CN101015798B - Platinum-ruthenium radical nano-electrocatalyst and preparing method based on metal cluster compound path - Google Patents
Platinum-ruthenium radical nano-electrocatalyst and preparing method based on metal cluster compound path Download PDFInfo
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- CN101015798B CN101015798B CN2007100376217A CN200710037621A CN101015798B CN 101015798 B CN101015798 B CN 101015798B CN 2007100376217 A CN2007100376217 A CN 2007100376217A CN 200710037621 A CN200710037621 A CN 200710037621A CN 101015798 B CN101015798 B CN 101015798B
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Abstract
The invention provides a method for preparing load-type and non-load-type palladium-ruthenium base electric catalyst, based on metal group, wherein the catalyst is mixture of palladium and ruthenium, or added with one or several components of transition metals IB-IIIB. The inventive method is characterized in that 1, in alkali condition, reacting carbonic oxide and precursor of catalyst at 20-100Deg. C to obtain metal group solution, 2, under inertia gas, CO or their mixture, adding different carbon carriers into precursor, mixing and removing solvent under inertia gas, CO or their mixture at30-120Deg. C, 3, thermal processing for 10min-8h, 4, washing, drying and obtaining final catalyst whose size is 1.5nm-20nm, with controllable size and components, and narrow particle distribution, tobe used as anode catalyst of atom exchange membrane fuel battery.
Description
Technical field
The present invention relates to a kind of platinum-ruthenium radical nano eelctro-catalyst and reach preparation method based on the metal cluster compound approach, prepared or rather anode electrocatalyst to Proton Exchange Membrane Fuel Cells, this catalyst is to methyl alcohol, hydrogen and CO, H
2Presented very high catalytic performance with the electrochemical oxidation of CO mist.Belong to the anode catalyst field.
Background technology
The fuel cell power generating system energy conversion efficiency is high, and environmental pollution is little, can be used as the future ideality electrical source of power, thereby receives countries in the world scientist's extensive concern, and for this reason, a large amount of human and material resources have all been dropped in countries in the world and financial resources are studied.Exploitation is that fuel cell (PEMFC) electric motor car of fuel has many-sided significance with hydrogen; It not only is related to the energy strategy safety of country; Solve the problem of environmental pollution that internal-combustion engines vehicle brings; Improve the proportion of utilization of clean fuel in energy resource consumption, and can promote China's scientific and technological development level, realize the Domestic Automotive Industry great-leap-forward development.In addition, in the face of the automobile market of rapid growth, the development fuel cell car also is extremely important.DMFC (DMFC) can be used as the portable power source of notebook computer, mobile phone, electric bicycle etc. owing to the advantage of self, has extremely wide application prospect.The Toshiba of the Smart Fuel Cell, Korea S Samsung high-tech research institute of U.S. Los Alamos National Laboratory, Germany and Japan etc. has developed the DMFC model machine in succession, its performance with several years ago compared large increase.To really realize the industrialization of these two kinds of fuel cells, also need reduce cost and improve on the battery performance and work hard.Wherein, Platinum consumption that platinum consumption that cathod catalyst is high and high polarization overpotential and anode catalyst are high and catalyst are prone to partly limited its business-like exploitation by problems such as impurity CO poison; Therefore, all press for the high-performance anode catalyst of developing antitoxinization for these two kinds of fuel cells.Because catalytic performance and Preparation of catalysts method are closely related, thus the appropriate preparation method of catalyst to cause the pass important to improving its performance.
The present invention has prepared a kind of high-performance of Proton Exchange Membrane Fuel Cells, anode catalyst of antitoxinization of being used for through metal cluster compound approach and suitable post processing.
Summary of the invention
The invention provides a kind of platinum-ruthenium radical nano eelctro-catalyst and reach preparation method based on the metal cluster compound approach; Its typical production comprises the synthetic of catalyst precursor～metal carbonyl clusters; The injection of carbon carrier, the heat treatment of presoma, and the post processing of catalyst.Concrete steps are following two kinds:
Method A. is metal carbonyl clusters synthetic 1.: take by weighing a certain amount of contain Pt, Ru or contain slaines such as Pt, Ru, Os, Pd, Ir, Rh, Ni, Co, Fe with certain proportion be dissolved in methyl alcohol, ethanol, acetone, water; Or in their mixture, wherein Pt content accounts for the 25%-95% (mass percent) of amount of metal, the 75%-5% (mass percent) that Ru content accounts for amount of metal.Used metal is chloride or nitrate etc.In being dissolved with metal ion solution, add a certain amount of NaOH, Na then
2CO
3, NaHCO
3, sodium acetate, organic amine; Or their mixture, the pH value of control solution is 7.5-14.Logical then inert gas or CO gas are removed the air in the system, under the mixed atmosphere of CO or CO and inert gas composition, more than 1～36 hour, promptly obtain metal cluster compound solution (component A) in 20～100 ℃ of reactions.
2. the injection of carbon carrier: at inert gas or CO or theirs is mixed gas protected down to a certain amount of carbon carrier of component (A) adding.Carbon carrier can be activated carbon, SWCN, multi-walled carbon nano-tubes, mesoporous carbon, carbon fiber, or the mixture between them etc., the mass fraction of carbon carrier in final catalyst is＞5～95wt.%.After stirring a period of time, under inert gas, CO or they mixed gas protected, remove solvent at 30～120 ℃ then, obtain component (B).
3. the heat treatment of catalyst precursor: the component (B) that step 2 is obtained places tube furnace, at room temperature logical earlier nitrogen, argon gas, hydrogen, CO; Or their mist to be to remove the air in the boiler tube, then in these atmosphere 150～200 ℃ of heat treatments 10 minutes to more than 8 hours, obtain component (C).
4. post processing: the component of cool to room temperature (C) repeated water washing repeatedly and with liquor argenti nitratis ophthalmicus check, does not have chlorion, then (Ar, H under certain atmosphere after the heat treatment in eluate
2, N
2, O
2, air or their mist) 100-200 ℃ drying, promptly obtain final catalyst.
Method B. is synthesizing of metal carbonyl clusters 1.: take by weighing the slaine that contains Pt, Ru or contain Pt, Ru and Ni, Co or Fe; And be dissolved in methyl alcohol, ethanol, acetone, water or their mixture, wherein to account for the mass percent of amount of metal be that the mass percent that 25%-95%, Ru content account for amount of metal is 75%-5% to Pt content; The mass percent that transition metal accounts for the Pt-Ru metal is that 5-30% adds NaOH, Na then in being dissolved with metal ion solution
2CO
3, NaHCO
3, sodium acetate, organic amine or their mixture, the pH value of control solution is 7.5-14; Logical then inert gas or CO gas are removed the air in the system, under the mixed atmosphere of CO or CO and inert gas composition, more than 1～36 hour, promptly obtain metal cluster compound solution (component A) in 20～100 ℃ of reactions;
2. the injection of carbon carrier: add carbon carrier to step component 1. down at inert gas or CO or the mixed gas protected of them, the mass percent of carbon carrier in final catalyst is 5～95wt.%; After the stirring, under inert gas, CO or they mixed gas protected, remove solvent at 30～120 ℃;
3. the heat treatment of catalyst precursor: the component that 2. step is obtained places tube furnace; Earlier at room temperature logical nitrogen, argon gas, hydrogen, CO or their mist to be to remove the air in the boiler tube, then in these atmosphere 100～140 ℃ of heat treatments 10 minutes to 8 hours;
4. post processing:, and, in eluate, do not have chlorion, then at Ar, H with the liquor argenti nitratis ophthalmicus check with the 3. component repeated water washing of cool to room temperature after the heat treatment of step
2, N
2, O
2, 100-200 ℃ of drying under air or their mixed-gas atmosphere;
5. with the 4. electrochemical agent of Pt-Ru base of flush away Ni, Co or Fe species of step, 3. identical set by step again atmosphere and time handle down, and heat treatment temperature is 150-200 ℃;
6. the component repeating step of heat treatment cool to room temperature 4. wash, drying.
By the size of the catalyst of two kinds of methods preparations of above-mentioned A, B be 1.5 nm to the 20nm and distribution of particles narrow; The composition of catalyst is controlled simultaneously, and these catalyst become the very high catalytic activity of filling material and stable preferably as the anode catalyst of Proton Exchange Membrane Fuel Cells.Especially method B; Because heat treatment temperature is lower than 150 ℃ for the first time, thus Ni, Co or Fe species, not with Pt and Ru alloying; After washing, be prone to remove, but the effect that they have the inhibition particle diameter to grow up again makes the particle diameter of the eelctro-catalyst of preparation be decreased to 1.5nm (seeing embodiment 3 for details).
Nanometer by method for preparing; The nanometer electrical catalyst that catalyst is made up of the metal carbon carrier; Wherein the mass percent of carbon carrier is 5-95%; Wherein metal is the mixture of platinum and ruthenium, or in the mixture of platinum and ruthenium, adds transition metal IB one or more assistant formations to IIIB, forms multi-component catalyst.Pt content accounts for the 25-95% (mass percent) of metal in the mixture of platinum and ruthenium, and Ru content accounts for the 75-5% (mass percent) of amount of metal; The transition metal that in platinum and ruthenium, adds is any or several kinds among Os, Pd, Rh, Ni, Co and the Fe; It is 5-30% that transition metal accounts for Pt-Ru metal quality percentage.
Description of drawings
The TEM photo of Fig. 1 embodiment of the invention 2 preparation catalyst
The particle diameter distribution schematic diagram of Fig. 2 embodiment 2
The X diffraction pattern of the eelctro-catalyst that Fig. 3 embodiment 3 provides
The TEM photo of the eelctro-catalyst that Fig. 4 embodiment 3 provides
The particle diameter distribution schematic diagram of the eelctro-catalyst that Fig. 5 embodiment 3 provides
The specific embodiment
Elaboration through specific embodiment below, further specifying substantive distinguishing features of the present invention and obvious improvement, but the present invention is limited to described embodiment absolutely not.
Embodiment 1～Pt: Ru (3: 2,54wt.%)/the C Preparation of catalysts
1, takes by weighing the Na of 316.5mg
2PtCl
66H
2The RuCl of O (metal platinum content 31.3%), 85.6mg
3H
2The NaAC of O (metal Ru content 40wt%), 336.7mg joins in the methyl alcohol of 30ml; Earlier logical high pure nitrogen 15 minutes is to remove the air in the solution; 55 ℃ are reacted 24h in CO atmosphere then, can obtain the methanol solution (component A) of glaucous carbonyl cluster compound.
2, the Vulcan XC-72R active carbon that under nitrogen protection, in the solution that obtains, adds 113.5mg, behind the stirring 6h, evaporate to dryness methyl alcohol in 60 ℃ of nitrogen atmospheres, cool to room temperature (B component).
3, B component 150 ℃ of heat treatment 2h of warp in hydrogen, cool to room temperature (component C).
4, component (C) repeated water washing repeatedly with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate, and then 120 ℃ of dry 2h, promptly obtains final catalyst (component D).The Pt of catalyst and ruthenium content are through icp analysis, and show Pt: the Ru atomic ratio is 3: 2, and metal quality percentage is 54wt%.Its analysis result and theoretical value basically identical.
5, the catalyst that obtains characterizes through X-ray diffraction, and mean particle diameter is about 2.6nm, and average grain diameter is less than business-like catalyst, and its electrocatalysis characteristic to the hydroxide of methanol oxidation and resisting CO poison surpasses business-like catalyst.
Embodiment 2～Pt: Ru: Ni (6: 3: 1,20wt%)/the C Preparation of catalysts
1, takes by weighing the Na of 159.7mg
2PtCl
66H
2The RuCl of O (metal platinum content 31.3%), 28.9mg
3H
2The NiCl of O (metal Ru content 40wt%), 11.1mg
26H
2The NaAC of O, 127.3mg joins the CH of 20ml
3Among the OH, 50 ℃ were reacted 12h to earlier logical high pure nitrogen in CO atmosphere then, obtained glaucous CH to remove the air in the solution in 15 minutes
3OH solution (component A).
2, the Vulcan XC-72R active carbon that under nitrogen protection, in the solution that obtains, adds 261.8mg, behind the stirring 6h, evaporate to dryness methyl alcohol in 60 ℃ of nitrogen atmospheres, cool to room temperature (B component).
3, B component 175 ℃ of heat treatment 2h of warp in hydrogen, cool to room temperature (component C).
4, component (C) repeated water washing repeatedly with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate, and then 120 ℃ of dry 2h, promptly obtains final catalyst (component D).The content of the Pt of catalyst, Ru and Ni is through icp analysis, and show Pt: Ru: the Ni atomic ratio is 6: 3: 1, and the metal quality percentage composition is 20wt%.Its analysis result and theoretical value basically identical.
5, the catalyst that obtains characterizes through the X-ray; Mean particle diameter＜2.1nm, the TEM picture of the catalyst of acquisition is shown in the following figure, the about 2.2nm of mean particle diameter; Less than business-like catalyst, its electrocatalysis characteristic to methanol oxidation obviously surpasses business-like catalyst.Narrow diameter distribution is described.
1, takes by weighing the Na of 356.1mg
2PtCl
66H
2The RuCl of O (metal platinum content 31.3%), 96.3mg
3H
2The NiCl of O (metal Ru content 40wt%), 69.3mg
26H
2The NaAC of O, 378.8mg joins the CH of 35ml
3Among the OH, earlier logical high pure nitrogen reacted 18h at 58 ℃ to remove the air in the solution in 15 minutes then in CO atmosphere, obtain the CH of metal cluster compound
3OH solution (component A).
2, the Vulcan XC-72R active carbon that under nitrogen protection, in the solution that obtains, adds 127.8mg, behind the stirring 6h, evaporate to dryness methyl alcohol in 60 ℃ of nitrogen atmospheres, cool to room temperature (B component).
3, B component 125 ℃ of heat treatment 2h of warp in hydrogen, cool to room temperature (component C).
4, component (C) repeated water washing repeatedly with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate, and then 120 ℃ of dry 2h, promptly obtains final catalyst (component D).The content of catalyst Pt and Ru is through icp analysis, and show Pt: the Ru atomic ratio is 3: 2, and the metal quality mark is 54wt%.The content of its Pt and Ru and theoretical value basically identical.Because the heat treatment temperature of step 3 is low, the nickel species do not have and Pt and Ru alloying, through being removed after the washing.The advantage that adds the nickel species here is that the particle diameter of the Pt-Ru bimetallic base eelctro-catalyst that obtains is especially little, helps the raising of subsequent heat treatment alloying level and still keeps alloy particle very little.The transition metal of sacrificing can also be generalized to species such as iron, cobalt, chromium except that the nickel species.
5, with component D 175 ℃ of heat treatment 2h of warp in hydrogen, cool to room temperature (component E).
6, component (E) repeated water washing repeatedly, and then 120 ℃ of dry 2h promptly obtain final catalyst (component F).The content of catalyst Pt and Ru is through icp analysis, and show Pt: the Ru atomic ratio is 3: 2, and the metal quality mark is 54wt%.The content of its Pt and Ru and theoretical value basically identical.
7, the catalyst F that obtains characterizes through X-ray diffraction, and mean particle diameter is about 2.2nm, and average grain diameter is significantly less than business-like catalyst, can find out on the TEM figure that the particle size of acquisition is suitable with XRD result.This catalyst obviously surpasses business-like catalyst to the electrocatalysis characteristic of methanol oxidation and anti-CO.
Above-mentioned three embodiment are merely typical instance, can add among Os except that Ni, Ir, Pd, Rh, Co, the Fe any in its Pt-Ru alloy, form different multi-component Pt-Ru base eelctro-catalysts, and its technical process is identical with the embodiment that is lifted.
Claims (3)
1. the preparation method of platinum-ruthenium radical nano eelctro-catalyst is characterized in that the preparation process comprises synthetic, the injection of carbon carrier of metal carbonyl clusters, the heat treatment of catalyst precursor and the post processing of catalyst, and concrete steps are divided in following two kinds a kind of:
Method A. is metal carbonyl clusters synthetic 1.: take by weighing and contain Pt, Ru or in Pt and Ru mixture, add Os, Pd, Ir, Ni, Co or Fe slaine; And be dissolved in methyl alcohol, ethanol, acetone, water or their mixture, the mass percent that wherein Pt content accounts for amount of metal in the mixture of Pt and Ru is that the mass percent that 25%-95%, Ru content account for amount of metal is 75%-5%; The mass percent that transition metal accounts for the Pt-Ru mixture is 5-30%, in being dissolved with metal ion solution, adds NaOH, Na then
2CO
3, NaHCO
3, sodium acetate, organic amine or their mixture, the pH value of control solution is 7.5-14; Logical then inert gas or CO gas are removed the air in the system, under the mixed atmosphere of CO or CO and inert gas composition, more than 1～36 hour, promptly obtain metal cluster compound solution in 20～100 ℃ of reactions;
2. the injection of carbon carrier: add carbon carrier to step component 1. down at inert gas or CO or the mixed gas protected of them, the mass percent of carbon carrier in final catalyst is greater than 5%～95wt.%; After the stirring, under inert gas, CO or they mixed gas protected, remove solvent at 30～120 ℃;
3. the heat treatment of catalyst precursor: the component that 2. step is obtained places tube furnace; Earlier at room temperature logical nitrogen, argon gas, hydrogen, CO or their mist to be to remove the air in the boiler tube, then in these atmosphere 150～200 ℃ of heat treatments 10 minutes to 8 hours;
4. the post processing of catalyst:, and, in eluate, do not have chlorion, then at Ar, H with the liquor argenti nitratis ophthalmicus check with the 3. component repeated water washing of cool to room temperature after the heat treatment of step
2, N
2, O
2, 100-200 ℃ of drying under air or their mixed-gas atmosphere;
Method B. is synthesizing of metal carbonyl clusters 1.: take by weighing the slaine that contains Pt, Ru or in Pt and Ru mixture, add Ni, Co or Fe; And be dissolved in methyl alcohol, ethanol, acetone, water or their mixture, the mass percent that wherein Pt content accounts for amount of metal in the mixture of Pt and Ru is that the mass percent that 25%-95%, Ru content account for amount of metal is 75%-5%; The mass percent that transition metal accounts for the Pt-Ru mixture is 5-30%, in being dissolved with metal ion solution, adds NaOH, Na then
2CO
3, NaHCO
3, sodium acetate, organic amine or their mixture, the pH value of control solution is 7.5-14; Logical then inert gas or CO gas are removed the air in the system, under the mixed atmosphere of CO or CO and inert gas composition, more than 1～36 hour, promptly obtain metal cluster compound solution in 20～100 ℃ of reactions;
2. the injection of carbon carrier: add carbon carrier to step component 1. down at inert gas or CO or the mixed gas protected of them, the mass percent of carbon carrier in final catalyst is 5～95wt.%; After the stirring, under inert gas, CO or they mixed gas protected, remove solvent at 30～120 ℃;
3. the heat treatment of catalyst precursor: the component that 2. step is obtained places tube furnace; Earlier at room temperature logical nitrogen, argon gas, hydrogen, CO or their mist to be to remove the air in the boiler tube, then in these atmosphere 100～140 ℃ of heat treatments 10 minutes to 8 hours;
4. the post processing of catalyst:, and, in eluate, do not have chlorion, then at Ar, H with the liquor argenti nitratis ophthalmicus check with the 3. component repeated water washing of cool to room temperature after the heat treatment of step
2, N
2, O
2, 100-200 ℃ of drying under air or their mixed-gas atmosphere;
5. with the 4. electrochemical agent of Pt-Ru base of flush away Ni, Co or Fe species of step, 3. identical set by step again atmosphere and time handle down, and heat treatment temperature is 150-200 ℃;
6. the component repeating step of heat treatment cool to room temperature 4. wash, drying.
2. by the preparation method of platinum as claimed in claim 1-ruthenium radical nano eelctro-catalyst, it is characterized in that described slaine is chloride or nitrate.
3. by the preparation method of platinum as claimed in claim 1-ruthenium radical nano eelctro-catalyst, it is characterized in that prepared catalyst composition is controlled, and distribution of particles is narrow.
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| CN111744473A (en) * | 2019-03-27 | 2020-10-09 | 宁波中科科创新能源科技有限公司 | Preparation method of Pt-based multi-component alloy nano electro-catalyst |
| CN111617774B (en) * | 2020-06-10 | 2022-11-08 | 贵州大学 | Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure |
| CN113889629A (en) * | 2021-09-28 | 2022-01-04 | 中钢集团南京新材料研究院有限公司 | Preparation method of platinum-ruthenium alloy catalyst for fuel cell anode |
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