CN101113525A - Pt-TiO2/Ti combination electrode and method for making same - Google Patents
Pt-TiO2/Ti combination electrode and method for making same Download PDFInfo
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- CN101113525A CN101113525A CNA2007100197518A CN200710019751A CN101113525A CN 101113525 A CN101113525 A CN 101113525A CN A2007100197518 A CNA2007100197518 A CN A2007100197518A CN 200710019751 A CN200710019751 A CN 200710019751A CN 101113525 A CN101113525 A CN 101113525A
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Abstract
A Pt-TiO2 / Ti complex electrode and a preparation thereof relates to electrode material and the preparation technology thereof, wherein a TiO2 nano-tube array is prepared at the vertical direction of the surface of a pure titanium substrate in hydrofluoric acid electrolyte liquid. The invention is characterized in that the invention also comprises nano platinum, the TiO2 nano-tube array is positioned into a mixed electrolyte liquid of chloroplatinic acid with a concentration of 0.5 to 1.5g/L and boric acid with a concentration of 20 to 40g/L, to be chemically deposited, and thus, nano particulate platinum or platelet platinum is grown at the surface of the TiO2 nano-tube array and in the nano-tube to form a Pt-TiO2 / Ti complex electrode. The preparation is characterized in that: the TiO2 nano-tube array is taken as cathode, a ruthenium titanium plated net is taken as anode, with a distance of 2cm between the cathode and the anode, a current density of 1 to 10mA/cm2 and time of 1 to 30 minutes, and a magnetic force stirring and an auxiliary ultrasonic are adopted. The specific surface area of the electrode is large, and the invention has a better electrocatalytic oxidation effect compared with ordinary electrode.
Description
One, technical field
The present invention relates to a kind of Pt-TiO with pure titanium-base
2/ Ti combined electrode and preparation method thereof relates to electrode materials and preparation technology.
Two, background technology
Titanium and titanium alloy thereof have fabulous erosion resistance, and titanium itself has fabulous electroconductibility.Therefore, these materials become the material that is used for electrode.TiO
2/ Ti is a kind of base electrode material of high corrosion resistance, and Pt is a kind of at widely used good electric catalyzer in field such as direct methanol fuel cell (DMFC) and electrolytic industries, uses Pt and TiO
2Making combined electrode has been the emphasis of research.
At present, to TiO
2Nano-powder, nanometer film and adulterated TiO
2The preparation of nano composite material, structural phase transition and Catalytic Performance are comparatively general, and to TiO
2The photoelectric properties of nanotube, applied research are reported seldom.TiO
2Nanotube is TiO
2Another existence form because nanotube ratio nano film has bigger specific surface area, thereby has higher adsorptive power, be expected to improve TiO
2Photoelectric transformation efficiency, photocatalysis performance, if particularly can pack in pipe littler inorganic, organic, metal or magnetic nano-particle are assembled into composite nano materials, that will improve TiO greatly
2Photoelectricity, electromagnetism and catalytic performance.
TiO
2The preparation method of nanotube at present report template, method of chemical treatment and electrochemistry anodic oxidation arranged.Template synthetic TiO
2The caliber of nanotube is big, thickness of pipe, and specific surface area is little, belongs to Detitanium-ore-type; Method of chemical treatment synthetic TiO
2The caliber of nanotube is little, and tube wall is thin, and specific surface area is big, belongs to unformed; Electrochemistry anodic oxidation synthetic TiO
2The TiO that the nanotube tube wall forms more naturally
2The nanotube thickness of pipe is a little, has characteristic of semiconductor, belongs to unformed.Preceding two kinds of methods all need preparation TiO 2 sol earlier, and calcining makes titania powder then.Template is a template with porous anodic aluminium oxide (PAA) normally, obtains TiO by technology such as electrochemical deposition method, sol-gel method, sol-gel-polymerizations then
2Nanotube.The problem that this method exists is: the internal diameter of the nanotube that obtains is generally bigger, and is subjected to the restriction of template pattern, and preparation process and complex process.Method of chemical treatment mainly is that the powder that obtains after by hydrothermal method TiO 2 sol being calcined is washed with alkali lye under hydrothermal condition, obtains TiO
2Nanotube.The problem that this method exists is: prepared TiO
2Nanotube electrode is not realized really integrated, poor stability, and TiO
2Nanotube peels off from matrix easily, the electrode in being not suitable for use in reacting; And complex process.
Platinum has excellent liberation of hydrogen electro catalytic activity, extensively applies in various batteries, the hydrogen reference electrode, and is the best eelctro-catalyst of fuel cell.But because platinum costs an arm and a leg, therefore, save consumption, in actual applications, in the inertia substrate, plate skim platinum usually for reducing cost.And have on the titanium matrix of fabulous erosion resistance the prepared electrode of platinum plating than polycrystalline platinum have bigger specific surface area, electro catalytic activity is better.
The matrix that adopts when depositing platinum at present is generally inert material, as the titanium matrix, and carbon nanotube, poriferous titanium dioxide film etc., the method for employing is generally dc electrodeposition.The electrode that obtains for the matrix platinum electrodeposition with the titanium, in the dimensional stability anode, electrolytic solution can produce passivation to the titanium matrix, the chemical property of impeded electrode is given full play to, therefore at the titanium matrix titanium oxide blocking layer being set between platinum oxide can stop the corrosion of ionogen to the titanium matrix, the stability on titanium oxide blocking layer and chemical property often depend on the preparation method of titanium matrix before zone of oxidation and the oxidation, so the preparation method on this and titanium oxide blocking layer has substantial connection.With the carbon nanotube matrix deposition platinum, preparation technology's more complicated, and the platinum that loads on the carbon nanotube reunites easily, and the platinum of load is limited, influences the performance of platinum electrocatalysis characteristic.In addition, deposition platinum also has research on the porous nano titanium dioxide film, but preparation porous nano titanium dioxide film generally adopts differential arc oxidation to carry out, required voltage is than higher, and experiment has certain risk, and the titanium dioxide that obtains is nanometer or micron-sized vesicular, be unfavorable for depositing the dispersion of platinum, specific surface area is little, can reduce the adsorptive capacity to degradation product, also influences the electrocatalysis characteristic performance of electrode.
Three, summary of the invention
Purpose of the present invention and task overcome prior art and exist: (1) can only prepare the TiO of powder
2Nanotube, and can not make TiO
2Nanotube electrode; (2) deficiency of complex manufacturing technology, and provide a kind of at pure titanium sheet or titanium alloy sheet surface preparation TiO
2Nanotube, and then can directly make the integrated TiO of getting
2Nanotube electrode, the deficiency that (3) complicated process of preparation and catalytic effect are not good provides a kind of simple method at TiO
2Depositing nano platinum obtains Pt-TiO on the nanotube electrode
2/ Ti combined electrode, and be applied to electrocatalysis degraded methyl alcohol, special proposition Pt-TiO of the present invention
2The technical solution of/Ti combined electrode and preparation method thereof.
Basic design of the present invention is according to being anode with pure titanium-base, and plating ruthenium titanium net is a negative electrode, and in ionogen, under electric field action, electrochemical oxidation can take place titanium, generates titanium dioxide; The control reaction conditions can generate TiO
2Nano-tube array; TiO to make then
2Nano-tube array is a negative electrode, and plating ruthenium titanium net is an anode, and in ionogen, under electric field action, platinum generation reduction reaction is at TiO
2Deposit in nano-tube array surface and the pipe, obtain Pt-TiO
2/ Ti combined electrode; And be applied in the catalytic oxidation of methyl alcohol.
Pt-TiO proposed by the invention
2/ Ti combined electrode comprises pure titanium-base, TiO
2Nano-tube array, wherein TiO
2Nano-tube array is with pure titanium-base, and under the effect of hydrofluoric acid electrolytic solution, producing caliber in the substrate surface vertical direction is 50～200nm, and pipe range is the TiO of 100～400nm
2Nano-tube array.It is characterized in that also comprising nanometer platinum, this nanometer platinum is with above-mentioned TiO
2Nano-tube array is put in the Platinic chloride and 20-40g/L boric acid mixed electrolytic solution that concentration is 0.5-1.5g/L, by electrochemical deposition, at TiO
2Growing nano particulate state or synusia shape platinum in nano-tube array surface and the pipe form Pt-TiO
2/ Ti combined electrode.
Pt-TiO
2The preparation method of/Ti combined electrode, the method steps of preparation is as follows:
The first step, the preparation of substrate
Pure titanium plate is cut into the substrate of certain size, with substrate ultrasonic cleaning oil removing in acetone earlier, after through after No. 600 sand paperings, clean with distilled water, be the mixing solutions polishing (method of etch is adopted in polishing, and vigorous stirring) of 1: 1 hydrofluoric acid and nitric acid again with volume ratio.Treated sample is clean with distilled water flushing, and it is standby to put into moisture eliminator after cold wind dries up;
Second step, TiO
2The preparation of nano-tube array
As anode, plating ruthenium titanium net is as negative electrode with the pure titanium-base that finishes of preparation in the first step, and two interpole gaps are from remaining on 4cm, and pressuring method is taked direct pressurization, promptly directly the two poles of the earth voltage is adjusted to the charged coupons of putting into behind the desirable value.Adding concentration in reactor is the hydrofluoric acid electrolytic solution of 0.5wt%, and its amount should make the height of pure titanium-base 25mm be immersed in the electrolytic solution.Entire test is all at room temperature carried out, and for keep whole system temperature and bath composition evenly, promote the heat radiation of system, adopt magnetic agitation in the entire test.Regulating voltage, stops behind the reaction 25min to 20V;
The 3rd step, TiO
2Calcining after the nanometer pipe array electrode preparation
Second step was prepared the TiO that finishes
2Nano-tube array is placed in the retort furnace, and calcining 3h behind the furnace cooling, promptly makes substrate and TiO under 280 ℃
2Nano-tube array constitutes incorporate TiO
2Nano-tube array.
The 4th step, Pt-TiO
2The preparation of/Ti combined electrode
TiO after the calcining that the 3rd step preparation is finished
2Nano-tube array is as negative electrode, and plating ruthenium titanium net is as anode, and two interpole gaps are from remaining on 2cm.Earlier circuit is connected, the two poles of the earth are immersed in the Platinic chloride and 20-40g/L boric acid mixed electrolytic solution of 0.5-1.5g/L, connect power supply then, by controlling the deposition current size and carry out dc electrodeposition with connect the outward milliampere reometer that joins of power supply.Entire test is all at room temperature carried out, and for keep whole system temperature and bath composition evenly, promote the heat radiation of system, adopt magnetic agitation in the entire test, in deposition process, add ultrasonic auxiliary, the deposition that helps platinum, its ultrasonic frequency size is 20-200KHz, and power is 0.1-2.0 kilowatt, and the selection of watt level is by electrolytic solution and sedimentary TiO
2The amount of nano-tube array decides.Regulate current density to 1-10mA/cm
2, behind the deposition 1-30min, what obtain is Pt-TiO
2/ Ti combined electrode.
Use Pt-TiO proposed by the invention
2/ Ti combined electrode is characterized in that in the application of catalytic oxidation methyl alcohol:
(a) use Pt-TiO
2/ Ti combined electrode is when catalytic oxidation methyl alcohol, with Pt-TiO
2/ Ti combined electrode is put into methanol solution, and at room temperature, through galvanic action, methyl alcohol generation redox is sent out should.
(b) use Pt-TiO
2/ Ti combined electrode is when catalytic oxidation methyl alcohol, with Pt-TiO
2/ Ti combined electrode is an anode, and platinized platinum or platinum filament are negative electrode, and saturated calomel electrode is a reference electrode, put in the methanol solution (sulphuric acid soln that comprises 0.5mol/L), at room temperature, and through galvanic action, methyl alcohol generation redox reaction.
Pt-TiO provided by the present invention
2The preparation method of/Ti combined electrode is when sizes of substrate is smaller, and used voltage is lower, and interelectrode distance is less, and the reaction times is shorter, can make Pt-TiO
2/ Ti combined electrode.
Major advantage of the present invention is:
(1) technology is simple, does not need expensive equipment, both can be used for experimental implementation, again can industrial scale operation, and preparation process only needs to add dc electrodeposition again after adding volts DS, calcining on the matrix and gets final product;
(2) Pt-TiO for preparing
2/ Ti combined electrode, its TiO
2Nano-tube array and the titanium substrate polarizing electrode that becomes one, specific surface area is big, high adsorption capacity, and the tiny distribution of nano-platinum particle disperses, and is beneficial to the whole electrocatalysis characteristic of performance combined electrode.
Four, description of drawings
Fig. 1 TiO
2The sem photograph of nanometer pipe array electrode.
Fig. 2 Pt-TiO
2The sem photograph of/Ti combined electrode.
The Pt-TiO of Fig. 3 special construction
2The sem photograph of/Ti combined electrode.
The catalytic oxidation cyclic voltammogram of Fig. 4 methyl alcohol.
The Pt-TiO of Fig. 5 special construction
2The sem photograph of/Ti combined electrode.
The catalytic oxidation cyclic voltammogram of Fig. 6 methyl alcohol.
Five, embodiment
Below by specific embodiment, further specify Pt-TiO
2The preparation method of/Ti combined electrode and application.
Embodiment 1
The TiO for preparing 25mm * 25mm with pure titanium-base
2The incorporate TiO of nano-tube array and substrate
2Nano-tube array.
The first step, the preparation of substrate
Pure titanium is cut into the substrate of 25mm * 35mm, with substrate ultrasonic cleaning oil removing in acetone earlier, after through after No. 600 sand paperings, clean with distilled water, be the mixing solutions polishing (method of etch is adopted in polishing, and vigorous stirring) of 1: 1 hydrofluoric acid and nitric acid again with volume ratio.Treated sample is clean with distilled water flushing, and it is standby to put into moisture eliminator after cold wind dries up;
Second step, TiO
2The preparation of nano-tube array
With the pure titanium-base that finishes of preparation in the first step is anode, and plating ruthenium titanium net is as negative electrode, and two interpole gaps are from remaining on 4cm, and pressuring method is taked direct pressurization, promptly directly the two poles of the earth voltage is adjusted to the charged coupons of putting into behind the desirable value.Adding concentration in reactor is the hydrofluoric acid electrolytic solution of 0.5wt%, and its amount should make the height of pure titanium-base 25mm be immersed in the electrolytic solution.Entire test is all at room temperature carried out, and for keep whole system temperature and bath composition evenly, promote the heat radiation of system, adopt magnetic agitation in the entire test.Regulating voltage, stops behind the reaction 25min to 20V;
The 3rd step, TiO
2Calcining after the nano-tube array preparation
Second step was prepared the TiO that finishes
2Nano-tube array is placed in the retort furnace, and calcining 3h behind the furnace cooling, promptly makes substrate and TiO under 280 ℃
2Nano-tube array constitutes incorporate TiO
2Nano-tube array.
Detected result: TiO
2Nanotube caliber 100-200nm, pipe range 300-400nm.TiO
2Nanotube is all perpendicular to substrate.As shown in Figure 1, this figure adopts the LEO1530VP field emission scanning electron microscope, perpendicular to substrate be parallel to that the substrate direction takes.As seen from the figure, the TiO of generation
2Nanotube is ordered arrangement on substrate, and caliber is 100-200nm, and pipe range is 300-400nm.
Embodiment 2
With the TiO after the calcining
2Nano-tube array prepares Pt-TiO
2/ Ti combined electrode.
With the TiO after the calcining
2Nano-tube array is as negative electrode, and plating ruthenium titanium net is as anode, and two interpole gaps are from remaining on 2cm.Earlier circuit is connected, the two poles of the earth are immersed in the Platinic chloride and 30g/L boric acid mixed electrolytic solution of 1.0g/L, connect power supply then, by controlling the deposition current size and carry out dc electrodeposition with connect the outward milliampere reometer that joins of power supply.Entire test is all at room temperature carried out, and for keep whole system temperature and bath composition evenly, promote the heat radiation of system, adopt magnetic agitation in the entire test.Regulate current density to 2.5mA/cm
2, reaction 10min stops.
Detected result: sedimentary platinum becomes the synusia structure of thick grass shape, attached to TiO
2The surface of nanotube electrode.Shown in accompanying drawing 2 (1), this figure adopts the S4800 of Hitachi field emission scanning electron microscope, takes perpendicular to the substrate direction.As seen from the figure, sedimentary platinum stratification sheet.
With the TiO after the calcining
2Nanometer pipe array electrode prepares Pt-TiO
2/ Ti combined electrode.
With the TiO after the calcining
2Nanometer pipe array electrode is as negative electrode, and plating ruthenium titanium net is as anode, and two interpole gaps are from remaining on 2cm.Earlier circuit is connected, the two poles of the earth are immersed in the Platinic chloride and 30g/L boric acid mixed electrolytic solution of 1.5g/L, connect power supply then, by controlling the deposition current size and carry out dc electrodeposition with connect the outward milliampere reometer that joins of power supply.Entire test is all at room temperature carried out, and for keep whole system temperature and bath composition evenly, promote the heat radiation of system, adopt magnetic agitation in the entire test.Regulate current density to 5mA/cm
2, behind the reaction 3min, stop.
Detected result: sedimentary platinum becomes grainy texture, attached to TiO
2The surface of nanotube electrode.Shown in accompanying drawing 2 (2), this figure adopts the S4800 of Hitachi field emission scanning electron microscope, takes perpendicular to the substrate direction.As seen from the figure, sedimentary platinum becomes particulate state.
Embodiment 4
With the TiO after the calcining
2Nano-tube array prepares Pt-TiO
2/ Ti combined electrode.
With the TiO after the calcining
2Nano-tube array is as negative electrode, and plating ruthenium titanium net is as anode, and two interpole gaps are from remaining on 2cm.Earlier circuit is connected, the two poles of the earth are immersed in the Platinic chloride and 40g/L boric acid mixed electrolytic solution of 1.0g/L, connect power supply then, by controlling the deposition current size and carry out dc electrodeposition with connect the outward milliampere reometer that joins of power supply.Entire test is all at room temperature carried out, and adopts ultrasonic assisting in the entire test, and ultrasonic frequency is 80KHz, 0.1 kilowatt of power.Regulate current density to 5mA/cm
2, reaction 1min stops.
Detected result: sedimentary platinum becomes small nano-scale particle shape, attached to TiO
2On the nanotube, and form the nanotube that the upper end constitutes for nano-platinum particle, the lower end is TiO
2The composite Nano pipe electrode of nanotube.As shown in Figure 3, this figure adopts the S4800 of Hitachi field emission scanning electron microscope, is parallel to the substrate direction and takes.As seen from the figure, its structure is that the upper end is nanometer Pt particle, and the lower end is TiO
2The packaging assembly of nano-tube array.
Embodiment 5
Pt-TiO
2/ Ti combined electrode is applied to catalytic oxidation methyl alcohol
Methanol solution: 0.5mol/LCH
3OH+0.5mol/L H
2SO
4Mixed liquid, volume 30mL.
Pt-TiO with 25mm * 25mm
2/ Ti combined electrode is put into methanol solution, anode as electrocatalytic reaction, platinized platinum is made negative electrode, saturated calomel electrode is a reference electrode, at ambient temperature, add the anodic bias of 1.0V, cyclic voltammetry curve that obtains such as accompanying drawing 4, this cyclic voltammetry curve are to obtain with the test of CHI1440 electrochemical workstation.As seen from the figure, the oxidization of methanol reduction peak clearly, oxidized degraded illustrates that its catalytic oxidation effect to methyl alcohol is very good.
Fig. 5 in the Figure of description is the Pt-TiO of special construction
2The sem photograph of/Ti combined electrode, Fig. 6 is the catalytic oxidation of the methyl alcohol excellent Antu of circulating.
Claims (3)
1. Pt-TiO
2/ Ti combined electrode comprises pure titanium-base, TiO
2Nano-tube array, wherein TiO
2Nano-tube array is with pure titanium-base, and under the effect of hydrofluoric acid electrolytic solution, producing caliber in the substrate surface vertical direction is 50～200nm, and pipe range is the TiO of 100～400nm
2Nano-tube array.It is characterized in that also comprising nanometer platinum, this nanometer platinum is with above-mentioned TiO
2Nano-tube array is put in the Platinic chloride and 20-40g/L boric acid mixed electrolytic solution that concentration is 0.5-1.5g/L, by electrochemical deposition, at TiO
2Growing nano particulate state or synusia shape platinum in nano-tube array surface and the pipe form Pt-TiO
2/ Ti combined electrode.
2. prepare Pt-TiO as claimed in claim 1
2/ Ti combined electrode, preparation process is as follows:
The first step, the preparation of substrate
Pure titanium plate is cut into the substrate of certain size, with substrate ultrasonic cleaning oil removing in acetone earlier, after through after No. 600 sand paperings, clean with distilled water, be the mixing solutions polishing of 1: 1 hydrofluoric acid and nitric acid again with volume ratio, treated sample is clean with distilled water flushing, and it is standby to put into moisture eliminator after cold wind dries up;
Second step, TiO
2The preparation of nano-tube array
With the pure titanium-base that finishes of preparation in the first step as anode, plating ruthenium titanium net is as negative electrode, two interpole gaps are from remaining on 4cm, pressuring method is taked direct pressurization, promptly directly the two poles of the earth voltage is adjusted to the charged coupons of putting into behind the desirable value, adding concentration in reactor is the hydrofluoric acid electrolytic solution of 0.5wt%, its amount should make the height of pure titanium sheet 25mm be immersed in the electrolytic solution, entire test is all at room temperature carried out, and in order to keep the even of whole system temperature and bath composition, magnetic agitation is adopted in the heat radiation of promotion system in the entire test, regulating voltage is to 20V, behind the reaction 25min, stop;
The 3rd step, TiO
2Calcining after the nano-tube array preparation
Second step was prepared the TiO that finishes
2Nano-tube array is placed in the retort furnace, and calcining 3h behind the furnace cooling, promptly makes substrate and TiO under 280 ℃
2Nano-tube array constitutes incorporate TiO
2Nano-tube array;
It is characterized in that also comprising:
The 4th step, Pt-TiO
2The preparation of/Ti combined electrode
TiO after the calcining that the 3rd step preparation is finished
2Nano-tube array is as negative electrode, plating nail titanium net is as anode, two interpole gaps are from remaining on 2cm, earlier circuit is connected, the two poles of the earth are immersed in the Platinic chloride and 20-40g/L boric acid mixed electrolytic solution of 0.5-1.5g/L, connect power supply then, by controlling the deposition current size and carry out dc electrodeposition with the power supply milliampere reometer that joins of connecting outward, entire test is all at room temperature carried out, and in order to keep the even of whole system temperature and bath composition, the heat radiation of promotion system, adopt magnetic agitation in the entire test, this process has also added assisting ultrasonic in addition, regulates current density to 1-10mA/cm
2, behind the reaction 1-30min, promptly obtain Pt-TiO
2/ Ti combined electrode.
3. in the 4th step as claimed in claim 2, the frequency that it is characterized in that assisting ultrasonic is 20-200KHz, and power is 0.1-2.0 kilowatt.
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| CN104868148A (en) * | 2015-04-22 | 2015-08-26 | 陈海辉 | Industrial amplification method and device of DC field-enhanced fuel cell reactor |
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| CN105177664A (en) * | 2015-09-21 | 2015-12-23 | 清华大学 | Method for manufacturing Cu/Ti double-layer nanoelectrode |
| CN111270288A (en) * | 2020-01-21 | 2020-06-12 | 黑龙江科技大学 | Preparation method of novel titanium dioxide negative electrode material |
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