, in 2L beaker, adds 1600mL deionized water, room temperature
Magnetic agitation 16h, until material is dissolved completely in water becomes colourless transparent solution.Then with the weak ammonia regulation of 2.7wt%
The pH of solution to 7.5, obtains precursor solution.
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 10
(1) precise 10.000g titanyl sulfate, 10.059g ammonium metatungstate (titanyl sulfate in terms of titanium with ammonium metatungstate with tungsten
The ratio of the amount of the material of meter is 1:0.1), 2.160g citric acid, in 2L beaker, adds 1600mL deionized water, normal temperature magnetic
Power stirring 16h, until material is dissolved completely in water becomes colourless transparent solution.Then molten with the weak ammonia regulation of 2.7wt%
The pH of liquid to 7.5, obtains precursor solution.
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 11
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 160 DEG C,
Material flow is 800mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 12
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 180 DEG C,
Material flow is 800mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 13
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 220 DEG C,
Material flow is 800mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 14
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 240 DEG C,
Material flow is 800mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 15
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 200 DEG C,
Material flow is 400mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 16
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 200 DEG C,
Material flow is 600mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 17
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 200 DEG C,
Material flow is 1000mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 18
(1) with embodiment 1 step (1).
(2) being spray-dried by step (1) gained precursor solution, spray dryer inlet temperature is set to 200 DEG C,
Material flow is 1200mL/h, and air pressure is 0.35MPa, obtains white powder samples.
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the FTO electro-conductive glass of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will
Electro-conductive glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h,
To mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 19
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied on the ITO electro-conductive glass of cleaning, coating thickness, about 15 μm, is treated under room temperature that slurry is dried, will be led
Electricity glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h, the most available
Mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 20
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied in the titanium sheet substrate of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will conduct electricity glass
Glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h, i.e. can get mesoporous
Hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 21
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied in the aluminium flake substrate of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will conduct electricity glass
Glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h, i.e. can get mesoporous
Hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 22
(1) with embodiment 1 step (1).
(2) with embodiment 1 step (2).
(3) with embodiment 1 step (3).
(4) by step (3) gained titanium dioxide/Tungstic anhydride. composite 0.08g and Kynoar (PVDF) 0.02g
Mix and grind uniformly, being subsequently adding 1-methyl-2-pyrrolidone (NMP) 0.1mL furnishing slurry, with scraper by this slurry
Being uniformly applied in the iron plate substrate of cleaning, coating thickness, about 15 μm, treats under room temperature that slurry is dried, will conduct electricity glass
Glass is put in Muffle furnace, is raised to 500 DEG C from 30 DEG C, and heating rate is 3 DEG C/min, and temperature retention time is 2h, i.e. can get mesoporous
Hollow ball-shape titania/Tungstic anhydride. composite film electrode.
Embodiment 23
Using mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode of obtaining in embodiment 1 as working electrode, Pt
Electrode is to electrode, and saturated calomel electrode is reference electrode, uses three-electrode system to measure the photoelectrochemical behaviour of this membrane electrode.
The used Na that electrolyte is 0.5mol/L2SO4Aqueous solution, the electrolysis bath of band quartz window, 300W xenon lamp as light source,
Incident illumination filters infrared light through quartz tank and obtains ultraviolet-visible light (wave-length coverage 200～700nm, light intensity is 85
mW·cm-2, the filtered ultraviolet light filtering off below 420nm obtains visible ray, and light intensity is 15m W cm-2.Will during test
The directional light that xenon lamp produces is irradiated to be coated with the surface of the working electrode of photocatalyst, and coated area is 1cm*1cm, other
Part politef defat unsintered tape wraps up.Transient photocurrents test uses the bias of 0.5V, and data point gathers
Interval time is 0.2s.The illumination intermittent time is 20s.
As shown in Figure 6, mesic hole hollow ball-shape titania/Tungstic anhydride. composite film electrode photoelectric current under simulated visible light
Numerical value is 0.9 μ A/cm2, the photoelectric current numerical value under simulated solar irradiation is 3.75 μ A/cm2.It is significantly higher than Chinese patent (CN
102188961 A) disclosed in report unadulterated TiO under the conditions of same test2The photoelectric current numerical value of sample is 0.08
μA/cm2, the sample TiO of doping2The photoelectric current numerical value of-Si is 0.11 μ A/cm2, this has absolutely proved mesic hole hollow ball-shape dioxy
Change titanium/Tungstic anhydride. composite film electrode and there is good photoelectrochemical behaviour and application prospect.
Claims (10)
1. mesic hole hollow ball-shape titania/Tungstic anhydride. composite application in prepared by membrane electrode.
Apply the most as claimed in claim 1, it is characterised in that the method for described application is: by described medium hole hollow ball
Shape titanium dioxide/Tungstic anhydride. composite is modulated into slurry, is then homogeneously applied to by this slurry in the conductive substrates of cleaning,
Treat that slurry carries out calcination processing after drying, obtain described membrane electrode.
Apply the most as claimed in claim 1, it is characterised in that described mesic hole hollow ball-shape titania/Tungstic anhydride. is multiple
Condensation material uses spray drying high-temperature calcination two-step method to prepare.
Apply the most as claimed in claim 3, it is characterised in that described mesic hole hollow ball-shape titania/Tungstic anhydride. is combined
Material method as follows prepares: titanyl sulfate, ammonium metatungstate, citric acid are dissolved in deionized water, stirring at normal temperature 8～24h,
Then regulate pH to 7.0～8.0 with 2.5wt%～2.8wt% ammonia, obtain precursor solution, gained precursor solution is entered successively
Row is spray-dried, high-temperature calcination, prepares described mesic hole hollow ball-shape titania/Tungstic anhydride. composite；Described sulphuric acid
Oxygen titanium count with titanium count with tungsten with ammonium metatungstate, the ratio of the amount of the material of citric acid, deionized water is as 1:0.01～0.2:0.1～0.5:
1000～3000.
Apply the most as claimed in claim 4, it is characterised in that the condition of described spray drying is: inlet temperature 140～240 DEG C,
Material flow 400～1200mL/h, air pressure 0.2～0.6MPa.
Apply the most as claimed in claim 4, it is characterised in that the temperature of described high-temperature calcination is 200～600 DEG C, heat up
Speed is 1～5 DEG C/min, and calcination time is 1～5h.
Apply the most as claimed in claim 2, it is characterised in that described application is carried out as follows: by medium hole hollow ball
Shape titanium dioxide/Tungstic anhydride. composite mixes with Kynoar and grinds uniformly, adds 1-methyl-2-pyrrolidone furnishing
Slurry, is homogeneously applied to this slurry in the conductive substrates of cleaning with scraper, and is dried at room temperature for, afterwards by this conductive base
The end, is placed in Muffle furnace and carries out calcination processing, obtains described membrane electrode；Described mesic hole hollow ball-shape titania/tri-aoxidize
Composite tungsten material is 1:0.15～0.4:1～3 with Kynoar, the mass ratio of 1-methyl-2-pyrrolidone.
Apply the most as claimed in claim 7, it is characterised in that described conductive substrates is selected from FTO electro-conductive glass, ITO
Electro-conductive glass, flexible conducting substrate, platinized platinum, aluminium flake or iron plate.
Apply the most as claimed in claim 7, it is characterised in that described slurry coating thickness in conductive substrates is
5～30 μm.
Apply the most as claimed in claim 7, it is characterised in that the temperature of described calcination processing is 400～700 DEG C, heat up
Speed is 1～5 DEG C/min, and calcination time is 1～5h.
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