CN1974890A - Nanometer porous tungsten trioxide material and its prepn and application - Google Patents
Nanometer porous tungsten trioxide material and its prepn and application Download PDFInfo
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Abstract
The present invention relates to nanometer porous WO3 material, and is especially nanometer porous WO3 material formed through molecule self-assembling and with homogeneous structure, pore diameter of 60-150 nm, regular arrangement and (002) face oriented monoclinic system structure. The nanometer porous WO3 material is prepared through a constant current anode oxidation process with metal W substrate and electrolyte solution, which consists of inorganic fluoride sodium fluoride, potassium fluoride or ammonium fluoride and inorganic strong acid hydrofluoric acid, hydrochloric acid or sulfuric acid and has F- ion concentration of 0.05-0.3 mol/L and H+ ion concentration of 0.05-0.5 mol/L. The nanometer porous WO3 material has high photocatalytic capacity and is one kind of high efficiency photocatalyst.
Description
Technical field:
The present invention relates to the tungsten trioxide nano material, relating in particular to a kind of is the nanometer porous tungsten trioxide material of substrate with the tungsten, and its production and application.
Background technology:
Tungstic oxide is a kind of semiconductor nano material of indirect band gap transition, has good photoelectricity and gas-sensitive property, for making full use of the photoelectric characteristic of tungstic oxide, need prepare the nanometer porous tungsten trioxide material that pattern is regular, specific surface area is high.
Electrochemistry anodic oxidation is a kind of cheap and can make up the method for the vesicular nano material that the aperture is adjustable, pattern is regular on than big area, its ultimate principle is to be anode with highly purified metal, another kind of metal or carbon are done negative electrode, put into electrolytic solution, under the effect of extra electric field, ion etching anodic metallic surface in the ionogen just builds up into the certain pattern and the metal oxide of structure.
People such as Grimes (Mukherjee, N.; M.Paulose; Varghese, O.K.; Mor, G.K.; Grimes, C.A.J.Mater.Res.2003,18,2296-2299.) reported first the employing constant current anode oxidation process, prepare porous tungsten trioxide with the tungsten sheet in the oxalic acid ionogen, its aperture is 50-150nm, but because oxalic acid is a kind of weak acid, its etching power is limited, the shape irregularity in prepared hole.People such as Schmuki (Tsuchiya, H.; Macak, J.M.; Sieber, I.; Taveira, L.; Ghicov, A.; Sirotna, K.; Schmuki, P.Electrochem.Comm.2005,7,295-298.) adopt the constant voltage anonizing in Sodium Fluoride (NaF) electrolytic solution, also to prepare porous tungsten trioxide, the aperture is 100-150nm, and the regularity of its pattern has had further raising, but the hole is different, and superficial, specific surface area is not high.Though the introducing of fluorion has reduced the chemical energy of material surface, it is neutral that the NaF electrolyte ph is, and the shape in the hole of formation is regular not enough, and is also superficial.
Except the pattern of material, the crystalline structure of material also is the important factor that influences its photoelectrochemistry feature.People such as Santato (Santato, C.; Odziemkowski, M.; Ulmann, M.; Augustynski, J.J.Am.Chem.Soc.2001,123,10639-10649.) find that monoclinic WO 3 film has photocatalytic activity preferably than the blue region of other crystalline form in solar spectrum.Can also be further from more the microcosmic level---the crystal face level is investigated the photocatalytic activity of material.Crystal is generally followed in epitaxially grown process along the rule of some or several orientation preferentially growths, if crystal along the direction growth of a certain crystal face, then can be referred to as certain high preferred orientation growth.Yet up to the present also do not find report about bond material pattern and high preferred orientation research tungstic oxide photo-catalysis capability.Pattern is regular and have particular crystal plane orientation owing to still be unrealized, so the photoelectric characteristic of nanometer porous tungsten trioxide material is not also used better.
Summary of the invention:
The object of the present invention is to provide that a kind of material pattern is regular, particular crystal plane orientation, photoelectric characteristic nanometer porous tungsten trioxide material and its production and application preferably.The preparation method adopts anonizing, selects specific electrolytic solution and processing condition for use; Analyze the material pattern and the high preferred orientation of this tungsten trioxide nano material, and investigate its photocatalytic activity, a kind of photocatalyst of efficient stable is provided.
Nanometer porous tungsten trioxide material of the present invention, with the tungsten is substrate, it is characterized in that: the porous tungsten trioxide that is the even structure that forms by the molecule self assembling process, the aperture is 60nm to 150nm and regular shape, arranges regularly that crystalline structure is the oblique system of (002) planar orientation.
The preparation method of nanometer porous tungsten trioxide material of the present invention, be to be substrate with the tungsten, adopt electrochemistry anodic oxidation, it is characterized in that, the used electrolytic solution of anodic oxidation is made up of inorganic fluoride and inorganic acid, wherein inorganic fluoride comprises Sodium Fluoride, Potassium monofluoride or ammonium fluoride, inorganic acid comprises hydrofluoric acid, hydrochloric acid or sulfuric acid, the concentration of fluorion is 0.05-0.3mol/L in the electrolytic solution, hydrionic concentration is 0.05-0.5mol/L, anodic oxidation voltage is 40-70V, and the time is 30-180 minute, and the temperature of electrolytic solution is 5-40 ℃.
This preparation method also comprise before the anodic oxidation polishing of tungsten sheet and clean dry up, the tungsten sheet soaked several seconds with diluent hydrofluoric acid solution after the oxidation and with deionized water rinsing, last in the atmosphere of oxygen in 400-600 ℃ of conventional steps such as calcining down.
Preparation method of the present invention adopts the mixing solutions of inorganic fluoride and inorganic acid as electrolytic solution, be to combine fluorion can reduce material surface energy, reach the characteristics of etching power by force that hydrogen ion has under electric field action, this mixing solutions has relative demulcent anodic oxidation environment than simple hydrofluoric acid ionogen.Gentle relatively, isostatic condition provided by the invention is the precondition that tungstic oxide is realized the molecule self-assembly.The cardinal principle of self-assembly is under the synergy of intermolecular forces and spatial complementary effect, and molecule can spontaneously be concluded into stable structure by the effect of non-equivalence key.Owing to formed self-assembled structures, tungsten trioxide nano pore distribution of the present invention is even, and pattern is regular, and the size in hole and shape be homogeneous relatively, and the surface topography of material was compared with former same type of material and had greatly improved.
In order to strengthen the self-assembly effect in preparation process, anodic oxidation voltage and time can be selected earlier under 50-60V oxidation 30-60 minute, reduce voltage rapidly to 40-45V, continue oxidation 30-60 minute again.
Consider of the influence of electrolyte ion radius for self assembling process, electrolytic solution can preferentially be selected the mixing solutions of Sodium Fluoride and hydrofluoric acid, the concentration of Sodium Fluoride is 0.05wt%-0.15wt%, the concentration of hydrofluoric acid is 0.10% (V/V)-0.20% (V/V), the concentration that is fluorion is 0.09-0.25mol/L, and hydrionic concentration is 0.08-0.20mol/L.
There are certain relation the aperture of nanoporous and bath composition, voltage and time, but temperature is most important factor, and the aperture is with anodised temperature variation, and temperature is high more, and the aperture of nanoporous is more little, and the optimum temperature range of electrolytic solution is 15-25 ℃.The pore diameter range of nanoporous of the present invention be 60nm to 150nm, the material nano aperture difference for preparing on same tungsten sheet is no more than 30nm.And the aperture of the porous tungsten trioxide nanoporous for preparing in other previous reports surpasses 50nm.
Calculation of parameter by X-ray diffraction (XRD) figure draws, and tungstic oxide crystalline structure of the present invention is an oblique system, and the crystalline growth is along (002) face preferred growth.
The application of nanometer porous tungsten trioxide material of the present invention on photochemical catalysis or photoelectrocatalysis.Light-catalyzed reaction can be adopted three-electrode system, makes the work electrode with porous tungsten trioxide, and platinum electrode or nickel electrode etc. is made counter electrode, and saturated calomel electrode or silver/silver chloride electrode are reference electrode.Respectively three electrodes are received on the electrochemical workstation, added the electrolytic solution that contains target compound then, under UV-light or visible light radiation, light-catalyzed reaction can take place.Photoelectrocatalysis and photochemical catalysis difference are to add a bias voltage between working electrode and reference electrode, and the electronics of photoexcitation is led away, can reduce separating of electronics and hole, thereby improve the effect of light-catalyzed reaction.
If less than the given preparation condition of unabridged version invention, the porous tungsten trioxide of formation (hereinafter to be referred as contrast material) has than big-difference with material of the present invention.For example anodic oxidation voltage and time were made as under 20V oxidation 30 minutes, the contrast material crystalline structure of preparing is (020) planar orientation, and pattern is a kind of disordered structure.Find that through experiment compare with this contrast material, material of the present invention has stronger photo-catalysis capability, this tungstic oxide that (002) of the present invention high preferred orientation is described to a certain extent has stronger photo-catalysis capability.
The nanometer porous tungsten trioxide material of the present invention's preparation has following characteristics and advantage:
1) porous tungsten trioxide of the present invention, the distribution in its hole is more even, and pattern is more regular, has formed the structure of self-assembly, and its crystalline structure is an oblique system, and crystalline growth is with the orientation preferentially growth of (002) face, and the crystal degree is very high.
2) preparation method of the present invention is simple, and operation is with low cost easily, and favorable reproducibility is fit to scale operation.
3) porous tungsten trioxide of the present invention has good photoelectrochemical property, has stronger photo-catalysis capability, is a kind of photocatalyst efficiently.
Description of drawings:
The stereoscan photograph on Fig. 1 nanometer porous tungsten trioxide material of the present invention surface, magnification is 10000 times.The tungsten oxide nanometer hole that forms is very orderly, and the size in hole and shape are more equal, has formed the structure of self-assembly.
The surface scan electromicroscopic photograph of a kind of contrast material that forms less than unabridged version invention preparation condition of Fig. 2.Magnification is 10000 times.Surface topography is a kind of unordered structure.
X-ray diffraction (XRD) figure of two kinds of nanometer porous tungsten trioxide materials of Fig. 3, X-coordinate is the diffraction angle (2 θ) of twice, ordinate zou is the intensity of diffraction peak.
The corresponding porous tungsten trioxide of the present invention of curve among the figure (a), the corresponding contrast material of curve (b).The crystal face of expression such as (002) among the figure, (200), (020) and (120) diffraction peak correspondence, the diffraction peak of the tungsten of W (110), W (200) and W (211) expression substrate.According to the diffraction angle of curve (a) diffraction peak correspondence, calculating porous tungsten trioxide of the present invention is that crystalline structure is the monoclinic crystal of (002) planar orientation; (b) calculates according to curve, and the crystalline structure of this contrast material is the monoclinic crystal of (020) planar orientation.
Fig. 4 photocatalytic degradation organic compound Pentachlorophenol synoptic diagram.
Four curves are corresponding respectively among the figure: natural degradation, directly in the degraded under the irradiation of high voltage mercury lamp, with of the irradiation of a kind of contrast material at high voltage mercury lamp under photocatalytic degradation, with nanometer porous tungsten trioxide material of the present invention photocatalytic degradation under high voltage mercury lamp radiation.
According to the curve among the figure, make photocatalyst with porous tungsten trioxide of the present invention, after two hours, 97.3% Pentachlorophenol is degraded, and can only degrade 66.0% at most with other materials and method at high voltage mercury lamp radiation.
Embodiment:
Embodiment 1 cuts into the size of 25 * 50mm with the tungsten sheet, polishes successively with 400 orders, 600 orders, 800 orders, 1000 orders and 1200 purpose sand paper respectively then, and links to each other with lead and to make electrode; Respectively the tungsten sheet is cleaned at acetone, Virahol, methyl alcohol and deionized water for ultrasonic ripple, and dry up with nitrogen; Pour the Sodium Fluoride (NaF) of 0.2wt% and 0.3% (V/V) hydrofluoric acid (HF) into electrolyzer by 1: 1 mixed after good, the concentration of fluorion is 0.11mol/L in the electrolytic solution, and hydrionic concentration is 0.086mol/L.With the tungsten sheet is anode, and platinum electrode is a negative electrode, the homo(io)thermism of control electrolytic solution in 20 ± 1 ℃, oxidation 60 minutes under 60V earlier, and then oxidation 30 minutes under 40V; Tungsten sheet after the oxidation is used several seconds of hydrofluoric acid dips of dilution, and use deionized water rinsing; The last 4h that in the atmosphere of oxygen, under 450 ℃, calcines.The nanometer porous tungsten trioxide material stereoscan photograph of the self-assembled structures that makes as shown in Figure 1, the tungsten oxide nanometer hole of Xing Chenging is very orderly as can be seen, and the size in hole and shape homogeneous relatively, having formed the structure of self-assembly, the measurement mean pore size is 80nm.X-ray diffraction (XRD) figure calculates the oblique system that crystalline structure is (a 002) planar orientation according to the angle gauge of diffraction peak correspondence shown in Fig. 3 curve (a).
The contrast experiment: the NaF and 0.3% of 0.2wt% (V/V) HF by the ionogen of 1: 1 mixed under 20V anode Tungsten oxide 99.999 sheet 30 minutes, the stereoscan photograph of the porous tungsten trioxide (contrast material) that forms as shown in Figure 2, the surface topography of Xing Chenging is a kind of unordered structure as can be seen.Its XRD figure is calculated the oblique system that crystalline structure is (a 020) planar orientation according to the angle gauge of diffraction peak correspondence shown in Fig. 3 curve (b).
Embodiment 2 presses the preparation method of the present invention of embodiment 1, just electrolytic solution is changed into Sodium Fluoride (NaF) and the 0.5mol/L sulfuric acid (H of 0.6wt%
2SO
4) by 1: 1 mixed, promptly the concentration of fluorion was 0.07mol/L, hydrionic concentration is 0.5mol/L.Make the nanometer porous tungsten trioxide material of self-assembled structures, its mean pore size is about 100nm, and crystalline structure is with embodiment 1.
Embodiment 3 presses the preparation method of the present invention of embodiment 1, just electrolytic solution is changed into the ammonium fluoride (NH of 1.0wt%
4F) and 0.5mol/L hydrochloric acid (HCl) by 1: 1 mixed, promptly the concentration of fluorion is 0.24mol/L, hydrionic concentration is 0.25mol/L.Make the nanometer porous tungsten trioxide material of self-assembled structures, its mean pore size is about 120nm, and crystalline structure is with embodiment 1.
Embodiment 5 presses the preparation method of the present invention of embodiment 1, and just anode oxidation method be first oxidation 60 minutes under 50V, and then oxidation 120 minutes under 40V.The nanometer porous tungsten trioxide material of the self-assembled structures that makes, its mean pore size are about 100nm, and crystalline structure is with embodiment 1.
Embodiment 6 presses the preparation method of the present invention of embodiment 1, and just the temperature with electrolytic solution is controlled at 35 ℃.The nanometer porous tungsten trioxide material of the self-assembled structures that makes, its mean pore size are about 70nm, and crystalline structure is with embodiment 1.
Embodiment 7 presses the preparation method of the present invention of embodiment 1, and just the temperature with electrolytic solution is controlled at 10 ℃.The nanometer porous tungsten trioxide material of the self-assembled structures that makes, its mean pore size are about 130nm, and crystalline structure is with embodiment 1.
Embodiment 8 is the contrast experiment of photocatalyst for degrading organic pollutant Pentachlorophenol by porous tungsten trioxide of the present invention and contrast material that the preparation method of embodiment 1 makes.Be reflected in the quartz glass reactor and carry out.
In the middle of the solution of target compound Pentachlorophenol, add and contain the sodium sulfate of 0.01mol/L as ionogen, porous tungsten trioxide with (002) of the present invention high preferred orientation is made the work electrode, electrode such as platinum electrode or nickel electrode is made counter electrode, saturated calomel electrode or silver/silver chloride electrode are that reference electrode constitutes three-electrode system, respectively three electrodes are received on the electrochemical workstation, can be begun light-catalyzed reaction.What light source used is the high voltage mercury lamp of 300W, and its predominant wavelength is 365nm.Through two hours UV-irradiation, 97.3% Pentachlorophenol was degraded.If add the bias voltage of 0.2V, the degradation rate of Pentachlorophenol can reach more than 99.0%.
Repeat above-mentioned experiment, just working electrode is changed into the contrast material of (020) high preferred orientation, have only 66.0% Pentachlorophenol to be degraded after two hours.
Photocatalytic degradation organic compound Pentachlorophenol effect synoptic diagram as shown in Figure 4.In Fig. 4, give the natural degradation of Pentachlorophenol, direct photolytic curve under the irradiation of high voltage mercury lamp.
The porous tungsten trioxide of proof the present invention preparation has the ability of stronger photocatalysis degradation organic contaminant, and has proved that to a certain extent (002) crystal face has higher photo-catalysis capability than (020) crystal face.The concentration of Pentachlorophenol is that (PU1580/UV1575) analysis obtains for HPLC, JASCO by high performance liquid chromatography.
Claims (6)
1. one kind is the nanometer porous tungsten trioxide material of substrate with the tungsten, it is characterized in that: the porous tungsten trioxide that is the even structure that in the molecule self assembling process, forms, the aperture is 60nm to 150nm and regular shape, arranges regularly that crystalline structure is the oblique system of (002) planar orientation.
2. the preparation method of the described nanometer porous tungsten trioxide material of claim 1, adopt constant current anode oxidation process, with the tungsten is anode, it is characterized in that: electrolytic solution is made up of inorganic fluoride and inorganic acid, wherein inorganic fluoride comprises Sodium Fluoride, Potassium monofluoride or ammonium fluoride, inorganic acid comprises hydrofluoric acid, hydrochloric acid or sulfuric acid, the concentration of fluorion is 0.05-0.3mol/L in the electrolytic solution, hydrionic concentration is 0.05-0.5mol/L, anodic oxidation voltage is a 40-70V voltage, time is 30-120 minute, the temperature of electrolytic solution is 5-40 ℃, form the porous tungsten trioxide of even structure in the molecule self assembling process, crystal is along the orientation preferentially growth of (002) crystal face.
3. preparation method according to claim 2 is characterized in that: anodic oxidation voltage and time were reduced voltage rapidly to 40-45V, continuation oxidation 30-60 minute under 50-60V oxidation 30-60 minute earlier.
4. preparation method according to claim 3, it is characterized in that: electrolytic solution is made up of Sodium Fluoride and hydrofluoric acid, wherein the weight percent concentration of Sodium Fluoride is 0.05%-0.15%, and the concentration of volume percent of hydrofluoric acid is 0.10%-0.20%, and the temperature of electrolytic solution is 15-25 ℃.
5. the described nanometer porous tungsten trioxide material of claim 1 is in the application of photochemical catalysis or photoelectrocatalysis.
6. nanometer porous tungsten trioxide material according to claim 5 is in the application of photochemical catalysis or photoelectrocatalysis, three-electrode system is adopted in photochemical catalysis or photoelectrocatalysis reaction, make the work electrode with crystalline structure for the oblique system porous tungsten trioxide of (002) planar orientation, platinum electrode or nickel electrode etc. are made counter electrode, saturated calomel electrode or silver/silver chloride electrode are reference electrode, add the electrolytic solution that contains target compound, under UV-light or visible light radiation, light-catalyzed reaction takes place.
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