CN1788847A - Carbon wool ball carried type catalyst and its preparation method and uses - Google Patents
Carbon wool ball carried type catalyst and its preparation method and uses Download PDFInfo
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- CN1788847A CN1788847A CNA2004100989227A CN200410098922A CN1788847A CN 1788847 A CN1788847 A CN 1788847A CN A2004100989227 A CNA2004100989227 A CN A2004100989227A CN 200410098922 A CN200410098922 A CN 200410098922A CN 1788847 A CN1788847 A CN 1788847A
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Abstract
The present invention relates to one kind of carbon floccule supported catalyst and its preparation process and use. The carbon floccule supported catalyst has Pt or PtM alloy in 1-80 wt% supported on carbon floccule material, where M is Ru, Sn or Mo, and is prepared through liquid phase process. It may be used directly in alcohol fuel cell. Electrochemical test shows that the carbon floccule supported Pt or PtM alloy catalyst has methanol electrochemically oxidizing activity in 1.6-3 times higher than that of similar available catalyst in the same supported amount and that the carbon floccule supported PtSn alloy catalyst has ethanol electrochemically oxidizing activity in 2-3 times higher than that of similar available catalyst in the same supported amount. In addition, the present invention has simple technological process, high repeatability, high product purity and stable product performance, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of carbon wool ball carried type catalyst, specifically relate to a kind of carbon wool ball carried Pt that is used for direct alcohol fuel battery or PtM (catalyst of (M-represents metal) alloy, and its production and use.
Background technology
Directly alcohol fuel battery is a kind of desirable power conversion device, have theoretical energy density height, conversion efficiency height, pollution-free, advantage such as the working time is long, volume is little, simple in structure and fuel source is abundant, on small portable power supplys such as electric powered motor source and laptop electric power, camera power supply, cellular phone power supplies and individual soldier's power supply, have broad application prospects.
At present, directly the alcohol fuel battery two big difficult points that need solve are: pure infiltration problem relevant with PEM and the relevant pure anodic oxidation efficiency with catalyst.About the anodic oxidation of alcohol, except composition, structure and the form of catalyst itself, carrier also is the key factor that influences the catalyst activity.At present, widely used carrier is a carbon black, yet because its particle less (about 50nm) is easily fine and close after hot pressing in the preparation electrode process, thereby hinder the mass transfer of threephase region, influence the performance of catalyst activity.In document [1]: Bessel CA, LauberndsK, Rodriguez NM, and Baker RTK.J.Phys.Chem.B 2001; 105 (6): 1115-8, and document [2]: Li WZ, Liang CH, Zhou WJ, Qiu JS, Zhou ZH, Sun G.Q, et al.J.Phys.Chem..B 2003; Among the 107:6292-9, reported and adopted carbon nano-fiber or CNT to improve activity of such catalysts as the catalyst carrier of Pt or Pt alloy.But because carbon nano-fiber or CNT lighter weight as carrier, are difficult for fixing when using in fluid media (medium); And be inhaled into respiratory tract easily, be unfavorable for people's health.Recently, Tsing-Hua University and this seminar of Inst. of Physics, CAS adopt carbonaceous mesophase spherules (mesocarbon microbeads, MCMB) and hard charcoal ball as the carrier material of Pt or Pt alloy catalyst, as document [3]: Yi-Cheng Liu, Xin-Ping Qiu, Yu-Qing Huang, Wen-Tao Zhu, J.Power Sources 111 (2002) 160-164, and document [4]: RuizhiYang, Xinping Qiu, Huairuo Zhang, Jianqi Li, Wentao Zhu, Zhaoxiang Wang, XuejieHuang, Liquan Chen, described in Carbon 43 (2005) 11-16, the carrier material of improved catalyst has improved the utilization rate of Pt, the threephase region when having improved the alcohols electro-oxidation reaction and the mass transfer of catalyst layer, thus reach the purpose that improves the catalyst activity.But because carbonaceous mesophase spherules that is adopted and hard charcoal ball have the low shortcoming of specific area, can't carry out the high-load load of Pt, thereby its application in direct alcohol fuel battery is very restricted.
Summary of the invention
It is less to the objective of the invention is to overcome the carbon black support particle, easily fine and close after hot pressing in the preparation electrode process, thereby hinders the mass transfer of threephase region, influences the performance of catalyst activity; And carbonaceous mesophase spherules and hard charcoal ball carrier have the low shortcoming of specific area, can't carry out the high-load load of Pt, thereby the defective that its application in direct alcohol fuel battery is very restricted, thereby a kind of Pt of making or PtM are provided, and (load capacity of (M-represents metal) alloy increases, and high degree of dispersion, help improving the carbon wool ball carried catalyst of gas phase and liquid phase reactor mass transfer, and its production and use.
The objective of the invention is to realize by the following technical solutions:
Carbon wool ball carried catalyst provided by the invention, it is to use carbon wool ball material as carrier, the Pt of load 1～80wt% or PtM alloy on it; Described M is Ru, Sn or Mo.
A kind of novel carbon/carbon compound material (separate case is applied for a patent) that described carbon wool ball material proposes first for the inventor, it is a core material with carbon element, and the 1-dimention nano carbon fiber of growth in its surface is or/and CNT; The average grain diameter of described core material with carbon element is 100nm～1mm, both can be graphited material with carbon element, also can be the material with carbon element of disordered structure, and preferred geometric shape is spherical; The diameter of described 1-dimention nano carbon fiber or CNT is 1～500nm, and length is 10nm～100 μ m, and draw ratio is 5～10
5This one dimension CNT can be single wall, double-walled or many walls; This 1-dimention nano carbon fiber and CNT both can have straight geometry appearance, also can have crooked geometry appearance; Both vertical core carbon material surface oriented growths also can the non-directional growth.
The average diameter of described Pt or PtM alloy is 1.0～50nm.
In the described PtM alloy, the atomic ratio that Pt accounts in alloy is 10～90%.
The invention provides a kind of above-mentioned carbon wool ball carried Preparation of catalysts method, it is by the liquid phase method preparation, mainly may further comprise the steps:
(1) preliminary treatment of carbon wool ball material: with carbon wool ball material at 70% HNO
3In refluxed 3～48 hours in 60～160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon bobbles through surface oxidation;
Described carbon wool ball material is by following method (separate case is applied for a patent) preparation: (a) preparation of catalyst solution: take by weighing in metallic iron, cobalt, nickel or the molybdenum salt one or more as catalyst, add alcohols solvent, put into container, stirring and dissolving makes the catalyst solution that concentration is 0.0001～0.1M; Described molysite is Fe (NO
3)
39H
2O, FeSO
47H
2O, Fe (OH) (CH
3COO)
2Described cobalt salt is Co (NO
3)
26H
2O, Co (CH
3COO)
24H
2O; Described nickel salt is Ni (NO
3)
26H
2O; Described molybdenum salt is (NH
4)
6Mo
7O
244H
2O; Described alcohols solvent is one or more in ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine solution; (b) catalyst cupport: take by weighing the alcoholic solution that the core material with carbon element adds above-mentioned metal ion---in the catalyst solution, metallic catalyst (M) is M: C=1 with the mass ratio (w/w) of core material with carbon element (C): 1～1: 1000; And abundant stir about 30 minutes～2 hours, left standstill about 1～72 hour, separate drying; (c) chemical vapour deposition (CVD): the material that step (b) is obtained is placed in the heatproof container (as graphite boat, aluminium oxide boat), the tube furnace that the air-tightness of packing into then is good (also can be with vacuum extractor), charge into the gaseous mixture of argon gas or argon gas and hydrogen, or carry out preliminary treatment, temperature programming to 400 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas being converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or being converted to the gaseous mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, after constant temperature 10 minutes carried out chemical vapour deposition (CVD) to 48 hours; Naturally cool to room temperature; (d) product purifies: product is packed in the container into the HNO 70%
3In refluxed 4～24 hours in 110～160 ℃ of temperature; Naturally after the cooling, fully dilute with deionized water, remove supernatant liquor after the centrifugation, lower floor's solid matter with deionized water cyclic washing promptly gets product more than three times---novel carbon wool ball material.
(2) carbon wool ball carried Pt Preparation of catalysts: take by weighing K
2PtCl
6Be dissolved in ethylene glycol and the water; fully stir after 1 hour; taking by weighing the carbon bobbles through surface oxidation that step 1) makes by Pt load capacity 1～80wt% adds in the solution for preparing; refluxed about 4～12 hours under argon shield in 140～180 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is carbon wool ball carried Pt catalyst;
(3) preparation of carbon wool ball carried PtM alloy catalyst: 1～80wt% takes by weighing H by PtM alloy load capacity
2PtCl
66H
2O and RuCl
3XH
2(content of Ru is 37.5% to O, w/w), SnCl
22H
2O or MoCl
4Wiring solution-forming soluble in water stirred after 30 minutes, took by weighing the carbon bobbles through surface oxidation that step 1) makes and added in the solution for preparing, and stirred after 30 minutes, HCHO solution was slowly splashed in the mixed liquor that continues stirring again; After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is carbon wool ball carried PtM alloy catalyst.
Above-mentioned carbon wool ball carried catalyst provided by the invention can directly used in the alcohol fuel battery.
Adopt method in common preparation and test electrode in the research.At first, carbon wool ball carried Pt that the present invention is obtained or PtRu alloy material catalyst add perfluorinated sulfonic acid solution (5wt%, Nafion , Du Pont) and ethylene glycol (1: 10: 10), magnetic agitation 4h; The slurry that makes is coated on the carbon paper (Toray) equably, and the Pt carrying capacity is 0.5mgcm in the electrode
-2About, make anode; Adopt the technology similar to anode to prepare negative electrode then, adopt the carbon wool ball material supporting Pt as oxygen reduction catalyst, the Pt carrying capacity is 0.5mg cm on the final negative electrode
-2Secondly, to Nafion-112
TMPEM carries out preprocessing process: at first handle in 3～5% aqueous hydrogen peroxide solution at 80 ℃; Take out the back and clean, handle in dilution heat of sulfuric acid at 80 ℃ again with deionized water, clean with washed with de-ionized water at last.At last, with anode, negative electrode and pretreated Nafion-112
TMPEM carries out hot pressing and obtains MEA (MembraneElectrode Assembly), and hot pressing temperature is 130 ℃, and hot pressing time is 3min, and the MEA thickness that finally obtains is about 1mm.
MEA is clipped in the middle of two blocks of high-density graphite plates, and groove is carved with in the graphite cake inboard, and the conversion zone on the graphite cake is 3cm
2Electro-chemical test adopts three-electrode system, and saturated calomel electrode (SCE) is inserted in anode graphite plate side.The electro-chemical test instrument is electrochemical workstation (CHI 660), adopts microcomputer control.
The result of electro-chemical test shows that this novel carbon wool ball material supporting Pt or PtM alloy catalyst are 1.6～3 times of catalytic activity of the Pt/Vulcan XC-72 that produces of the commercial U.S. ETEK company of identical load amount or PtRu/Vulcan XC-72 catalyst to the catalytic activity of methanol electrooxidation; This novel carbon wool ball material supporting Pt Sn alloy is 2～3 times of catalytic activity of the PtRu/Vulcan catalyst produced of the commercial U.S. ETEK company of identical load amount to the catalytic activity of ethanol electrochemical oxidation.
Compared with prior art, the advantage of carbon wool ball carried catalyst provided by the invention is, its with carbon wool ball material as carrier, this carbon wool ball material is that 1-dimention nano carbon fiber or carbon nano tube growth form at the core carbon material surface, it combines the core material with carbon element and has Stability Analysis of Structures, good dispersion be difficult for to be reunited, and epontic Nano carbon fibers peacekeeping CNT has than macroporosity with than the advantage of bigger serface.Thereby, Pt or PtM alloy are carried on carbon bobbles surface, can make Pt or PtM alloying pellet have small size and with higher load amount, high degree of dispersion be carried on carbon bobbles surface; And because the bigger porosity that exists on the carbon bobbles, gas phase and liquid phase reactor material help improving the transmission of material on the catalyst after the load.In addition, technology of the present invention is simple, and good reproducibility, required instrument and equipment all are chemistry and material industry equipment commonly used; The prepared product purity height that goes out, stable performance is suitable for large-scale industrialization production.
Description of drawings
The field emission scan electron microscopic pattern of the carbon wool ball carried 20wt%Pt catalyst that Fig. 1 obtains for embodiment 3; (Fig. 1-1 amplifies 5000 times, and Fig. 1-2 amplifies 400000 times)
The comparison of the catalytic performance of Pt/VulcanXC-72 (20wt%Pt) catalyst that carbon wool ball carried 20wt%Pt catalyst that Fig. 2 obtains for embodiment 3 and U.S. ETEK company are produced; Fig. 2-1 is a cyclic voltammetry curve, and Fig. 2-2 is the constant current polarization curve, and wherein curve a represents carbon wool ball carried 20wt%Pt catalyst, curve b represent Pt/Vulcan XC-72 (ETEK, 20wt%Pt);
The PtRu/VulcanXC-72 that carbon wool ball carried 10wt%PtRu catalyst that Fig. 3 obtains for embodiment 7 and U.S. ETEK company are produced (10wt%PtRu, Pt: Ru=1: the 1) comparison of the catalytic performance of catalyst; Fig. 3-1 is a cyclic voltammetry curve, and Fig. 3-2 is the constant current polarization curve, and wherein curve a represents carbon wool ball carried 10wt%PtRu catalyst, and curve b represents Pt/Vulcan XC-72 (ETEK, 10wt%PtRu, Pt: Ru=1: 1).
The specific embodiment
Embodiment 1, carbon wool ball carried 1wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 48 hours in 60 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.01g K
2PtCl
6Be dissolved in 10ml ethylene glycol and the 0.25ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; further stir after 30 minutes; refluxed about 6 hours under argon shield in 140 ℃; after naturally cooling to room temperature, product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is a carbon wool ball carried Pt catalyst (1wt%Pt), the Pt high degree of dispersion is in its surface, its average diameter is 1.0nm.
The preparation of electrode and test: with the carbon wool ball carried Pt catalyst of gained add perfluorinated sulfonic acid solution (5wt%, Nafion , Du Pont) and ethylene glycol (1: 10: 10, w/w) in, magnetic agitation 4 hours.Be coated on equably after pulp preparation is finished on the carbon paper (Toray), the Pt carrying capacity is 0.3mg cm in the electrode
-2About.Negative electrode also adopts the technology preparation similar to anode, adopts carbon wool ball carried Pt catalyst (1wt%Pt) as oxygen reduction catalyst, and the Pt carrying capacity is 0.5mg cm on the final negative electrode
-2To Nafion-112
TMThe preprocessing process of PEM is: at first handle in 3～5% aqueous hydrogen peroxide solution at 80 ℃; Take out the back and clean, handle in dilution heat of sulfuric acid at 80 ℃ again with deionized water, clean with washed with de-ionized water at last.With anode, negative electrode and pretreated Nafion-112
TMPEM hot pressing obtains MEA (Membrane Electrode Assembly), and hot pressing temperature is 130 ℃, and hot pressing time is 3min, and the MEA thickness that finally obtains is about 1mm.
MEA is clipped in the middle of two blocks of high-density graphite plates, and groove is carved with in the graphite cake inboard, and the conversion zone on the graphite cake is 3cm
2Electro-chemical test adopts three-electrode system, and saturated calomel electrode (SCE) is inserted in anode graphite plate side.The electro-chemical test instrument is electrochemical workstation (CHI 660), adopts microcomputer control.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 238.0m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 85.0%.
Embodiment 2, carbon wool ball carried 10wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 48 hours in 60 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.1g K
2PtCl
6Be dissolved in 100ml ethylene glycol and the 2.5ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; further stir after 30 minutes; refluxed about 6 hours under argon shield in 140 ℃; after naturally cooling to room temperature, product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h.Products therefrom is a carbon wool ball carried Pt catalyst (10wt%Pt), and the Pt high degree of dispersion is in its surface, and its average diameter is 1.3nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (10wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 189.8m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 88.0%; At 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is Pt/Vulcan XC-72 (ETEK, 10wt%Pt) 2.5 of catalyst times, in addition, carbon wool ball carried Pt electrode has shown (E-TEK, the anode polarization performance that 10wt%Pt) electrode is lower than Pt/Vulcan XC-72.
Embodiment 3, carbon wool ball carried 20wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.2g K
2PtCl
6Be dissolved in 200ml ethylene glycol and the 5ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; refluxed about 6 hours under argon shield in 150 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is a carbon wool ball carried Pt catalyst (20wt%Pt), the Pt high degree of dispersion is in its surface, its average diameter is 2.3nm.Its emission scan electron microscopic shape appearance figure is seen Fig. 1.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (20wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 102.2m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 83.8%.At 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, Pt/VulcanXC-72 (20wt%Pt) catalyst of being produced in 25 ℃ of tests carbon wool ball carried 20wt%Pt catalyst and U.S. ETEK companies is to the catalytic performance of the electrochemical oxidation of methyl alcohol, by the cyclic voltammetry curve of Fig. 2-1 as can be known, the catalytic activity of carbon wool ball carried 20wt%Pt catalyst is Pt/Vulcan XC-72 (ETEK, 20wt%Pt) 2.4 of catalyst times.By the constant current polarization curve of Fig. 2-2 as can be known, carbon wool ball carried Pt electrode has shown (E-TEK, the anode polarization performance that 20wt%Pt) electrode is lower than Pt/VulcanXC-72.
Embodiment 4, carbon wool ball carried 40wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 12 hours in 100 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.4g K
2PtCl
6Be dissolved in 400ml ethylene glycol and the 10ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; refluxed about 6 hours under argon shield in 160 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is a carbon wool ball carried Pt catalyst (40wt%Pt), the Pt high degree of dispersion is in its surface, its average diameter is 2.9nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (40wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 80.2m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 83.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is Pt/Vulcan XC-72 (ETEK, 40wt%Pt) 2.6 of catalyst times, in addition, carbon wool ball carried Pt electrode has shown (E-TEK, the anode polarization performance that 40wt%Pt) electrode is lower than Pt/Vulcan XC-72.
Embodiment 5, carbon wool ball carried 60wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 6 hours in 140 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Carbon wool ball carried Pt Preparation of catalysts.Take by weighing 0.6g K
2PtCl
6Be dissolved in 600ml ethylene glycol and the 15ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; refluxed about 4 hours under argon shield in 180 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h.Products therefrom is a carbon wool ball carried Pt catalyst (60wt%Pt), and the Pt high degree of dispersion is in its surface, and its average diameter is 3.9nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (60wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 60.4m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 84.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, in 25 ℃ record its catalytic activity to the electrochemical oxidation of methyl alcohol be Pt/Vulcan XC-72 (ETEK, 60wt%Pt) 3 of catalyst times, in addition, carbon wool ball carried Pt electrode has shown (E-TEK, the anode polarization performance that 60wt%Pt) electrode is lower than Pt/Vulcan XC-72.
Embodiment 6, carbon wool ball carried 80wt%Pt Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 12 hours in 100 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.8g K
2PtCl
6Be dissolved in 800ml ethylene glycol and the 20ml water; fully stir after 1 hour; take by weighing through the carbon bobbles 0.722g of surface oxidation and add in the solution for preparing; refluxed about 12 hours under argon shield in 180 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is a carbon wool ball carried Pt catalyst (80wt%Pt), the Pt high degree of dispersion is in its surface, its average diameter is 11.0nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (80wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 21.3m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried Pt
2/ g, the utilization rate of Pt is 83.5%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is Pt/Vulcan XC-72 (ETEK, 80wt%Pt) 3.0 of catalyst times, in addition, carbon wool ball carried Pt electrode has shown (E-TEK, the anode polarization performance that 80wt%Pt) electrode is lower than Pt/Vulcan XC-72.
Embodiment 7, carbon wool ball carried 10wt%PtRu Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 10 hours in 110 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.26g H
2PtCl
66H
2O is made into 50ml solution, adds 0.135g RuCl
3XH
2(content of Ru is 37.5% to O, w/w), make Pt: Ru=1 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, taking by weighing 1.48g adds in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 50ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (10wt%PtRu, Pt: Ru=1: 1), wherein the average diameter of PtRu is 1.4nm to carbon wool ball carried PtRu catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (10wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 174.2m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 87.0%.At 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, Pt/VulcanXC-72 (the ETEK that is produced in 25 ℃ of tests carbon wool ball carried 10wt%PtRu catalyst and U.S. ETEK companies, 10wt%PtRu, Pt: Ru=1: 1) catalyst is to the catalytic performance of the electrochemical oxidation of methyl alcohol, by the cyclic voltammetry curve of Fig. 3-1 as can be known, the catalytic activity of carbon wool ball carried 10wt%PtRu catalyst is Pt/Vulcan XC-72 (ETEK, 10wt%PtRu, Pt: Ru=1: 1) 2.8 of catalyst times.By the constant current polarization curve of Fig. 3-2 as can be known, carbon wool ball carried PtRu electrode has shown (ETEK, 10wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than Pt/Vulcan XC-72.
Embodiment 8, carbon wool ball carried 20wt%PtRu Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 10 hours in 110 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.52g H
2PtCl
66H
2O is made into 100ml solution, adds 0.27g RuCl
3XH
2(content of Ru is 37.5% to O, w/w), make Pt: Ru=1 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, taking by weighing 1.48g adds in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 100ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (20wt%PtRu, Pt: Ru=1: 1), wherein the average diameter of PtRu is 2.2nm to carbon wool ball carried PtRu catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (20wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 109.6m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 86.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is PtRu/Vulcan XC-72 (ETEK, 20wt%PtRu, Pt: Ru=1: 1) 2.0 of catalyst times, in addition, carbon wool ball carried PtRu electrode has shown (E-TEK, 20wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/Vulcan XC-72.
Embodiment 9, carbon wool ball carried 20wt%PtSn Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.52g H
2PtCl
66H
2O is made into 100ml solution, adds 0.23gSnCl
22H
2O, make Pt: Sn=1 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, take by weighing 1.569g and add in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 100ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (20wt%PtSn, Pt: Sn=1: 1), wherein the average diameter of PtSn is 3.0nm to carbon wool ball carried PtSn catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (20wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 79.4m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 85.0%, at 1.0M H
2SO
4+ 1.0M CH
3CH
2In the OH solution, recording its catalytic activity to the electrochemical oxidation of ethanol in 25 ℃ is commercial PtRu/Vulcan XC-72 (ETEK, 20wt%PtRu, Pt: Ru=1: 1) 3 of catalyst times, in addition, carbon wool ball carried PtSn electrode has shown (20wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/Vulcan XC-72.
Embodiment 10, carbon wool ball carried 40wt%PtSn Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 1.04g H
2PtCl
66H
2O is made into 200ml solution, adds 0.46g SnCl
22H
2O, make Pt: Sn=1 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, take by weighing 1.569g and add in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 200ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (40wt%PtSn, Pt: Sn=1: 1), wherein the average diameter of PtSn is 3.7nm to carbon wool ball carried PtSn catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (40wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 63.7m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 84.0%, at 1.0M H
2SO
4+ 1.0M CH
3CH
2In the OH solution, recording its catalytic activity to the electrochemical oxidation of ethanol in 25 ℃ is commercial PtRu/Vulcan XC-72 (ETEK, 40wt%PtRu, Pt: Ru=1: 1) 2 of catalyst times, in addition, carbon wool ball carried PtSn electrode has shown (ETEK, 40wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/Vulcan XC-72.
Embodiment 11, carbon wool ball carried 60wt%PtMo Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 1.04g H
2PtCl
66H
2O is made into 300ml solution, adds 0.59g MoCl
4Make Pt: Mo=3 in the solution: 2 (ratios of amount of substance), stir after 30 minutes, take by weighing 0.97g and add in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 150ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (20wt%PtMo, Pt: Mo=3: 2), wherein the average diameter of PtMo is 5.3nm to carbon wool ball carried PtMo catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (60wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 43.4m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtMo
2/ g, the utilization rate of Pt is 82.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is PtRu/VulcanXC-72 (ETEK, 60wt%PtRu, Pt: Ru=1: 1) 1.6 of catalyst times, in addition, carbon wool ball carried PtMo electrode has shown (E-TEK, 60wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/Vulcan XC-72.
Embodiment 12, carbon wool ball carried 60wt%PtRu Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Carbon takes by weighing 4.670g H
2PtCl
66H
2O is made into 300ml solution, adds 0.269g RuCl
3XH
2(content of Ru is 37.5% to O, w/w), make Pt: Ru=9 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, taking by weighing 3.093g adds in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 300ml0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h.The gained material is carbon wool ball carried PtRu catalyst (60wt%PtRu, Pt: Ru=9: 1, Pt accounts for 90% in alloy), and wherein the average diameter of PtRu is 6.2nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (60wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 38.0m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 84.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, in 25 ℃ of catalytic activity and PtRu/Vulcan XC-72 (ETEK that record it to the electrochemical oxidation of methyl alcohol, 60wt%PtRu, Pt: Ru=1: 1) catalyst is suitable, in addition, carbon wool ball carried PtRu electrode has shown (E-TEK, 60wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/Vulcan XC-72.
Embodiment 13, carbon wool ball carried 80wt%PtRu Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 2.08g H
2PtCl
66H
2O is made into 400ml solution, adds 1.08g RuCl
3XH
2(content of Ru is 37.5% to O, w/w), make Pt: Ru=1 in the solution: 1 (ratio of amount of substance), stir after 30 minutes, taking by weighing 1.48g adds in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 400ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is that (80wt%PtRu, Pt: Ru=1: 1), wherein the average diameter of PtRu is 15.0nm to carbon wool ball carried PtRu catalyst.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (80wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 15.5m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 83.0%, at 1.0M H
2SO
4+ 1.0M CH
3In the OH solution, recording its catalytic activity to the electrochemical oxidation of methyl alcohol in 25 ℃ is PtRu/Vulcan XC-72 (80wt%PtRu, Pt: Ru=1: 1) 2.8 of catalyst times, in addition, carbon wool ball carried PtRu electrode has shown (80wt%PtRu, Pt: Ru=1: the anode polarization performance that 1) electrode is lower than PtRu/VulcanXC-72.
Embodiment 14, carbon wool ball carried 80wt%PtRu Preparation of catalysts
With carbon wool ball material at 70% HNO
3In refluxed 3 hours in 160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon wool ball material through surface oxidation.
Take by weighing 0.52g H
2PtCl
66H
2O is made into 400ml solution, adds 2.42g RuCl
3XH
2(content of Ru is 37.5% to O, w/w), make Pt: Ru=1 in the solution: 9 (ratios of amount of substance), stir after 30 minutes, taking by weighing 1.38g adds in the solution for preparing through the carbon bobbles of surface oxidation, stir after 30 minutes, the HCHO solution with 400ml 0.5M slowly splashes in the mixed liquor that continues to stir again.After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, the gained material is carbon wool ball carried PtRu catalyst (80wt%PtRu, Pt: Ru=1: 9, Pt accounts for 10% in alloy), wherein the average diameter of PtRu is 50nm.
The preparation of electrode and test are with embodiment 1.Wherein, adopt carbon wool ball carried Pt (80wt%Pt) as oxygen reduction catalyst.
The result of electro-chemical test is: at 0.5M H
2SO
4In the solution, be 4.21m in 25 ℃ of electrochemistry specific areas that record carbon wool ball carried PtRu
2/ g, the utilization rate of Pt is 75.0%.
Claims (10)
1, a kind of carbon wool ball carried catalyst, it is to use carbon wool ball material as carrier, the Pt of load 1～80wt% or PtM alloy on it; Described M is Ru, Sn or Mo.
2, carbon wool ball carried catalyst as claimed in claim 1 is characterized in that: described carbon wool ball material is a core material with carbon element, and the 1-dimention nano carbon fiber of growth in its surface is or/and CNT; The average grain diameter of described core material with carbon element is 100nm～1mm; The diameter of described 1-dimention nano carbon fiber or CNT is 1～500nm, and length is 10nm～100 μ m, and draw ratio is 5～10
5
3, carbon wool ball carried catalyst as claimed in claim 2 is characterized in that: described core material with carbon element is the material with carbon element of graphited material with carbon element or disordered structure.
4, carbon wool ball carried catalyst as claimed in claim 2 is characterized in that: the geometric shape of described core material with carbon element is for spherical.
5, carbon wool ball carried catalyst as claimed in claim 2 is characterized in that: described one dimension CNT is single wall, double-walled or many walls.
6, carbon wool ball carried catalyst as claimed in claim 2 is characterized in that: described 1-dimention nano carbon fiber and CNT are to have straight geometry appearance, or have crooked geometry appearance; It is perpendicular to core carbon material surface oriented growth, or the non-directional growth.
7, carbon wool ball carried catalyst as claimed in claim 1 is characterized in that: the average diameter of described Pt or PtM alloy is 1.0～50nm.
8, carbon wool ball carried catalyst as claimed in claim 1 is characterized in that: in the described PtM alloy, the atomic ratio that Pt accounts in alloy is 10～90%.
9, the described carbon wool ball carried Preparation of catalysts method of a kind of claim 1, it is by the liquid phase method preparation, mainly may further comprise the steps:
1) preliminary treatment of carbon wool ball material: with carbon wool ball material at 70% HNO
3In refluxed 3～48 hours in 60～160 ℃, fully clean with high purity water, after the filtration, in 100 ℃ of baking ovens dry 8 hours, obtain carbon bobbles through surface oxidation;
2) carbon wool ball carried Pt Preparation of catalysts: take by weighing K
2PtCl
6Be dissolved in ethylene glycol and the water; fully stir after 1 hour; the carbon bobbles that takes by weighing through surface oxidation by Pt load capacity 1～80wt% adds in the solution for preparing; refluxed about 4～12 hours under argon shield in 140～180 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and high purity water, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is carbon wool ball carried Pt catalyst;
3) preparation of carbon wool ball carried PtM alloy catalyst: 1～80wt% takes by weighing H by the PtM load capacity
2PtCl
66H
2O and RuCl
3XH
2(content of Ru is 37.5% to O, w/w), SnCl
22H
2O or MoCl
4Wiring solution-forming soluble in water stirred after 30 minutes, and the carbon bobbles that takes by weighing through surface oxidation adds in the solution for preparing, and stirs after 30 minutes, slowly splashes into HCHO solution in the mixed liquor while stirring; After reaction is finished, catalyst is fully cleaned with high purity water, filter, remove the Cl that is adsorbed on the surface
-, clean finish after in 80 ℃ of baking ovens dry 5h, products therefrom is carbon wool ball carried PtM alloy catalyst.
10, the described carbon wool ball carried application of catalyst in direct alcohol fuel battery of a kind of claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2452259A (en) * | 2007-08-25 | 2009-03-04 | Montford University De | Method of catalysing a chemical reaction and preparation of the catalyst used therein |
| CN105789641A (en) * | 2014-12-24 | 2016-07-20 | 上海汽车集团股份有限公司 | Fuel cell, platinum-carbon catalyst and preparation method of platinum-carbon catalyst |
| CN105817240A (en) * | 2016-04-15 | 2016-08-03 | 华中科技大学 | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst |
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| EP1254712B1 (en) * | 2001-05-05 | 2005-07-20 | Umicore AG & Co. KG | A noble metal-containing supported catalyst and a process for its preparation |
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| JP4289662B2 (en) * | 2003-05-15 | 2009-07-01 | 独立行政法人産業技術総合研究所 | Sheet-like catalyst structure using carbon nanotube and method for producing the same |
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| GB2452259A (en) * | 2007-08-25 | 2009-03-04 | Montford University De | Method of catalysing a chemical reaction and preparation of the catalyst used therein |
| GB2452259B (en) * | 2007-08-25 | 2012-02-29 | Montford University De | Catalyst |
| CN105789641A (en) * | 2014-12-24 | 2016-07-20 | 上海汽车集团股份有限公司 | Fuel cell, platinum-carbon catalyst and preparation method of platinum-carbon catalyst |
| CN105817240A (en) * | 2016-04-15 | 2016-08-03 | 华中科技大学 | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst |
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| CN110161099A (en) * | 2019-05-21 | 2019-08-23 | 河南大学 | Using titanium dioxide nano-rod composite material as the construction method of the electrochemical aptamer sensor of electrochemistry tracer |
| CN113903933A (en) * | 2021-09-29 | 2022-01-07 | 清华大学深圳国际研究生院 | Carbon-supported platinum-tin nano catalyst for long-life proton exchange membrane fuel cell and preparation method thereof |
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