CN101560669A - Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array - Google Patents
Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array Download PDFInfo
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Abstract
The invention relates to a method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array. The method comprises the following steps: adopting a method for using ultrasound to assist pulse electrodeposition, taking titanium dioxide nano tubes growing on the titanium base as carriers, and preparing a composite catalyst system which has stable structure and high catalytic activity and is dispersed in the nano tube by means of Pd with high dispersive property. The spherulitic crystal structure with high-dispersive property can provide more surface catalysis activity sites and specific surface area of catalytic reaction. The technique has simple and convenient operation, can obtain Pt-Pd falling type composite spherulitic crystal stable catalysis system which is dispersed highly in the nano tube and can improve catalytic activity and stability of the catalytic electrode when being applied to the energy fields of fuel cells and the like.
Description
Technical field
The invention belongs to the materials chemistry field, relating to a kind of is that carrier adopts chemical process to prepare the method for precious metal bimetal composite catalyzing electrode with the titanium-based titanium dioxide nanotube.
Background technology
In the research of eelctro-catalyst, obtain high dispersing, high-specific surface area, constitutionally stable catalyzer is for improving the catalyst activity, and anti-poisoning performance and life-span are significant.And this is also with the selection of catalytic carrier with prepare closely related.Suitable catalysis dispersible carrier not only has good physical and chemical stability in catalyzed reaction, and can realize the quick transmission of electronics between eelctro-catalyst and carrier.Traditional eelctro-catalyst preparation method will have the noble metal supports such as Pt, Pd of high catalytic activity very to the carbon back catalytic carrier, as carbon black, activated carbon, activated carbon fiber etc.In some recent research work, people attempt adopting single wall or many walls carbon
[1]Nanotube disperses metallics thereon as support of the catalyst, has not only greatly improved catalytic activity, and has effectively prevented the polymerization of the particle in the catalyzed reaction.Compare with traditional carbon black carrier, carbon nanotube loaded noble metal electrocatalyst shows better catalytic performance.But because its rigidity is relatively poor, mechanical deformation takes place in reaction process easily, thereby cause catalyst loss.In addition, because conventional carbon base carrier surface stability is relatively poor, catalytic species loads on the surface polymerization takes place easily, influences catalytic activity, and in reaction process, the easy poisoning and deactivation of catalyzer.Therefore, select suitable high-specific surface area, the high stability support of the catalyst can effectively solve catalyzer and in reaction process polymerization may take place, thereby influence the problem of catalytic performance.
Compare with carbon support, metallic carrier has stable appearance, the physical strength height, and characteristics such as chemical property is good can solve to a great extent because the catalyst loss problem that mechanical deformation causes.Metal titanium is a kind of high-quality light metal material, and is tough and tensile and corrosion-resistant.Yet because the metal titanium any surface finish, undressed titanium is what to be not suitable for directly as the load of noble metal electrocatalyst.Therefore, if, can improve the carrier specific surface area greatly at titanium carrier surface in situ growing nano-tube oxide skin, lot of documents report, original position TiO
2Nanotube layer just can easy preparing by electrochemical anodic oxidation.Compare TiO with the disordered carbon nanotube
2Nanotube is the axial conductor oxidate nanotube of a kind of high-sequential, caliber has than higher specific surface area equally usually greater than 50nm, and bigger freeboard, its porous tubular structure has good dispersing property for noble metal catalyst, more helps the load of catalyzer.Simultaneously, the upright TiO of growth in situ
2Nano-tube array preparation technology is easier, economical, has good physical and chemical stability and electrochemical activity, and its plank frame can need not to be coated on other carriers directly as being the catalysis electrode solid support material.Therefore, this material has more and more entered the fuel cell studies field.
Based on TiO
2Nanotube high-specific surface area and freeboard, the noble metal loading that platinum (Pt), palladium (Pd), rhodium (Rh) etc. is had very high catalytic activity disperses thereon, can further improve catalyst catalytic performance and stability.For example, Macak etc. is distributed to TiO with Pt, Ru nanoparticle
2On the nanotube, improved catalytic oxidation ability to methyl alcohol.Wang etc. arrive TiO with the Pd dispersed deposition
2On the nanotube, thereby obtain methanol oxidation is had the new catalyst of high catalytic activity.But traditional chemistry and galvanic deposit carrying method are difficult to realize the high dispersing of precious metal in pipe, and still having in the loading process reunites occurs, and has influenced the raising of catalytic activity., in metal deposition process, be difficult to and the solution thorough mixing on the one hand, so noble metal nano particles is difficult to homodisperse and is attached on the nanotube because the nanotube of growth in situ is on dull and stereotyped carrier.On the other hand, precious metal directly is deposited on the nanotube, forms to reunite, and often stops up the nanometer mouth of pipe, causes catalytic performance to descend.
Summary of the invention
The present invention relates to a kind of is that carrier adopts chemical process to prepare the novel method of precious metal bimetal composite catalyzing electrode with the titanium-based titanium dioxide nanotube.Pulse electrodeposition and ultrasonic technique are combined, selecting the TiO2 nanotube with good physical chemical stability, high-specific surface area and template effect for use is electrode holder, under ultrasonic booster action, precious metals pt, the Pd that will have high catalytic activity by the pulsed current deposition deposit in the TiO2 nanotube, obtain Stability Analysis of Structures, the catalytic activity height, the composite catalyzing electrode that the life-span is long.The present invention has designed a kind of method for preparing the bimetallic catalytic system of high dispersive in nanotube.This invention principle of work is to promote the dispersion of noble metal nano crystal to grow by ultrasonic wave and pulsed current, simultaneously, the high dispersing freeboard that tubular structure provided of TiO2 nanotube and the eelctro-catalyst formed component that crashes into inserted spherocrystal in nanotube is relevant with structure.The spherulitic crystal structure of this high dispersing can provide more surface catalysis avtive spot, and the catalyzed reaction specific surface area.This technological operation is easy, can obtain the Pt-Pd of high dispersing in nanotube and crash into the stably catalyzed system of the compound spherocrystal of formula.Be applied to fuel cell equal energy source field, be expected to improve the catalytic activity and the stability of catalysis electrode.
The purpose of this invention is to provide a kind of is carrier with the orderly Nano tube array of titanium dioxide that stands on the metal titanium primary surface, adopts chemical assemble method to prepare the method for Pt-Pd noble metal nano spherocrystal composite catalyzing electrode.
Utilize anonizing on the metal titanium base, to prepare upright orderly Nano tube array of titanium dioxide, adopt ultrasonic satellite pulse electro-deposition method in nanotube, to prepare the compound spherocrystal catalyst system of Pt-Pd.
This preparation method can realize by following concrete steps:
(1) with pure titanium plate surface mechanical grinding polishing, cleans up.
(2) preparation electrolytic solution, solute is NaF and supporting electrolyte, solvent is a water, and adds the alcohols additive.
(3) be working electrode with the titanium sheet in the step (1), platinized platinum is that counter electrode carries out the electrochemical anodic oxidation processing, can obtain upright orderly TiO2 nano-tube array at titanium-based surface.
(4) nano-tube array that step (3) is prepared in retort furnace with temperature programming to certain temperature, and under this temperature the thermal treatment certain hour, obtain anatase octahedrite and stablize crystal formation TiO
2The nanotube matrix.
(5) Pt, the Pd mixing electroplate liquid of preparation certain mol proportion, supporting electrolyte is certain density sulfuric acid.
(6) TiO for preparing with step (4)
2NTs/Ti is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode (SCE) is a reference electrode.Whole electrochemical reaction cell places ultrasonic cleaner, adopts the pulsed current deposition technique to deposit in the nanotube Pt, Pd are nanocrystalline under adding the ultrasonic field condition.
Method as mentioned above, the pure titanium sheet thickness in the step (1) is 0.02～0.1mm, size 1～6cm
2
The concentration of NaF is 0.05-1.0wt% in the method as mentioned above, step (2), and supporting electrolyte is 1.6-2.0wt%Na
2SO
4The alcohols additive is 10-50wt% polyoxyethylene glycol (PG400).
Working electrode and counter electrode spacing are 0.5～1.0cm in the method as mentioned above, step (3), and anodizing voltage is 5～20V, and the anodizing time is 3～5h.
Thermal treatment temp is 450～550 ℃ in the method as mentioned above, step (4), and heat treatment time is 3～5h, heats up and rate of temperature fall is 1～2 ℃/min.
In the method as mentioned above, step (5) in Pt and the Pd mixing electroplate liquid Pt, Pd ionic concn be respectively 0～0.10mol/L, sulfuric acid concentration is 0.02～0.1mol/L.
Ultrasonic field power is 30～50W in the method as mentioned above, step (6), and frequency is 15～30KHz, and pulsed current is 1～3mA/cm
2, burst length 0.05～1s, rest time 1～2s.Effectively depositing time is 1200～2400s.
Compared with prior art, the present invention has following advantage:
1. to have adopted the orderly Nano tube array of titanium dioxide that stands on the metal titanium base be the carrier electrode material in the present invention, this nano-tube array high-sequential, and physical and chemical performance is stable, and very big specific surface area and freeboard can be provided.Its porous tubular structure has good dispersing property and template effect for noble metal catalyst, more helps the load of catalyzer.Simultaneously, the upright TiO of growth in situ
2Nano-tube array preparation technology is easier, economical, and its plank frame can need not to be coated on other carriers directly as being the catalysis electrode solid support material.
2. the present invention has adopted ultrasonic supplementary means to combine with pulse electrodeposition.Cavitation effect of ultrasonic waves can realize the high-speed mixing of water body inside, and the solid-liquid mass transfer process in the enhancing electrochemical reaction process between electrode and the solution promotes the precious metal nucleus to disperse growth.The bubble that ultrasonic cavitation effect in addition produced can increase noble metal nano spherocrystal specific surface area, thereby improves its catalytic activity.Pulse electrodeposition helps noble metal nanocrystalline and enters in the nanotube, forms the high dispersing structure.
3. the introducing of precious metals pd not only can form double-metal composite catalyst, improve catalytic activity, and because the good distribution performance that Pd itself has, can be used as a kind of dispersion agent, induce bimetal composite Nano spherocrystal to deposit in the nanotube, formation crashes into the formula spherulitic crystal structure, has improved the degree of scatter of catalyzer on carrier.
Description of drawings
Upright scanning electron microscope (SEM) photo of Nano tube array of titanium dioxide in order of the titanium base of Fig. 1 the present invention preparation.
The stereoscan photograph of the Pt nanometer spherocrystal-titania nanotube composite catalyzing electrode of Fig. 2 embodiment of the invention 1 preparation.
The stereoscan photograph of the Pd nanometer spherocrystal-titania nanotube composite catalyzing electrode of Fig. 3 embodiment of the invention 2 preparations.
The stereoscan photograph of the Pt-Pd bimetal nano spherocrystal-titania nanotube composite catalyzing electrode of Fig. 4 embodiment of the invention 3 preparations.
Embodiment
Following examples will the invention will be further described in conjunction with the accompanying drawings.
Embodiment 1
The pure titanium sheet (99%) of 0.80mm is used 100 successively
#, 300
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface level and smooth, and each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water then.Anodizing electrolytic solution consists of 0.5wt%NaF, 2%wtNaSO
4, 10wt% polyoxyethylene glycol (400).Anodizing voltage is 20V, anodizing time 5h.Thermal treatment temp is 450 ℃, and the intensification rate of temperature fall is 1 ℃/min.
Electroplate liquid is 0.1mol/L H
2PtCl
6Supporting electrolyte is the sulfuric acid of 0.1mol/L.Three-electrode system is adopted in the galvanic deposit experiment, on the CHI660C electrochemical workstation, with TiO
2NTs/Ti is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode (SCE) is a reference electrode.Whole electrochemical reaction cell places 50W, in the 30KHz ultrasonic cleaner, adopts the pulsed current deposition technique with the nanocrystalline TiO of depositing to of precious metals pt adding under the ultrasonic field condition
2Electrode surface, pulsed current are 2mA/cm
2, burst length 0.2s, rest time in recurrent interval 1s.Effectively depositing time is 2400s.
Fig. 1 and Fig. 2 are respectively Pt nanometer spherocrystal-titania nanotube composite catalyzing electrode that the Nano tube array of titanium dioxide for preparing according to embodiment 1 condition anodic oxidation and pulse electrodeposition prepare.As can be seen, formed on the titanium matrix and arranged closely from Fig. 1, pore size distribution is than the nano-tube array of homogeneous, and average caliber is about 50～90nm, and thickness of pipe is about 10～15nm, and the gap is about 20nm between the tube and tube.As seen from Figure 2, Pt is at TiO
2Forming diameter on the nanotube is the microballoon of 500-1000 μ M, because TiO
2The template effect of nano-tube support, microballoon spherocrystal in forming process sink, and then the growth of clad nano pipe, and the top forms a plurality of micropores, and bore dia is in 90nm, and is identical with the nanotube diameter.In whole electrodeposition process, we have added hyperacoustic auxiliary, and the main effect that ultrasonic wave plays is to stir and dispersion, effectively prevent to reunite in the nanoparticle nucleating process, and promote nucleus growth.Simultaneously, because the existence of the bubble that ultrasonic wave produces prepares the vesicular structure noble metal catalyst by the bubble collapse in electrodeposition process.Compare with potentiostatic electrodeposition, under the pulsed current effect, the platinum microsphere surface forms more staggered laminated structures of interting (Fig. 2 illustration), and these laminated layer thickness have greatly improved the external surface area of microballoon all less than 20nm.Thereby increased the catalytic activity site, helped the raising of electrocatalysis efficient.
Embodiment 2
The pure titanium sheet (99%) of 0.50mm is used 100 successively
#, 300
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface level and smooth, and each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water then.Anodizing electrolytic solution consists of 0.05wt%NaF, 2%wtNaSO
4, 10wt% polyoxyethylene glycol (400).Anodizing voltage is 15V, anodizing time 3h.Thermal treatment temp is 550 ℃, and the intensification rate of temperature fall is 1 ℃/min.
Electroplate liquid is 0.1mol/L PdCl
2Supporting electrolyte is the sulfuric acid of 0.05mol/L.Three-electrode system is adopted in the galvanic deposit experiment, on the CHI660C electrochemical workstation, with TiO
2NTs/Ti is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode (SCE) is a reference electrode.Whole electrochemical reaction cell places 50W, in the 30KHz ultrasonic cleaner, adopts the pulsed current deposition technique that precious metals pd is deposited to TiO adding under the ultrasonic field condition
2Electrode surface, strobe pulse electric current are 1mA/cm
2, burst length 0.5s, rest time in recurrent interval 1s.Effectively depositing time is 1800s.
Fig. 3 is the Pd nanometer spherocrystal-titania nanotube composite catalyzing electrode for preparing by embodiment 2 pulse electrodepositions.As shown in Figure 3, at 2mA/cm
2The pulsed deposition current density under, because palladium has good dispersiveness, the nano particle diameter that its galvanic deposit obtains is little, be dispersed in the nanotube walls and the pipe end, from Electronic Speculum figure, can see, the phenomenon that particle agglomeration do not occur mainly exists with dispersive nanometer spherical crystal, and diameter is about 100nm.
Embodiment 3
The pure titanium sheet (99%) of 0.20mm is used 100 successively
#, 300
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface level and smooth, and each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water then.Anodizing electrolytic solution consists of 0.8wt%NaF, 1.6%wtNaSO
4, 20wt% polyoxyethylene glycol (400).Anodizing voltage is 10V, anodizing time 2h.Thermal treatment temp is 500 ℃, and the intensification rate of temperature fall is 1 ℃/min.
Electroplate liquid is 0.1mol/L H
2PtCl
6With 0.1mol/L PdCl
2Mixing solutions.Supporting electrolyte is the sulfuric acid of 0.05mol/L.Three-electrode system is adopted in the galvanic deposit experiment, on the CHI660C electrochemical workstation, with TiO
2NTs/Ti is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode (SCE) is a reference electrode.Whole electrochemical reaction cell places 50W, in the 30KHz ultrasonic cleaner, adopts the pulsed current deposition technique that Pt-Pd bimetal nano crystalline substance is deposited to TiO adding under the ultrasonic field condition
2Electrode surface, strobe pulse electric current are 2mA/cm
2, burst length 0.5s, rest time in recurrent interval 1s.Effectively depositing time is 2400s.
Fig. 4 is the Pt-Pd bimetal nano spherocrystal-titania nanotube composite catalyzing electrode for preparing by embodiment 3 condition pulse electrodepositions.As shown in Figure 4, bimetal nano microsphere surface pattern is similar to the Pt microballoon that ultrasonic deposition obtains, and certain concavo-convex fluctuating is arranged.Because the good dispersiveness of Pd itself, its nanoparticle and Pt particulate form the alloy that dissolves each other, and are embedded in the microballoon.And the structure of whole microballoon and pattern are mainly determined by the Pt of macrobead yardstick.Its diameter is greater than 500nm.Under the acting in conjunction of ultrasonic and pulsed current, grow in the vertical bimetal microballoon of the nanometer mouth of pipe and sink gradually, crash in the nanotube, expose nanotube again, crash into formula compound ball crystal structure thereby form.The spherocrystal of this structure is because high dispersing in nanotube, thereby has very high specific surface area and active space.
Above-mentioned example proves: the TiO2 nanotube is as a kind of special upright tubulose structural semiconductor metallic carrier, very high specific surface area and freeboard can be provided for the load of catalyzer, utilize its tubular type template effect, on the TiO2 nanotube, compare with single Pt, Pd are nanocrystalline, the Pt that codeposition prepares, Pd bimetal nano crystalline substance produce bigger difference on the microtexture pattern, mainly exist, further improved the dispersity and the catalytic activity area of catalyzer thus to crash into formula compound ball crystal structure.
The above-mentioned description to embodiment 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 embodiment, 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 embodiment 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 (8)
- One kind prepare noble metal nanocrystalline-titania nanotube composite catalyzing electrode method, it is characterized in that: the method that adopts ultrasonic satellite pulse galvanic deposit, titania nanotube with vertical growth on the titanium base is a carrier, by means of the high dispersing performance of Pd, preparation is scattered in the high composite catalyst system of Stability Analysis of Structures, catalytic activity in the nanotube.
- 2. the method for claim 1 is characterized in that: may further comprise the steps:(1) with pure titanium plate surface mechanical grinding polishing, cleans up;(2) preparation electrolytic solution, solute is NaF and supporting electrolyte, solvent is a water, and adds the alcohols additive;(3) be working electrode with the titanium sheet in the step (1), platinized platinum is that counter electrode carries out the electrochemical anodic oxidation processing, can obtain upright orderly TiO at titanium-based surface 2Nano-tube array;(4) nano-tube array that step (3) is prepared is heat-treated;(5) Pt, the Pd mixing electroplate liquid of preparation certain mol proportion, supporting electrolyte is certain density sulfuric acid;(6) TiO for preparing with step (4) 2NTs/Ti is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode (SCE) is a reference electrode; Whole electrochemical reaction cell places ultrasonic cleaner, adopts the pulsed current deposition technique to deposit in the nanotube Pt, Pd are nanocrystalline under adding the ultrasonic field condition.
- 3. method as claimed in claim 2 is characterized in that: the pure titanium sheet thickness in the step (1) is 0.02～0.1mm, is of a size of 1～6cm 2
- 4. method as claimed in claim 2 is characterized in that: the concentration of NaF is 0.05-1.0wt% in the step (2), and supporting electrolyte is 1.6-2.0wt%Na 2SO 4The alcohols additive is 10-50wt% polyoxyethylene glycol (PG400).
- 5. method as claimed in claim 2 is characterized in that: working electrode and counter electrode spacing are 0.5～1.0cm in the step (3), and anodizing voltage is 5～20V, and the anodizing time is 3～5h.
- 6. method as claimed in claim 2 is characterized in that: thermal treatment temp is 450～550 ℃ in the step (4), and heat treatment time is 3～5h, and intensification and rate of temperature fall are 1～2 ℃/min.
- 7. method as claimed in claim 2 is characterized in that: Pt, Pd ionic concn are respectively 0～0.10mol/L in middle Pt of step (5) and the Pd mixing electroplate liquid, and sulfuric acid concentration is 0.02～0.1mol/L.
- 8. method as claimed in claim 2 is characterized in that, ultrasonic field power is 30～50W in the step (6), and frequency is 15～30KHz, and pulsed current is 1～3mA/cm 2, burst length 0.05～1s, rest time 1～2s; Effectively depositing time is 1200～2400s.
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| CN105609788B (en) * | 2015-12-30 | 2018-06-29 | 中国科学院上海高等研究院 | The construction method of ordering membrane electrode based on noble metal hollow pipe array |
| CN107604168A (en) * | 2017-09-28 | 2018-01-19 | 上海至铂环保科技服务有限公司 | The method of recovering copper, nickel, cobalt from the sludge containing non-ferrous metal |
| WO2021038502A1 (en) * | 2019-08-28 | 2021-03-04 | Manufacturing Systems Limited | Materials and methods of manufacture |
| CN110988074A (en) * | 2019-12-20 | 2020-04-10 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN110988074B (en) * | 2019-12-20 | 2021-12-21 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN111370706A (en) * | 2020-02-12 | 2020-07-03 | 童圣富 | Positive electrode material of metal-air battery and preparation method thereof |
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