CN1418725A - Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube - Google Patents

Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube Download PDF

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Publication number
CN1418725A
CN1418725A CN02155256A CN02155256A CN1418725A CN 1418725 A CN1418725 A CN 1418725A CN 02155256 A CN02155256 A CN 02155256A CN 02155256 A CN02155256 A CN 02155256A CN 1418725 A CN1418725 A CN 1418725A
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cnts
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catalyst
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CN1171671C (en
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朱红
孙正贵
许韵华
杨玉国
申阎春
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Technology Center Of Shengli Oil Administration Bereau
Beijing Jiaotong University
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Technology Center Of Shengli Oil Administration Bereau
Beijing Jiaotong University
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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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The preparation method of Pt-Ru series CO resistant electrode catalyst is characterized by that it uses carbon nano tube as carrier, utilizes the in-situ chemical reduction homogeneous precipitation method and makes the ions of Pt, Ru and Sn into compounding ion respectively (called complex ion for short), then it uses two kinds of three kinds of complex ions and mixes them together to obtain metastable colloid, them adopts cheap reduction agent formaldehyde (or sodium borohydride or ethyl alcohol or hydrogen gas) to make the metastable colloid be reduced and deposited on the activated carbon nano tube so as to obtain the invented electrode catalyst for proton-exchange membrane fuel cell. It possesses good electric catalytic activity and resistance to Co, and features large specific area, high porosity, good dispersion property and low ptatinum use level.

Description

CNT carries the preparation method of the anti-CO electrode catalyst of platinum ruthenium series
One, technical field
The present invention is a kind of preparation method of anti-CO electrode catalyst of used in proton exchange membrane fuel cell, belongs to the technical field that catalyst is made.
Two, technical background
Fuel cell has caused the great attention of countries in the world as the green energy resource of 21 century.Proton membrane fuel battery (PEMFC) wherein, the research of DMFC (DMFC) more makes one notice.One of their advantage be can be extensively as the power supply of destination.Yet, no matter Proton Exchange Membrane Fuel Cells or DMFC, all exist CO to Pt catalyst poisoning problem, because contain a spot of CO in the reformation gas, also have the intermediate gas of similar CO in the methanol oxidation process, and the CO of trace can make the performance of battery descend significantly, and therefore, solving anti-CO problem has become countries in the world fuel cell studies circle problem anxious to be solved.
Three, summary of the invention
Technical problem solved by the invention is that the CNT that proposes a kind of used in proton exchange membrane fuel cell carries platinum ruthenium (Pt-Ru/CNTs), platinum tin (Pt-Sn/CNTs), platinum ruthenium tungsten (Pt-Ru-HxWO y/ CNTs) preparation method of serial anti-CO electrode catalyst.
Technical scheme of the present invention is, the employing CNT is a carrier, utilization in-situ chemical reduction homogeneous deposition method, at first Pt, Ru, Sn plasma are made respectively and cooperated ion (be called for short: complex ion is a complex ion), two or three complex ion mixes and makes the metastable state colloid then, adopt reducing agent formaldehyde (or sodium borohydride or ethanol or hydrogen) again, metastable state colloid reduce deposition is made on the CNT after the activation processing.Used in proton exchange membrane fuel cell Pt-Ru/CNTs, Pt-Sn/CNTs, Pt-Ru-H that the present invention proposes xWO yThe preparation method of/CNTs electrode catalyst comprises following each step:
1. carbon nanotube carrier is carried out activation processing:
(1) washing: CNT is added in the round-bottomed flask, wetting with absolute ethyl alcohol, add a certain amount of redistilled water heating again and boil, backflow 1h filters, and 80 ℃ of dry 2h obtain washing activated carbon nanotube sample.
(2) pickling: washing the salt acid dip 10h of activated carbon nanotube sample with 10%, backflow 1h filters, and washes no Cl -Till, 80 ℃ of vacuum drying 2h.
The pretreated purpose of carrier:
1. improve the adsorption capacity of carbon;
2. remove alkaline metal oxide;
3. improve the specific area of CNT.
The raw material proportioning: CNT is 1 with the ratio of platinum ruthenium series: 0.02-1: 0.40, and platinum ruthenium series is abbreviated as Pt-M, and M is Ru, Sn, H among the Pt-M xWO y, addition makes Pt: M=1: 0.1-1: 1.
2. adopt in-situ chemical reduction homogeneous deposition method
(1) preparation of complex ion (being complex ion)
1. get chloroplatinic acid aqueous solution and add NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5;
2. get RuCl in addition 3Solution (or is got SnCl 2Solution, Na 2WO 4Solution) add a small amount of dense HCl, add NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5.
(2) preparation of metastable state colloid
With above-mentioned 1. 2. complex ion solution mix, slowly drip H 2O 2, regulate pH=5 with 5%NaOH solution.
(3) in-situ chemical reduction homogeneous deposition
CNT in the metastable state colloid that (2) make after the adding activation processing, (80 ℃) stir 30min in hot bath, dropping reducing agent formaldehyde (excessive 6-10 times, or use other reducing agent: sodium borohydride or hydrogen).Ultrasonic wave stirring reaction 3-4 hour.
(4) product warm water filters, and fully no Cl is checked in washing -Till.Promptly get Pt-Ru/CNTs or Pt-Sn/CNTs or Pt-H at 80-100 ℃ of air drying xWO y/ CNTs catalyst series.
The evaluation of Pt-Ru/CNTs series CO-resistance catalyst battery performance is carried out in a homemade small-sized monocell test macro.Electrode preparation adopts pressure sintering to make " three-in-one " membrane electrode, and promptly the Pt-Ru/CNTs catalyst is mixed into sticking paste with excessive 5%Nafion solution and other auxiliary agent etc. earlier, evenly sprays to then on the carbon paper, and dried carbon paper is cut into 5cm 2Square and with PEM (Nafion-115) hot pressing together, form " three-in-one " membrane electrode, this electrode is assembled in the monocell test macro, measure electric current, voltage, current density, the battery performance of catalyst is estimated.The battery testing condition is: 75 ℃ of electrode temperatures, the pressure of anode hydrogen gas and negative electrode oxygen is 0.2MPa, 90 ℃ of gas humidification temperature, the theoretical Pt-Ru carrying capacity of electrode 0.6mg/cm 2
The beneficial effect that the present invention has: the CNT that the fuel cell that adopts this method to prepare is used carries platinum ruthenium series CO-resistance catalyst and has good dispersion, and is active high, the PEM with anti-CO ability.The catalyst particle size of preparation is little, and dispersive property is good, has higher specific surface area.
Four, Figure of description
Fig. 1 is the TEM pattern of Pt-Ru/CNTs
Fig. 2 is the TEM pattern of Pt-Sn/CNTs
Fig. 3 is the TEM pattern of Pt-Ru-HxWOy/CNTs
Fig. 4 is that the particle diameter of Pt-Ru-HxWOy/CNTs distributes
Fig. 5 is that the battery performance of Pt/CNTs, Pt-Ru/CNTs compares (is fuel with pure hydrogen)
Fig. 6 is that the CO resistance performance of Pt-Ru/CNTs battery compares (with H 2/ 50ppmCO gaseous mixture is a fuel)
Transmission electron microscope (TEM) shape appearance figure and analysis by Fig. 1 Pt-Ru/CNTs know that average grain diameter is 3.0nm.
Transmission electron microscope (TEM) shape appearance figure and analysis by Fig. 2 Pt-Sn/CNTs know that average grain diameter is 4.2nm.
Transmission electron microscope (TEM) shape appearance figure and analysis by Fig. 3 Pt-Ru-HxWOy/CNTs know that average grain diameter is 3.2nm.
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 show, active component average grain diameter＜4.2mm, and be dispersed on the CNT.
Among Fig. 5, fuel is H 2, when being fuel with pure hydrogen, Pt/CNTs is better than PtRu/CNTs.
Among Fig. 6, H 2When/50ppmCO was fuel, PtRu/CNTs was much better than Pt/CNTs.
Know relatively that by Fig. 5,6 when being fuel with pure hydrogen, Pt/CNTs is better than PtRu/CNTs; With H 2When/50ppmCO was fuel, PtRu/CNTs was much better than Pt/CNTs, illustrated that Ru plays the effect of anti-CO therein.
Five, the specific embodiment
Introduce embodiments of the invention below:
Embodiment one:
1. nanotube (system provides by the Tsing-Hua University chemical industry) activation processing
Washing: CNT is added in the round-bottomed flask, wetting with absolute ethyl alcohol, add a certain amount of redistilled water heating again and boil, refluxed 1 hour, filtration, 80 ℃ of dryings 2 hours obtain washing activated carbon nanotube sample.
Pickling: washing activated carbon nanotube sample with 10% salt acid dip 10 hours, was refluxed 1 hour, and no Cl is washed in filtration -Till, 80 ℃ of vacuum drying 2 hours.
2. adopt in-situ chemical reduction homogeneous deposition legal system to be equipped with the Pt-Ru/CNTs catalyst
Raw material proportioning: Pt: Ru=1: 0.5
(1) preparation of complex ion (being complex ion)
1. get chloroplatinic acid aqueous solution and add NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5;
2. get RuCl in addition 3Solution adds a small amount of dense HCl, adds NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5.
(2) preparation of metastable state colloid
With above-mentioned 1. 2. complex ion solution mix, slowly drip H 2O 2, regulate pH=5 with 5%NaOH solution.
(3) in-situ chemical reduction homogeneous deposition
CNT in the metastable state colloid that (2) make after the adding activation processing, (80 ℃) stir 30min in hot bath, dropping reducing agent formaldehyde (excessive 6-10 times, or use other reducing agent: sodium borohydride or hydrogen).Ultrasonic wave stirring reaction 3-4 hour.
(4) product warm water filters, and fully no Cl is checked in washing -Till.Promptly get the Pt-Ru/CNTs catalyst 80 ℃ of vacuum drying.
(5) with above-mentioned Pt-Ru/CNTs Preparation of Catalyst " three-in-one " membrane electrode, survey its battery performance.
Embodiment two:
1. CNT (being provided by chemical industry system of Tsing-Hua University) activation processing is the same.
2. adopt in-situ chemical reduction homogeneous deposition legal system to be equipped with the Pt-Sn/CNTs catalyst
Raw material proportioning Pt: Sn=1: 1
(1) preparation of complex ion (being complex ion)
1. get chloroplatinic acid aqueous solution and add NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5;
2. get SnCl in addition 2Solution adds a small amount of dense HCl, adds NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5.
(2) preparation of metastable state colloid
With above-mentioned 1. 2. complex ion solution mix, slowly drip H 2O 2, regulate pH=5 with 5%NaOH solution.
(3) homogeneous phase in-situ chemical reduce deposition
CNT in the metastable state colloid that (2) make after the adding activation processing, (80 ℃) stir 30min in hot bath, dropping reducing agent formaldehyde (excessive 6-10 times, or use other reducing agent: sodium borohydride or hydrogen).Ultrasonic wave stirring reaction 3-4 hour.
(4) product warm water filters, and fully no Cl is checked in washing -Till.Promptly get the Pt-Sn/CNTs catalyst 80 ℃ of vacuum drying.
(5) with above-mentioned Pt-Sn/CNTs Preparation of Catalyst " three-in-one " membrane electrode, survey its battery performance.
Embodiment three:
1. CNT (being provided by chemical industry system of Tsing-Hua University) activation processing is the same.
2. adopt in-situ chemical reduction homogeneous deposition legal system to be equipped with Pt-Ru-H xWO y/ CNTs catalyst
Raw material proportioning Pt: Ru: H xWO y=1: 1: 1
(1) preparation of complex ion (being complex ion)
1. get chloroplatinic acid aqueous solution and add NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5; Other gets RuCl 3Solution adds a small amount of dense HCl, adds NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5.
2. get Na in addition 2WO 4Solution adds a small amount of dense HCl, adds NaHSO 3Powder, stirring reaction 20 minutes adds Na 2CO 3Solution is regulated pH=5.
(2) preparation of metastable state colloid
With above-mentioned 1. 2. 3. complex ion solution mix, slowly drip H 2O 2, regulate pH=5 with 5%NaOH solution.
(3) in-situ chemical reduction homogeneous deposition
In the metastable state colloid that (2) make, the CNT after the adding activation processing, (80 ℃) stir 30min in hot bath, dropping reducing agent formaldehyde (excessive 6-10 times, or use other reducing agent: sodium borohydride or hydrogen).Ultrasonic wave stirring reaction 3-4 hour.
(4) product warm water filters, and fully no Cl is checked in washing -Till.Promptly get Pt-Ru-H 80 ℃ of vacuum drying xWO y/ CNTs catalyst.
(5) use above-mentioned Pt-Ru-H xWO y/ CNTs Preparation of Catalyst " three-in-one " membrane electrode is surveyed its battery performance.

Claims (2)

1. a CNT carries the preparation method of the anti-CO electrode catalyst of platinum ruthenium series, it is characterized in that:
(1) CNT is a carrier, carries out activation processing;
Washing: CNT is added in the round-bottomed flask, wetting with absolute ethyl alcohol, add the heating of a certain amount of redistilled water again and boil, refluxed 1 hour, filtration, 80 ℃ of dryings 2 hours obtain washing activated carbon nanotube sample
Pickling: the sample after the washing refluxed 1 hour with 10% salt acid dip 10 hours, filtered, and washed no Cl -Till, 80 ℃ of vacuum drying 2 hours
(2) raw material proportioning: CNT is 1 with the ratio of platinum ruthenium series: 0.02-1: 0.40, and platinum ruthenium series is abbreviated as Pt-M, and M is Ru, Sn, H among the Pt-M xWO y, addition makes Pt: M=1: 0.1-1: 1;
(3) adopt in-situ chemical reduction homogeneous deposition method, at first respectively with Pt, Ru (or other metal ion) and NaHSO 3Effect generates cooperation ion separately, they is mixed again, and uses H 2O 2Oxidation makes metastable colloid, pH value of solution=5 in the control course of reaction;
(4) behind the CNT after the adding activation processing, with reducing agent formaldehyde (or sodium borohydride or H 2) reduction, the excessive 6-10 of reducing agent times, ultrasonic wave stirred 3 hours;
(5) the pH value in the control course of reaction is 5, reaction time 4-8 hour;
(6) react completely after, with product filter, washing, air drying 80-100 ℃.
2. CNT according to claim 1 carries the preparation method of platinum ruthenium series CO-resistance catalyst, it is characterized in that earlier CNT being activated, adopt in-situ chemical reduction homogeneous deposition method during preparation, at first respectively platinum, ruthenium, tin plasma are formed complex ion and make metastable colloid, the homogeneous deposition that reduces afterwards gets corresponding catalyst, and reducing agent is formaldehyde (or sodium borohydride or ethanol or H 2), ph=5.
CNB021552568A 2002-12-12 2002-12-12 Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube Expired - Fee Related CN1171671C (en)

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CN100368079C (en) * 2006-02-23 2008-02-13 华南理工大学 Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide
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CN100503044C (en) * 2004-12-15 2009-06-24 中国科学院物理研究所 Carbon wool ball carried type catalyst and its preparation method and uses
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CN101787502B (en) * 2010-01-19 2011-10-05 中国科学院化学研究所 Method for preparing metal, metallic oxide or metallic hydroxide and carbon nano tube composite
CN102064321A (en) * 2010-11-23 2011-05-18 浙江大学 Preparation method of composite material containing multi-walled carbon nanotubes and tin-cobalt alloy nanoparticles
CN102064321B (en) * 2010-11-23 2012-11-21 浙江大学 Preparation method of composite material containing multi-walled carbon nanotubes and tin-cobalt alloy nanoparticles
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CN102068983B (en) * 2010-12-20 2012-07-18 宁波工程学院 Preparation method of proton exchange membrane fuel cell catalyst
CN102157741A (en) * 2011-03-07 2011-08-17 中国科学院等离子体物理研究所 Manufacturing method of membrane electrode of novel ultrathin proton exchange membrane fuel cell
CN102157741B (en) * 2011-03-07 2012-11-28 中国科学院等离子体物理研究所 Manufacturing method of membrane electrode of novel ultrathin proton exchange membrane fuel cell
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