CN102949990A - Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method - Google Patents
Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method Download PDFInfo
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Abstract
The invention relates to a macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method. The inner layer of the electrode is a titanium matrix, and the surface layer is a composite layer of SnO2 and TiO2 nanotubes (TiO2NTs). On the surface of a titanium matrix TiO2NTs array obtained by an anodization treatment, Sb doped SnO2 is assembled by a block copolymer soft template method, thus obtaining the macroporous tin dioxide-titanium dioxide nanotube composite electrode (Mp-SnO2/TiO2NTs) with a cribriform surface. The composite electrode prepared by the invention has large SnO2 loading capacity, the particle diameter is small, the pore size distribution is uniform, and light transmission of an SnO2 film is strong. The SnO2 film is tightly combined with a titanium matrix TiO2NTs skeleton. The electrode surface is smooth and even. The electrode not only has the characteristics of wide light absorption range, strong photocurrent response, excellent electrocatalytic property and high photoelectric synergetic catalytic efficiency, but also has stable chemical properties. In addition, with a simple preparation process and a low preparation cost, the electrode provided in the invention can be effectively used for degradation treatment of dye wastewater and organic wastewater difficult to conduct biochemical oxidation, thus having extensive economic and social benefits.
Description
Technical field
The present invention relates to materials chemistry, Environmental Chemistry and photoelectrocatalysis technical field, especially relate to a kind of macropore tin ash with optoelectronic integration catalysis-titania nanotube combination electrode material and preparation method thereof.
Background technology
Electro-catalysis and photocatalysis are as two kinds of different high-level oxidation technologies, and increasing environmental science worker is applied to the degradation treatment of organic wastewater.Photocatalysis has distinct catalysis characteristics and different Conversion of Energy forms with electro-catalysis.If these two kinds of high-level oxidation technologies can be realized at same electrode surface simultaneously, be expected between two kinds of catalytic reactions, realize synergy, be conducive to improve photoelectrocatalysioxidization oxidization ability and the degradation efficiency of electrode.Therefore, the emphasis of this technology also is difficult point, is to find or to construct the catalytic electrode material that has simultaneously excellent electrocatalysis characteristic and photocatalysis performance.
Titanium dioxide is a kind of good photochemical catalyst, wherein upright orderly titanium-based titanium dioxide nanotube (TiO
2NTs) than the TiO of other structures
2More efficient, can easily make by the electrochemical anodic oxidation method.The TiO of this high-sequential array arrangement
2NTs has larger specific area and high surface energy, so it has higher photocatalysis efficiency.Yet, TiO
2Have low electric conductivity and poor electro-catalysis ability, so TiO
2NTs is suitable as a kind of high efficiency photochemical catalyst, but is not suitable as eelctro-catalyst.From the electrochemical oxidation angle, dimensionally stable anode (DSA) owing to having low chlorine evolution potential and be used widely in chlorine industry.But, can't be widely applied to the processing aspect of pollutant because the oxygen evolution potential of DSA is lower.And antimony-doped stannic oxide anodic coating electrode has higher oxygen evolution potential and excellent electrocatalysis characteristic, can reduce and analyse the energy consumption of oxygen at hydrolysis, and then raising current efficiency, therefore it is fit to use be combined at electrochemistry oxygen very much, especially the environment degradable of the electrochemical oxidation in aqueous medium and difficult biochemical pollutant.Tin ash is a kind of semi-conducting material, and energy gap is 3.88eV, although it is good eelctro-catalyst, its photocatalysis efficiency is very low, and ultraviolet light is had cut-off effect.
We consider and can take full advantage of TiO
2The structure of NTs, it can be used as desirable " container " or " support " assembles the antimony-doped stannic oxide eelctro-catalyst from microstructure, and then constructs out the photoelectrocatalysis agent material of novel structure.The methods such as the dipping by collosol and gel or spin coating can be easily be assembled into TiO with the tin ash of antimony dopant
2NTs is inner and surperficial, is easy to prepare SnO
2/ TiO
2-NTs catalyst.Yet a small amount of antimony must mix SnO
2Improving its electrocatalysis characteristic, but the doping of Sb can affect TiO
2The light absorption of NTs.Therefore, we set about two-dimentional macropore SnO
2Be assembled into the TiO of one dimension
2Construct out the photoelectrocatalysis agent material of novel structure on the NTs, Self-Assembling of Block Copolymer becomes orderly liquid crystal (LC) structure as soft template, the SnO that then Sb is mixed
2Be assembled into TiO
2On the NTs.Soft template prepares sequential 2 D macropore SnO after removing by roasting
2The preparation of this catalyst is a step assembling process, and operation is simple and save time.The combination electrode material of this structure of gained has following advantage.At first, the SnO of this macropore
2Film is conducive to passing through of light and TiO
2NTs is to the ultraviolet Optical Absorption; Secondly, according to band theory SnO
2And TiO
2Between be anti-phase doping, this combination is suitable for separating of light induced electron and hole, has improved photoelectric transformation efficiency; At last, this preparation method has given SnO
2Particle diameter is little, ordered arrangement and the large characteristics of load capacity, and these will improve the electrocatalysis characteristic of catalyst greatly.This electrode material research and development not only have important theory significance, and satisfied the demand of practical application.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of electrochemical impedance to reduce for the defective that overcomes above-mentioned prior art existence, the macropore tin ash that electricity conversion and photoelectrocatalysioxidization oxidization degradation efficiency improve-titania nanotube combination electrode material and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
Macropore tin ash-titania nanotube combination electrode is characterized in that, this combination electrode internal layer is the titanium substrate, and the top layer is SnO
2And TiO
2The composite bed of NTs, SnO in this layer
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Film is penetrating coarse pored, and the combination electrode smooth surface is smooth, and the light absorption wavelength scope is widened 425nm, and energy gap is 2.93eV.
The thickness of described titanium substrate is 0.1～0.5mm, described SnO
2And TiO
2The thickness of the composite bed of NTs is 500～800nm, SnO
2Particle diameter is 10～20nm.
The preparation method of macropore tin ash-titania nanotube combination electrode is characterized in that, the method prepares titanium matrix TiO by the anodic titanium sheet
2Then the NTs array mixes the Sn of antimony (Sb) at its area load with the block copolymer soft template method
2+Colloidal sol namely obtains macropore tin ash-titania nanotube combination electrode finally by heat treatment.
The method specifically may further comprise the steps:
(1) be that 0.1～0.5mm pure metallic titanium sheet carries out sanding and polishing with sand paper and cleans up with thickness, to contain 0.5～1wt%NH
4F, 1.0～1.5wt%Na
2SO
4, the aqueous solution of 5～15wt%PEG400 is electrolyte solution, take the titanium sheet as working electrode, platinized platinum is to electrode in solution, carries out electrochemical anodic oxidation and processes 1～3h, obtains orderly TiO at titanium-based surface
2The NTs array electrode adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and program temperature is 1～5 ℃ of min
-1, heat treatment temperature is 400～550 ℃, heat treatment time is 3～5h, obtains orderly TiO
2NTs;
(2) high-molecular block copolymer is soluble in water, the mass ratio of control high-molecular block copolymer and water is (1～2): 1, form solution A, with SnCl
22H
2O, SbCl
3Be dissolved in the 18wt% hydrochloric acid solution control SnCl
22H
2O, SbCl
3And the mass ratio of 18wt% hydrochloric acid be (1～3): (0.05～0.15): 3, form solution B, solution A and solution B are (4～6) in mass ratio: (10～15) mix and stir transparent, must C colloidal sol behind ageing 10～24h;
(3) the orderly TiO for preparing with step (1)
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C colloidal sol and the submergence TiO of step (2) preparation
2Leave standstill 10～30min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 24～48h, at 100 ℃～300 ℃ lower oven dry 1～3h, at last at 450～600 ℃ of lower pyrolysis oxidation 1～3h, is namely obtained Mp-SnO
2/ TiO
2The NTs combination electrode.
High-molecular block copolymer described in the step (2) is the nonionic molecules surfactants such as styrylphenol polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether or polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer (PEO-PPO-PEO or EOn-POm-EOn).
Compared with prior art, it is photochemical catalyst that the present invention chooses the TiO2 with good ultraviolet photoresponse, then it is designed to upright orderly nanostructured TiO2NTs, again the eelctro-catalyst SnO of excellent in design
2Macropore film and TiO
2NTs assembles, the photocatalysis effect that the combination electrode of acquisition not only shows, and the stability that this structure can the Effective Raise electrode.Compare with traditional oxide electrode, the present invention has following advantage:
(1) the present invention adopts the upright orderly TiO on the metal titanium sheet
2The NTs array is carrier material, and this nano-tube array high-sequential is easy to use, and very large specific area and load volume can be provided, and has excellent photocatalysis performance.Its porous pipe type structure has good dispersive property and template effect for eelctro-catalyst, more is conducive to strong bonded and the load of catalyst.Simultaneously, the upright TiO of growth in situ
2The NTs array preparation is easier, economical, and its plank frame can directly as the electro-catalyst carrier material, need not to be coated on other carriers;
(2) will mix the Sn of Sb by the method for block copolymer soft template
2+Collosol and gel successfully is assembled into has good light catalytic activity TiO
2The NTs surface makes macropore SnO
2/ TiO
2The NTs electrode has been realized the perfect adaptation of photocatalysis and electro-catalysis at same electrode surface.Optical Electro-Chemistry by system experimental results show that combination electrode has overcome the SnO that mixes Sb again
2Film has kept TiO to weakening and the interference of ultraviolet light
2The photocatalysis performance that NTs is good has overcome SnO simultaneously
2And TiO
2NTs respectively separately as the shortcoming of eelctro-catalyst and photochemical catalyst poor efficiency, dispersion, demonstrates efficient synergy, is embodied in electrochemical impedance and reduces, and electricity conversion improves and the raising of photoelectrocatalysioxidization oxidization degradation efficiency;
(3) the eelctro-catalyst SnO that physicochemical properties are stable
2Introducing not only effectively protected photochemical catalyst TiO
2NTs improves its stability, and can be with coupling because mutual doping produces between two kinds of oxides, and the band gap width of combination electrode narrows down, and absorbs the band edge red shift, effectively promote it to the visible waveband Optical Absorption, and the method is simple to operate, a load moulding.
Description of drawings
Fig. 1 is the Mp-SnO of embodiment 1 preparation
2/ TiO
2The scanning electron microscope (SEM) photograph of NTs combination electrode, illustration are titanium base TiO
2The scanning electron microscope (SEM) photograph of NTs;
Fig. 2 is the Mp-SnO of embodiment 1 preparation
2/ TiO
2The UV-vis DRS spectrogram of NTs combination electrode;
Fig. 3 is the Mp-SnO of embodiment 1 preparation
2/ TiO
2The NTs combination electrode is the variation of photoelectric current under UV-irradiation (365nm) in 1M KOH solution, (a) TiO
2NTs is dark; (a ") TiO
2The NTs ultraviolet lighting; (b) SnO
2/ TiO
2NTs is dark; (b ") SnO
2/ TiO
2The NTs ultraviolet lighting
Fig. 4 is the Mp-SnO of embodiment 1 preparation
2/ TiO
2The NTs combination electrode is to the photoelectrochemical degradation of p-nitrophenol (PNP) and independent light degradation and electric degradation efficiency contrast of degrading.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Macropore tin ash-titania nanotube combination electrode and preparation method specifically may further comprise the steps:
(1) 0.15mm titanium sheet (99.9%) is used 120 successively
#, 320
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface smooth, and then each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water.Anodization electrolyte consists of the NaF of 0.5wt%, 1.0wt%Na
2SO
4With 5wt%PEG400 ethylene glycol be in the mixed solution of solvent, take the titanium sheet as working electrode, platinized platinum is to electrode, control both end voltage constant 20V, constant 25 ℃ of reaction temperature is carried out electrochemical anodic oxidation and is processed 1h.Adopt temperature programming to heat-treat in tube furnace at the electrode for preparing, program temperature is 2 ℃ of min
-1, heat treatment temperature is 450 ℃, heat treatment time is 3h;
(2) the 5g high-molecular block copolymer is dissolved in the 5g water, forms solution A.With 1gSnCl
22H
2O, 0.05gSbCl
3Be dissolved in the 3.0g 18wt% hydrochloric acid solution, form solution B.A and B solution is more transparent than mix and blend with 2: 5 quality, get C colloidal sol behind the ageing 10h.
(3) the orderly TiO that step (1) is prepared
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C solution and the submergence TiO of step (2) preparation
2Leave standstill 10min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 24h, is dried 1h at 100 ℃, 300 ℃ of lower 1h that keep, pyrolysis oxidation 1h in 450 ℃ of lower oxygen atmospheres makes Mp-SnO at last
2/ TiO
2The NTs combination electrode.
Mp-SnO
2/ TiO
2NTs combination electrode surface topography uses SEM to characterize, and sees Fig. 1, and wherein illustration is highly upright orderly titanium base TiO
2The SEM photo of NTs substrate can be found out TiO on scheming
2NTs forms the circular ports of rule mostly, and caliber is 60～100nm, and each independent nanotube Diameter distribution is even, arranges fine and close.Mp-SnO
2/ TiO
2NTs combination electrode surface, SnO
2The macroporous structure of film is penetrating, and diameter is distributed as 150～400nm; SnO
2Load capacity is large, and particle diameter is little, the particle diameter distribution uniform, diameter 10～20nm and with titanium base TiO
2The NTs skeleton is in conjunction with tight, and electrode surface is smooth smooth.This sieve shape macroporous structure is conducive to seeing through of light, thereby has improved substrate titanium dioxide to ultraviolet Optical Absorption and photocatalysis efficiency.
Fig. 2 is TiO
2NTs is with the SnO of spin-coating method preparation
2/ TiO
2NTs and Mp-SnO
2/ TiO
2The UV, visible light of NTs combination electrode overflows launches figure, as can be seen from the figure SnO
2And TiO
2After compound, owing to being with coupling, the absorption band edge is from the 385nm red shift of original titanium dioxide to 420nm, and compares Mp-SnO
2/ TiO
2The NTs combination electrode does not weaken in the absorption in ultraviolet light zone, keeps original good UV absorption ability.
Adopt three-electrode electro Chemical to measure system, on the CHI660c electrochemical workstation, the TiO to prepare respectively
2NTs and SnO
2/ Fe
2O
3The NTs combination electrode is working electrode, and platinum electrode is to electrode, and saturated calomel electrode (SCE) is reference electrode, measures the illumination front and back photoelectric current of electrode with executing biased variation in 1M KOH solution, sees Fig. 3, TiO before and after the UV-irradiation
2The dark current of NTs and photoelectric current are respectively 0.01mA cm
-2(a) and 0.7mA cm
-2(a '), and Mp-SnO
2/ TiO
2The dark current of NTs and photoelectric current are respectively 0.2mA cm
-2(b) and 1.2mAcm
-2(b ').
The macropore tin ash of the employing embodiment 1 preparation-titania nanotube combination electrode photoelectric integral highly toxic p-nitrophenol of catalyzing oxidizing degrading high concentration (PNP) dye wastewater.
Light, Electrocatalysis Degradation carry out in the semicircle electrochemical reaction cell in single pond, add a set of cups with recirculated water, and the maintenance temperature of reaction system is room temperature.Take the preparation electrode as anode, the titanium sheet is to electrode, electrode spacing 1cm, electrode area is 8cm
2, to contain 0.1mol L
-1Na
2SO
4Electrolytical 200mg L
-1PNP solution is as dye wastewater, and reaction volume is 100mL, degraded current density 20mAcm
-2, visible light source is that optical energy density is 3mW/cm
2UV-irradiation (365nm), analyze in the sampling of different degradation time.Use Agilent1100 high performance liquid chromatograph (HPLC) to analyze the immediate reaction concentration of PNP.The result shows, as shown in Figure 4, use combination electrode to process 4h after, (PCMp-SnO in the independent ultraviolet catalytic degradation process
2/ TiO
2NTs), the clearance of PNP is 17%, compares TiO
2The upper independent photocatalysis (PCTiO of NTs
2NTs) clearance has improved 4.5%; (ECMp-SnO in the independent By Electro-catalytic Oxidation Process process
2/ TiO
2NTs), the clearance of PNP is 75.5%; Yet, (PEC Mp-SnO in the photoelectric integral catalyzing oxidizing degrading process
2/ TiO
2NTs), the clearance of PNP is 98%, and the photoelectric-synergetic effect is so that the PNP clearance has improved 5.5%.
Embodiment 3
2,4 of the macropore tin ash of employing embodiment 1 preparation-titania nanotube combination electrode photoelectric integral catalyzing oxidizing degrading high toxicity bio-refractory, 6-trichlorophenol, 2,4,6,-T (TCP) simulated wastewater.
Light, Electrocatalysis Degradation carry out in the semicircle electrochemical reaction cell in single pond, add a set of cups with recirculated water, and the maintenance temperature of reaction system is room temperature.Take the preparation electrode as anode, the titanium sheet is to electrode, electrode spacing 1cm, electrode area is 8cm
2, to contain 0.1mol L
-1Na
2SO
4Electrolytical 100mg L
-1TCP solution is as dye wastewater, and reaction volume is 100ml, degraded current density 20mA cm
-2, light source is that optical energy density is 3mW/cm
2Ultraviolet light (365nm), analyze in the sampling of different degradation times.Use Agilent1100 high performance liquid chromatograph (HPLC) to analyze the immediate reaction concentration of TCP, the result shows, after processing through combination electrode 3h, in the independent Photocatalytic Degradation Process, the clearance of TCP is 20%; In the independent By Electro-catalytic Oxidation Process process, the clearance of TCP is 65%; Yet in the photoelectric integral catalyzing oxidizing degrading process, the clearance of TCP reaches 96%, and the photoelectric-synergetic effect is so that the clearance of TCP has improved 11%.
Embodiment 4
Macropore tin ash-titania nanotube combination electrode and preparation method is by preparing titanium matrix TiO in anodization
2On the NTs array surface, soft template method is constructed macropore SnO
2Film prepares Mp-SnO
2/ TiO
2The NTs combination electrode specifically may further comprise the steps:
1) 0.25mm titanium sheet (99.9%) is used 120 successively
#, 320
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface smooth, and then each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water.Anodization electrolyte consists of the NaF of 0.8wt%, 1.2wt%Na
2SO
4With 10wt%PEG400 ethylene glycol be in the mixed solution of solvent, take the titanium sheet as working electrode, platinized platinum is to electrode, control both end voltage constant 20V, constant 25 ℃ of reaction temperature is carried out electrochemical anodic oxidation and is processed 2h.Adopt temperature programming to heat-treat in tube furnace at the electrode for preparing, program temperature is 3 ℃ of min
-1, heat treatment temperature is 500 ℃, heat treatment time is 2h;
(2) the 8g high-molecular block copolymer is dissolved in the 5g water, forms solution A.With 1.5gSnCl
22H
2O, 0.1gSbCl
3Be dissolved in the 3.0g 18wt% hydrochloric acid solution, form solution B.A and 1: 3 quality of B solution is more transparent than mix and blend, get C colloidal sol behind the ageing 18h.
(3) the orderly TiO that step (1) is prepared
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C solution and the submergence TiO of step (2) preparation
2Leave standstill 20min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 36h, is dried 1.5h at 100 ℃, 300 ℃ of lower 1.5h that keep, pyrolysis oxidation 2h in 500 ℃ of lower oxygen atmospheres makes Mp-SnO at last
2/ TiO
2The NTs combination electrode.
The internal layer of the macropore tin ash for preparing-titania nanotube combination electrode is the titanium substrate, and thickness is 0.25mm, and the top layer is macropore SnO
2Film and TiO
2The composite bed of NTs, thickness are 500nm, SnO
2Large bore dia about 300nm, SnO in the composite bed
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Grain diameter is 12nm, electrode surface is smooth smooth, the visible light-responded scope of this combination electrode reaches 420nm, energy gap is 2.90eV, and the visible light photoelectric transformation efficiency has reached 35%, and impedance is reduced to 150 Ω, PhotoelectrocatalytiPerformance Performance is excellent, in the optoelectronic integration Oxidative Degradation Process of high concentration poisonous organic wastewater, show very strong photoelectrocatalysis synergy, greatly improved the efficient of catalyzing oxidizing degrading.
Embodiment 5
Macropore tin ash-titania nanotube combination electrode and preparation method is by preparing titanium matrix TiO in anodization
2On the NTs array surface, soft template method is constructed macropore SnO
2Film prepares Mp-SnO
2/ TiO
2The NTs combination electrode specifically may further comprise the steps:
1) 0.35mm titanium sheet (99.9%) is used 120 successively
#, 320
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface smooth, and then each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water.Anodization electrolyte consists of the NaF of 1wt%, 1.5wt%Na
2SO
4With 15wt%PEG400 ethylene glycol be in the mixed solution of solvent, take the titanium sheet as working electrode, platinized platinum is to electrode, control both end voltage constant 20V, constant 25 ℃ of reaction temperature is carried out electrochemical anodic oxidation and is processed 3h.Adopt temperature programming to heat-treat in tube furnace at the electrode for preparing, program temperature is 5 ℃ of min
-1, heat treatment temperature is 550 ℃, heat treatment time is 3h;
(2) the 10g high-molecular block copolymer is dissolved in the 5g water, forms solution A.With 3gSnCl
22H
2O, 0.15gSbCl
3Be dissolved in the 3.0g 18wt% hydrochloric acid solution, form solution B.A and 1: 2 quality of B solution is more transparent than mix and blend, get C colloidal sol behind the ageing 24h.
(3) the orderly TiO that step (1) is prepared
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C solution and the submergence TiO of step (2) preparation
2Leave standstill 30min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 48h, is dried 2h at 100 ℃, 300 ℃ of lower 1h that keep, pyrolysis oxidation 3h in 600 ℃ of lower oxygen atmospheres makes Mp-SnO at last
2/ TiO
2The NTs combination electrode.
The internal layer of the macropore tin ash for preparing-titania nanotube combination electrode is the titanium substrate, and thickness is 0.25mm, and the top layer is macropore SnO
2Film and TiO
2The composite bed of NTs, thickness are 700nm, SnO
2Large bore dia about 400nm, SnO in the composite bed
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Grain diameter is 15nm, electrode surface is smooth smooth, the visible light-responded scope of this combination electrode reaches 425nm, energy gap is 2.93eV, and the visible light photoelectric transformation efficiency has reached 35.2%, and impedance is reduced to 100 Ω, PhotoelectrocatalytiPerformance Performance is excellent, in the optoelectronic integration Oxidative Degradation Process of high concentration poisonous organic wastewater, show very strong photoelectrocatalysis synergy, greatly improved the efficient of catalyzing oxidizing degrading.
Above-mentioned examples prove: with TiO
2The NTs array is matrix, adopts the soft template sol-gal process, at the SnO of its surface construction macroporous structure
2Film, thereby the Mp-SnO that acquisition has the electrical integrated catalytic oxidation effect of good light
2/ TiO
2The NTs combination electrode is at load SnO
2After, the UV Absorption of electrode is strong, and the photoresponse scope broadens, and shows the feature of photoelectric-synergetic catalysis.This electrode can be used for the electrochemical degradation of high concentrated organic wastewater to be processed.
Embodiment 6
Macropore tin ash-titania nanotube combination electrode, this combination electrode internal layer is the titanium substrate, the top layer is SnO
2And TiO
2The composite bed of NTs, SnO in this layer
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Film is penetrating coarse pored, and the combination electrode smooth surface is smooth, and the light absorption wavelength scope is widened 425nm, and energy gap is that the thickness of 2.93eV titanium substrate is 0.1mm, SnO
2And TiO
2The thickness of the composite bed of NTs is 500nm, SnO
2Particle diameter is 10nm.
The preparation method of macropore tin ash-titania nanotube combination electrode, the method prepares titanium matrix TiO by the anodic titanium sheet
2Then the NTs array mixes the Sn of antimony (Sb) at its area load with the block copolymer soft template method
2+Colloidal sol namely obtains macropore tin ash-titania nanotube combination electrode finally by heat treatment.Specifically may further comprise the steps:
(1) be that 0.1mm pure metallic titanium sheet carries out sanding and polishing with sand paper and cleans up with thickness, to contain 0.5wt%NH
4F, 1.0wt%Na
2SO
4, the aqueous solution of 5wt%PEG400 is electrolyte solution, take the titanium sheet as working electrode, platinized platinum is to electrode in solution, carries out electrochemical anodic oxidation and processes 1h, obtains orderly TiO at titanium-based surface
2The NTs array electrode adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and program temperature is 1 ℃ of min
-1, heat treatment temperature is 400 ℃, heat treatment time is 5h, obtains orderly TiO
2NTs;
(2) the high-molecular block copolymer styrylphenol polyoxyethylene ether is soluble in water, the mass ratio of control high-molecular block copolymer and water is 1: 1, forms solution A, with SnCl
22H
2O, SbCl
3Be dissolved in the 18wt% hydrochloric acid solution control SnCl
22H
2O, SbCl
3And the mass ratio of 18wt% hydrochloric acid is 1: 0.05: 3, forms solution B, with solution A and solution B be in mass ratio mix and stir at 4: 10 transparent, behind the ageing 24h C colloidal sol;
(3) the orderly TiO for preparing with step (1)
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C colloidal sol and the submergence TiO of step (2) preparation
2Leave standstill 10min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 24h, at 100 ℃～300 ℃ lower oven dry 1h, at last at 450 ℃ of lower pyrolysis oxidation 1h, is namely obtained Mp-SnO
2/ TiO
2The NTs combination electrode.
Embodiment 7
Macropore tin ash-titania nanotube combination electrode, this combination electrode internal layer is the titanium substrate, the top layer is SnO
2And TiO
2The composite bed of NTs, SnO in this layer
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Film is penetrating coarse pored, and the combination electrode smooth surface is smooth, and the light absorption wavelength scope is widened 425nm, and energy gap is 2.93eV.The thickness of titanium substrate is 0.5mm, described SnO
2And TiO
2The thickness of the composite bed of NTs is 800nm, SnO
2Particle diameter is 20nm.
The preparation method of macropore tin ash-titania nanotube combination electrode, the method prepares titanium matrix TiO by the anodic titanium sheet
2Then the NTs array mixes the Sn of antimony (Sb) at its area load with the block copolymer soft template method
2+Colloidal sol namely obtains macropore tin ash-titania nanotube combination electrode finally by heat treatment.The method specifically may further comprise the steps:
(1) be that 0.5mm pure metallic titanium sheet carries out sanding and polishing with sand paper and cleans up with thickness, to contain 1wt%NH
4F, 1.5wt%Na
2SO
4, the aqueous solution of 15wt%PEG400 is electrolyte solution, take the titanium sheet as working electrode, platinized platinum is to electrode in solution, carries out electrochemical anodic oxidation and processes 1～3h, obtains orderly TiO at titanium-based surface
2The NTs array electrode adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and program temperature is 5 ℃ of min
-1, heat treatment temperature is 550 ℃, heat treatment time is 3h, obtains orderly TiO
2NTs;
(2) the high-molecular block copolymer alkyl phenol formaldehyde resin polyoxyethylene ether is soluble in water, the mass ratio of control high-molecular block copolymer and water is 2: 1, forms solution A, with SnCl
22H
2O, SbCl
3Be dissolved in the 18wt% hydrochloric acid solution control SnCl
22H
2O, SbCl
3And the mass ratio of 18wt% hydrochloric acid is 3: 0.15: 3, forms solution B, with solution A and solution B be in mass ratio mix and stir at 6: 15 transparent, behind the ageing 24h C colloidal sol;
(3) the orderly TiO for preparing with step (1)
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C colloidal sol and the submergence TiO of step (2) preparation
2Leave standstill 30min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 48h, at 100 ℃～300 ℃ lower oven dry 3h, at last at 600 ℃ of lower pyrolysis oxidation 3h, is namely obtained Mp-SnO
2/ TiO
2The NTs combination electrode.
Above-mentioned description to example is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these examples, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the examples of implementation here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (5)
1. macropore tin ash-titania nanotube combination electrode is characterized in that, this combination electrode internal layer is the titanium substrate, and the top layer is SnO
2And TiO
2The composite bed of NTs, SnO in this layer
2With titanium base TiO
2The combination of NTs skeleton is tight, SnO
2Film is penetrating coarse pored, and the combination electrode smooth surface is smooth, and the light absorption wavelength scope is widened 425nm, and energy gap is 2.93eV.
2. macropore tin ash according to claim 1-titania nanotube combination electrode is characterized in that, the thickness of described titanium substrate is 0.1～0.5mm, described SnO
2And TiO
2The thickness of the composite bed of NTs is 500～800nm, SnO
2Particle diameter is 10～20nm.
3. the preparation method of macropore tin ash as claimed in claim 1-titania nanotube combination electrode is characterized in that, the method prepares titanium matrix TiO by the anodic titanium sheet
2Then the NTs array mixes the Sn of antimony (Sb) at its area load with the block copolymer soft template method
2+Colloidal sol namely obtains macropore tin ash-titania nanotube combination electrode finally by heat treatment.
4. the preparation method of macropore tin ash according to claim 3-titania nanotube combination electrode is characterized in that, the method specifically may further comprise the steps:
(1) be that 0.1～0.5mm pure metallic titanium sheet carries out sanding and polishing with sand paper and cleans up with thickness, to contain 0.5～1wt%NH
4F, 1.0～1.5wt%Na
2SO
4, the aqueous solution of 5～15wt%PEG400 is electrolyte solution, take the titanium sheet as working electrode, platinized platinum is to electrode in solution, carries out electrochemical anodic oxidation and processes 1～3h, obtains orderly TiO at titanium-based surface
2The NTs array electrode adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and program temperature is 1～5 ℃ of min
-1, heat treatment temperature is 400～550 ℃, heat treatment time is 3～5h, obtains orderly TiO
2NTs;
(2) high-molecular block copolymer is soluble in water, the mass ratio of control high-molecular block copolymer and water is (1～2): 1, form solution A, with SnCl
22H
2O, SbCl
3Be dissolved in the 18wt% hydrochloric acid solution control SnCl
22H
2O, SbCl
3And the mass ratio of 18wt% hydrochloric acid be (1～3): (0.05～0.15): 3, form solution B, solution A and solution B are (4～6) in mass ratio: (10～15) mix and stir transparent, must C colloidal sol behind ageing 10～24h;
(3) the orderly TiO for preparing with step (1)
2NTs vertically puts into surge flask, and vavuum pump is evacuated to 6 * 10
-2Behind the Pa, with the adding of C colloidal sol and the submergence TiO of step (2) preparation
2Leave standstill 10～30min behind the NTs, the electrode after the biofilm at 40 ℃ of lower aging 24～48h, at 100 ℃～300 ℃ lower oven dry 1～3h, at last at 450～600 ℃ of lower pyrolysis oxidation 1～3h, is namely obtained Mp-SnO
2/ TiO
2The NTs electrode.
5. the preparation method of macropore tin ash according to claim 4-titania nanotube combination electrode, it is characterized in that, the high-molecular block copolymer described in the step (2) is styrylphenol polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether or polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer (PEO-PPO-PEO or EOn-POm-EOn) nonionic molecules surfactant.
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