CN103949246A - Method for preparing platinum catalyst using porous foamed titanium as carrier for methanol reforming combustion chamber - Google Patents

Method for preparing platinum catalyst using porous foamed titanium as carrier for methanol reforming combustion chamber Download PDF

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Publication number
CN103949246A
CN103949246A CN201410210578.XA CN201410210578A CN103949246A CN 103949246 A CN103949246 A CN 103949246A CN 201410210578 A CN201410210578 A CN 201410210578A CN 103949246 A CN103949246 A CN 103949246A
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combustion chamber
titanium
carrier
catalyst
platinum
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CN201410210578.XA
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CN103949246B (en
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张雪林
马泽众
刘晓为
张宇峰
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a method for preparing a platinum catalyst using porous foamed titanium as a carrier for a methanol reforming combustion chamber, belonging to the field of proton exchange ceramic membrane fuel cells. According to the method, the porous foamed titanium is used as an anode and is put into an aluminate-containing electrolyte, direct current or alternating current is applied for micro-arc oxidation treatment, a generated ceramic membrane is sintered at high temperature to form a porous and compact oxide ceramic membrane, the oxide ceramic membrane is used as the carrier for carrying a platinum-based catalyst, and thus the platinum-based catalyst for the methanol reforming combustion chamber is formed. Compared with the conventional method for preparing the catalyst, the method has the advantage of effectively solving the problems of insufficient platinum carrying quantity, relatively small contact area with reactants and low catalytic activity in the present methanol reforming combustion chamber, so as to effectively improve the overall performance of cells.

Description

For the preparation method of the platinum catalyst of methanol recapitalization combustion chamber taking porous foam titanium as carrier
Technical field
The invention belongs to proton exchange ceramic membrane fuel cells field, relate to a kind of preparation method of the platinum based catalyst for methanol recapitalization fuel chambers.
Background technology
Along with continuous transition and the revolution of energy resource structure, novel energy technology due to its have clean, pollute the feature such as little, renewable and more and more receive people's concern, and fuel cell technology is because the combination of itself and micromachining technology makes it have more advantage in performance and price, therefore becomes one of focus.DMFC (PEMFC) is as a kind of high-new fuel cell technology, because it has efficiently, high-energy-density, good portability, fuel price is cheap and be easy to supplement, pollute the advantages such as little, in MEMS, microrobot, mini-medical apparatus, personal mobile communication equipment, all have wide practical use.For solving the intrinsic problem that causes open-circuit voltage and current density to reduce due to methanol crossover of DMFC, a kind of novel methanol recapitalization fuel cell arises at the historic moment, its feature is to carry out fuel supply with the form of gas reactant after high concentration methanol is restructured as to hydrogen, and its chief component is reformation reative cell and combustion chamber.Reformer chamber is the place that liquid methanol is restructured as gaseous hydrogen; Combustion chamber provides heat for reforming reaction.
Combustion chamber is as the source of reforming reaction heat, and its performance quality determines the degree that reforming reaction is carried out, and also determines the performance of whole battery.In combustion chamber, be common redox reaction, hydrogen or methanol aqueous solution and oxygen react under the effect of catalyst, produce Joule heat simultaneously.Combustion chamber catalyst mostly is platinum based catalyst, its catalyst lift-launch situation and catalyst activity are the key factor of conditioned response, only have the combustion chamber that meets the demands can provide enough long-term heats to react condition is provided for reformer chamber, and existing catalyst lift-launch mode can not meet the demands completely.
Summary of the invention
Object of the present invention aims to provide a kind of platinum catalyst preparation method taking the porous foam titanium based on differential arc oxidization technique processing as carrier, compared with existing catalyst preparation method, the platinum that the present invention can effectively solve current methanol recapitalization combustion chamber carries quantity not sufficient, problem with the less and catalytic activity of reactant contact area, thereby effectively improves cell integrated performance.
The object of the invention is to be achieved through the following technical solutions:
One, the surface modification treatment of porous foam titanium.First, taking porous foam titanium as anode, be placed in the electrolyte that contains aluminate, and pass to direct current or alternating current carries out differential arc oxidation processing, form alumina titanate ceramics film on porous foam titanium surface.In above-mentioned electrolyte, electrolytical content is 5 ~ 20g/L, and the processing time is 20 ~ 180min, and the alumina titanate ceramics film of formation is inner compact layer, outer loose structure.Secondly, formed aluminium titanates oxide ceramic membrane is carried out to sintering processes, make its decomposition be sintered to the secondary porous oxide ceramic membrane structure taking aluminium oxide and titanium oxide as main component.Above-mentioned sintering processes temperature is 600 ~ 1000 DEG C, and the sintering processes time is 10 ~ 120 minutes.
Two, the supporting and building of platinum based catalyst.Taking the porous foam titanium after above-mentioned differential arc oxidation and sintering processes as matrix, carry out supporting of platinum based catalyst on its surface: surface-treated porous foam titanium floods after the solution that contains Pt ion, dry and heat make presoma decompose, before use, reduce, activated catalyst.
Existing oxide ceramic membrane processing method mostly is by carrying out dry mode at metal base surface immersion oxide colloid again and forms membrane of oxide ceramics, and this kind of mode can cause the phenomenons such as oxide is inhomogeneous, ceramic membrane is imperfect.And the membrane of oxide ceramics that the present invention forms by differential arc oxidization technique and high temperature sintering technology can accomplish to cover at difform POROUS TITANIUM matrix the membrane of oxide ceramics of even, fine and close, complete and porous, and its film constituent, thickness are all adjustable.It is for methanol recapitalization combustion chamber, using under the condition of original reactant and reaction principle, two aspects are improved: one, as mentioned above, adopt differential arc oxidization technique and high temperature sintering technology to carry out surface modification treatment to POROUS TITANIUM, the ceramic membrane that forming component thickness is controlled, has strengthened reliability and the bond strength of film; They are two years old, by adopting POROUS TITANIUM to cover the structure of porous oxidation ceramic membrane, adopt infusion process to carry platinum based catalyst simultaneously, make porous oxidation ceramic membrane carrier more carry catalyst by the capillarity of catalyst in lift-launch process, thereby accomplish the increase of catalyst lift-launch amount under same matrix porosity condition, strengthened the contact area of reactant and catalyst, also strengthened the bond strength of catalyst and carrier simultaneously, thereby strengthen the extent of reaction, improved the utilization rate of reactant.
Advantage of the present invention is as follows:
(1) adopt the porous foam titanium of high-specific surface area as matrix skeleton structure, catalyst lift-launch amount obviously improves compared with existing carrier is under equal-volume condition, and the contact area of reactant and catalyst increases, and it is more complete that reaction is carried out;
(2) adopt differential arc oxidization technique and high temperature sintering technology to form porous ceramics membrane structure, further increase its surface area, catalyst enters porous ceramic film inside by capillarity simultaneously, has improved the bond strength of catalyst and matrix, has further improved reaction efficiency and catalyst stability;
(3) porous ceramic film is covered in Titanium skeleton matrix surface, has strengthened the corrosion resistance of metal, has improved the stability of metallic framework, has extended service life;
(4) the lift-launch process of catalyst is simple and convenient, can use infusion process, also can use finished catalyst directly to support.
Brief description of the drawings
Fig. 1 is chamber structure schematic diagram.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited to this; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1:
The porous foam titanium cutting is placed in to electrolytic cell, and using it as anode, electrolytic cell is negative electrode, with the Na of 5 ~ 15g/L 3alO 3for electrolyte, with 300 ~ 600V DC voltage, 0.05 ~ 0.30A/cm 2constant current density carry out differential arc oxidation processing, the processing time is 20 ~ 180 minutes, makes alumina titanate ceramics film.
The porous foam titanium of the covering aluminium titanates membrane of oxide ceramics of generation is placed in tube furnace, under 600 ~ 900 DEG C of conditions, carries out high temperature sintering processing, the processing time is 10 ~ 120 minutes, forms salic and titanium oxide ceramics film.
Porous foam titanium after surface modification treatment is immersed in to (the NH containing Pt 3) 4(NO 3) 2complex catalyst precursor liquid solution in, wherein the concentration of Pt is 0.01 ~ 0.1mol/L.After flooding 5-30 minute, be dried, then at N 2under atmosphere, at 400 ~ 800 DEG C, carry out calcination processing.Use front at H 2(25%, v%) N 2in atmosphere, reductase 12 hour at 300 ~ 500 DEG C.
Above-mentioned catalyst carrier of finishing dealing with is put into combustion chamber as shown in Figure 1, as previously mentioned, hydrogen contacts with catalyst and oxygen on porous foam titanium surface the operation principle of combustion chamber simultaneously, oxidation reaction occurs and generate water, emit a large amount of heat simultaneously, supply with reforming reaction.Combustion chamber shown in Fig. 1 is the groove being consistent with carrier bulk, and left side is air admission hole, for inputting methanol aqueous solution or H 2and air; Right side is steam vent, for discharging reaction product and unreacted reactant.
embodiment 2:
The difference of this example and embodiment 1 is, in described electrolyte, contain 10g/L Na 3alO 3, DC voltage is that 500V, current density are 0.10A/cm 2, the processing time is 60 minutes.
embodiment 3:
This example is with the difference of embodiment 1, adopt alternating voltage to carry out differential arc oxidation processing to porous foam titanium, treatment conditions are: forward voltage is that 300 ~ 700V, negative voltage are that 0 ~ 200V, operating frequency are that 10 ~ 3000Hz, dutycycle are 10 ~ 60%, the processing time is 20 ~ 180min.
embodiment 4:
The difference of this example and embodiment 3 is, forward current density is 10A/cm 2, negative current density is 10A/cm 2, operating frequency is that 500Hz, dutycycle are 30%, the processing time is 100min.
embodiment 5:
The difference of this example and embodiment 3 is, forward current density is 15A/cm 2, negative current density is 15A/cm 2, operating frequency is that 1000Hz, dutycycle are 50%, the processing time is 60min.
embodiment 6:
The difference of this example and embodiment 1 is, in the time that high temperature sintering is processed, fixed temperature is 900 DEG C and carries out constant temperature sintering processes.

Claims (9)

1. a preparation method for the platinum catalyst taking porous foam titanium as carrier for methanol recapitalization combustion chamber, is characterized in that described method step is as follows:
One, taking porous foam titanium as anode, be placed in the electrolyte that contains aluminate, apply direct current or alternating voltage and carry out differential arc oxidation processing 20 ~ 180 minutes, form the porous oxide ceramic membrane taking aluminium titanates as main component on its surface;
Two, porous oxidation ceramic membrane is carried out to high temperature sintering processing, obtain being coated with the titanium foam of aluminium oxide and titanium oxide ceramics film;
Three, using the titanium foam that is coated with aluminium oxide and titanium oxide ceramics film as substrate, carry out supporting of platinum based catalyst on its surface, obtain the platinum based catalyst for methanol recapitalization combustion chamber.
According to claim 1 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, the content that it is characterized in that aluminate in described electrolyte is 5-20g/L.
According to claim 1 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, it is characterized in that applying DC voltage carry out differential arc oxidation process time, DC voltage is that 300V ~ 600V, current density are 0.05 ~ 0.30A/cm 2, the processing time is 20 ~ 180 minutes.
According to claim 1 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, it is characterized in that applying alternating voltage and carry out differential arc oxidation while processing, forward voltage is that 300 ~ 700V, negative voltage are that 0 ~ 200V, operating frequency are that 10 ~ 3000Hz, dutycycle are 10 ~ 60%, the processing time is 20 ~ 180min.
According to claim 1 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, it is characterized in that carrying out high temperature sintering while processing, its treatment temperature is 600 ~ 1000 DEG C, the processing time is 10 ~ 120 minutes.
According to claim 1 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, the loading method that it is characterized in that described platinum based catalyst is infusion process.
According to claim 6 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, the concrete steps that it is characterized in that described infusion process are: by the titanium foam that is coated with aluminium oxide and titanium oxide ceramics film after the catalyst based presoma dipping of Pt, drying and heating decomposes presoma, before use, reduce, activated catalyst.
According to claim 7 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, it is characterized in that the catalyst based presoma of described Pt is Pt (NH 3) 4(NO 3) 2solution.
According to claim 8 for methanol recapitalization combustion chamber the preparation method of the platinum catalyst taking porous foam titanium as carrier, it is characterized in that described Pt (NH 3) 4(NO 3) 2in solution, the concentration of Pt is 0.01 ~ 0.1mol/L.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107754754A (en) * 2017-09-19 2018-03-06 浙江工业大学 A kind of composite of titanium sponge loading alumina particle and its preparation method and application

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US7067453B1 (en) * 2001-07-13 2006-06-27 Innovatek, Inc. Hydrocarbon fuel reforming catalyst and use thereof
CN101185891A (en) * 2007-11-29 2008-05-28 申靓博 Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof

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Publication number Priority date Publication date Assignee Title
CN107754754A (en) * 2017-09-19 2018-03-06 浙江工业大学 A kind of composite of titanium sponge loading alumina particle and its preparation method and application

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Inventor after: Zhang Xuelin

Inventor after: Zhang Yufeng

Inventor after: Chen Hailong

Inventor after: Liu Xiaowei

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Inventor before: Ma Zezhong

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Free format text: CORRECT: INVENTOR; FROM: ZHANG XUELIN MA ZEZHONG LIU XIAOWEI ZHANG YUFENG TO: ZHANG XUELIN ZHANG YUFENG CHEN HAILONG LIU XIAOWEI

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