CN102751511A - H2O2-based fuel cell cathode catalyst with nanometer oxide serving as carrier and preparation method - Google Patents

H2O2-based fuel cell cathode catalyst with nanometer oxide serving as carrier and preparation method Download PDF

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CN102751511A
CN102751511A CN2012102538255A CN201210253825A CN102751511A CN 102751511 A CN102751511 A CN 102751511A CN 2012102538255 A CN2012102538255 A CN 2012102538255A CN 201210253825 A CN201210253825 A CN 201210253825A CN 102751511 A CN102751511 A CN 102751511A
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solution
catalyst
carrier
oxide
precious metal
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CN102751511B (en
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孙丽美
陈庆标
刘宗瑞
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Inner Mongolia University for Nationlities
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Inner Mongolia University for Nationlities
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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

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Abstract

The invention discloses a H2O2-based fuel cell cathode catalyst with a nanometer oxide serving as a carrier and a preparation method. The carrier of the catalyst is a composite comprises one or more of copper, iron, nickel, tin and antimony oxides, and precious metal palladium serves as an active substance. The preparation method of the catalyst includes: dissolving chloride salt of the palladium, adding the nanometer oxide carrier, adding reducing agents after sufficient dispersion, and performing vacuum drying so as to form the H2O2-based fuel cell cathode catalyst with the nanometer oxide serving as the carrier. Compared with a traditional carbon carrier, the nanometer oxide has less pore structures to be beneficial to anchoring of precious metal active points on the carrier surface; and an oxide intrinsically has catalytic activity for H2O2 electro-reduction so that double-catalysis effects are achieved. The catalyst has the advantages of high catalytic activity, abundance in material source, low cost, simple preparation process and the like.

Description

A kind of is the H of carrier with the nano-oxide 2O 2Base fuel battery cathod catalyst and preparation method
Technical field
The present invention relates to, in particular a kind of is the H of carrier with the nano-oxide 2O 2Base fuel battery cathod catalyst and preparation method.
Background technology
Metal-H 2O 2Semi-fuel cell (MSFC) is a kind of novel chemical power source of developing in recent years under water, outstanding advantage such as have that energy density height, discharge voltage are stable, long, safe in utilization, the no ecological pollution of storage life and mechanical charging interval lack.Because cathode oxidant H 2O 2Overcome and carried O 2The a large amount of inconvenience that produce, metal-H 2O 2Semi-fuel cell is by the power supply of broad research as electronic instrument such as unmanned vehicle, underwater navigation, communication and data acquisition under water and oil gas production equipment.Activity of such catalysts and electrode structure are having a strong impact on cell discharge performance and service conditions.At present, precious metals pd is catalyst based is catalysis H 2O 2A kind of catalyst that the electro-reduction reaction activity is the highest.For reducing the use amount of Pd, increase utilance, people use carbon black as catalyst carrier usually, and this is because carbon black has higher specific surface area and has good electrical conductivity and preferable pore structure, helps improving the dispersiveness of precious metals pd particulate.But because a large amount of Pd particulates enters into the micropore of carbon surface, can not contact, therefore be difficult to form more reaction zone, so reduced the utilance of precious metals pd with electrolyte.
Summary of the invention
The objective of the invention is to overcome above-mentioned H 2O 2Existing technical problem in production of base fuel battery cathod catalyst and the use provides a kind of new H 2O 2Base fuel battery cathod catalyst and preparation method thereof.
A kind of is the H of carrier with the nano-oxide 2O 2The preparation method of base fuel battery cathod catalyst may further comprise the steps:
(1) salt with precious metal palladium is added to the water, and makes its dissolving, forms solution A; The addition of precious metal palladium salt and water use magnitude relation: the required water of 0.01～0.05mol palladium ion is 1000mL;
(2) in the solution A that step (1) is prepared, add alkaline solution, form solution B; Wherein aqueous slkali is a sodium hydrate aqueous solution, and the ratio of the mole of precious metal palladium is 50: 1～150: 1 in the adding mole of its NaOH and the solution A.
(3) in the solution B that step (2) is prepared, add nano-metal-oxide, be fully mixed to evenly, form suspension-turbid liquid C.Used oxide is one or more the compound in copper, iron, nickel, tin, the sb oxide.Its addition is controlled according to following method: the quality of precious metal palladium element and the ratio of nano oxidized amount are 5%～30%.
(4) in the suspension-turbid liquid C that step (3) is prepared, add reductant solution, form suspension-turbid liquid D, reductant solution that wherein adds and the mass ratio of suspension-turbid liquid C are 5: 1～10: 1; Wherein reducing agent is a sodium borohydride aqueous solution, and the amount of substance of sodium borohydride is 1: 10～1: 100 with the ratio of the volume of water.
(5) the suspension-turbid liquid D of step (4) gained is filtered, vacuum 40-80 ℃ of drying, be 4-15h drying time, both H according to the invention 2O 2The base fuel battery cathod catalyst.
Of the present invention a kind of be the H of carrier with the nano-oxide 2O 2Base fuel battery cathod catalyst, the carrier of this catalyst are one or more the compound in the transition metal oxide, and active material is a precious metal palladium; Have the catalytic activity height, the raw material source is abundant, and cost is lower; Technical process is simple, is easy to characteristics such as control.
The present invention adopts the oxide with conductivity as catalyst carrier, compared with prior art, has the following advantages:
1) the oxide particle surface micropore is few, and the precious metals pd particulate can be anchored on carrier surface, thereby improves the utilance of noble metal catalyst; 2) nano-oxide itself is to H 2O 2Electro-reduction reaction just has catalytic activity, has formed two catalytic effects; 3) the transition metal oxide material source is abundant, and cost is lower, and this preparation technology is simple, is beneficial to production.
Description of drawings
The XRD figure of the catalyst that Fig. 1 instance 1 provides.
The cyclic voltammetry curve of the catalyst that Fig. 2 instance 1 provides.
The XRD figure of the catalyst that Fig. 3 instance 2 provides.
The cyclic voltammetry curve of the catalyst that Fig. 4 instance 2 provides.
The XRD figure of the catalyst that Fig. 5 instance 3 provides.
The cyclic voltammetry curve of the catalyst that Fig. 6 instance 3 provides.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Embodiment 1
Get 500mg Fe 3O 4Powder, particle diameter 30nm～80nm adds 25mL 1mol/L hydrochloric acid solution, 50～70 ℃ of sonicated 1 hour, obtains comparatively pure Fe 3O 4Powder; With 6.3mL0.0225mol/L PdCl 2With 3.7ml H 2O solution mixes, and in solution, directly adds 15mL 1mol/LNaOH, adds the Fe that 60mg handled then 3O 4Powder stirs 20min, drips 15mL 0.0484mol/L NaBH 4Solution stirs 1h.Filtration washing, 60 ℃ of vacuumize 12h promptly get Pd/Fe according to the invention 3O 4Catalyst.
The XRD figure of the catalyst that Fig. 1 provides for instance 1 calculates relatively through the Scherrer formula, can know with Fe 3O 4For the Pd particle of carrier littler.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that this instance of 5mg is synthesized, mix ultrasonic 30min with the 2mL redistilled water.The suspension-turbid liquid 15 μ L that get ultrasonic dispersion drop in the glass-carbon electrode surface of diameter 5mm, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.The glass-carbon electrode of the surface catalyst layer that makes more than using is work electrode, and high-purity carbon-point is to electrode, and saturated calomel electrode (SCE) is a reference electrode.In the mixed solution of 0.1mol/L sulfuric acid and 0.5mol/L hydrogen peroxide, room temperature condition is measured the linear polarization curve down.
The cyclic voltammetry curve of the catalyst that Fig. 2 provides for embodiment 1.Can find out that from figure the catalyst that is synthesized is that the catalyst of carrier has stronger electro-chemical activity with carbon.
Embodiment 2
Get 500mg ATO powder, particle diameter 10nm～50nm adds 25mL 1mol/L hydrochloric acid solution, 50～70 ℃ of sonicated 1 hour, obtains comparatively pure ATO powder; With 6.3mL 0.0225mol/L PdCl 2+ 3.7mlH 2O solution mixes, and in solution, directly adds 15mL 1mol/LNaOH, adds the Fe that 60mg handled then 3O 4Powder stirs 20min, drips 15mL0.0484mol/L NaBH 4Solution stirs 1h.Filtration washing, 60 ℃ of vacuumize 12h promptly get Pd/ATO catalyst according to the invention.
The XRD figure of the catalyst that Fig. 3 provides for embodiment 2 calculates relatively through the Scherrer formula, can know with ATO to be that the Pd particle of carrier is littler.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that this instance of 5mg is synthesized, mix ultrasonic 30min with 2mL secondary water.The suspension-turbid liquid 15 μ L that get ultrasonic dispersion drop in the glass-carbon electrode surface of diameter 5mm, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.The glass-carbon electrode of the surface catalyst layer that makes more than using is work electrode, and high-purity carbon-point is to electrode, and saturated calomel electrode (SCE) is a reference electrode.In the mixed solution of 1mol/L NaOH and 0.5mol/L hydrogen peroxide, room temperature condition is measured the linear polarization curve down.
The cyclic voltammetry curve of the catalyst that Fig. 4 provides for embodiment 2.Can find out that from figure the catalyst that is synthesized is that the catalyst of carrier has stronger electro-chemical activity with carbon.
Embodiment 3
Get 500mg Cu 2The O powder, particle diameter 30nm～80nm adds 25mL 1mol/L hydrochloric acid solution, 50～70 ℃ of sonicated 1 hour, obtains comparatively pure Cu 2The O powder; With 6.3mL0.0225mol/L PdCl 2+ 3.7mlH 2O solution mixes, and in solution, directly adds 15mL 1mol/L NaOH, adds the Fe that 60mg handled then 3O 4Powder stirs 20min, drips 15mL0.0484mol/L NaBH 4Solution stirs 1h.Filtration washing, 60 ℃ of vacuumize 12h promptly get Pd/Cu according to the invention 2The O catalyst.
The XRD figure of the catalyst that Fig. 5 provides for embodiment 3 calculates relatively through the Scherrer formula, can know with Cu 2O is that the Pd particle of carrier is littler.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that this instance of 5mg is synthesized, mix ultrasonic 30min with 2mL secondary water.The suspension-turbid liquid 15 μ L that get ultrasonic dispersion drop in the glass-carbon electrode surface of diameter 5mm, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.The glass-carbon electrode of the surface catalyst layer that makes more than using is work electrode, and high-purity carbon-point is to electrode, and saturated calomel electrode (SCE) is a reference electrode.In the mixed solution of 0.1mol/L sulfuric acid and 0.5mol/L hydrogen peroxide, room temperature condition is measured the linear polarization curve down.
The cyclic voltammetry curve of the catalyst that Fig. 6 provides for embodiment 3.Can find out that from figure the catalyst that is synthesized is that the catalyst of carrier has stronger electro-chemical activity with carbon.
Should be understood that, concerning those of ordinary skills, can improve or conversion, and all these improvement and conversion all should belong to the protection range of accompanying claims of the present invention according to above-mentioned explanation.

Claims (2)

1. one kind is the H of carrier with the nano-oxide 2O 2The preparation method of base fuel battery cathod catalyst is characterized in that, may further comprise the steps:
(1) salt with precious metal palladium is added to the water, and makes its dissolving, forms solution A; The addition of precious metal palladium salt and water use magnitude relation: the required water of 0.01～0.05mol palladium ion is 1000mL;
(2) in the solution A that step (1) is prepared, add alkaline solution, form solution B; Wherein aqueous slkali is a sodium hydrate aqueous solution, and the ratio of the mole of precious metal palladium is 50: 1～150: 1 in the mole of its NaOH and the solution A;
(3) in the solution B that step (2) is prepared, add nano-metal-oxide, be fully mixed to evenly, form suspension-turbid liquid C; Used oxide is one or more the compound in copper, iron, nickel, tin, the sb oxide; Its addition is controlled according to following method: the quality of precious metal palladium element and the ratio of nano oxidized amount are 5%～30%;
(4) in the suspension-turbid liquid C that step (3) is prepared, add reductant solution, form suspension-turbid liquid D, reductant solution that wherein adds and the mass ratio of suspension-turbid liquid C are 5: 1～10: 1; Wherein reducing agent is a sodium borohydride aqueous solution, and the amount of substance of sodium borohydride is 1: 10～1: 100 with the ratio of the volume of water;
(5) the suspension-turbid liquid D of step (4) gained is filtered, vacuum 40-80 ℃ of drying, be 4-15h drying time, both H according to the invention 2O 2The base fuel battery cathod catalyst.
2. the H of method preparation according to claim 1 2O 2The base fuel battery cathod catalyst.
CN201210253825.5A 2012-07-23 2012-07-23 A kind of take nano-oxide as the H of carrier 2o 2base fuel battery cathod catalyst and preparation method Expired - Fee Related CN102751511B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617314A (en) * 2013-11-04 2015-05-13 中国科学院大连化学物理研究所 Fuel cell catalyst Pt/ATO, and preparation method and application thereof
CN105655610A (en) * 2014-12-01 2016-06-08 中国科学院大连化学物理研究所 Ultrathin catalytic layer attached to anion exchange membrane, preparation and application thereof
CN109713325A (en) * 2018-12-29 2019-05-03 四川大学 A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389294A (en) * 2002-07-15 2003-01-08 武汉化工学院 Catalyst for synthesis of caromatic phenyl carbonate and its prepn.
CN101767018A (en) * 2009-01-06 2010-07-07 北京大学 Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389294A (en) * 2002-07-15 2003-01-08 武汉化工学院 Catalyst for synthesis of caromatic phenyl carbonate and its prepn.
CN101767018A (en) * 2009-01-06 2010-07-07 北京大学 Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617314A (en) * 2013-11-04 2015-05-13 中国科学院大连化学物理研究所 Fuel cell catalyst Pt/ATO, and preparation method and application thereof
CN105655610A (en) * 2014-12-01 2016-06-08 中国科学院大连化学物理研究所 Ultrathin catalytic layer attached to anion exchange membrane, preparation and application thereof
CN105655610B (en) * 2014-12-01 2018-02-06 中国科学院大连化学物理研究所 The ultra-thin Catalytic Layer adhered on a kind of anion-exchange membrane and its preparation and application
CN109713325A (en) * 2018-12-29 2019-05-03 四川大学 A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell

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