CN106299396B - A kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof - Google Patents

A kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof Download PDF

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CN106299396B
CN106299396B CN201510239085.3A CN201510239085A CN106299396B CN 106299396 B CN106299396 B CN 106299396B CN 201510239085 A CN201510239085 A CN 201510239085A CN 106299396 B CN106299396 B CN 106299396B
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ptsn
catalyst
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ethanol
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CN106299396A (en
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于苏平
姜倩
朱红
韩克飞
汪中明
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Beijing University of Chemical Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention provides a kind of Direct Ethanol Fuel Cell anode catalysts and preparation method thereof, are expressed as：PtSn-ZrO2/ GN is with graphene (GN) for carrier, ZrO2The PtSn of the alloy part of doping is the catalyst of active component, ZrO2The Uniform Doped in PtSn/GN；By PtSn-ZrO2Anode catalysts of/the GN as Direct Ethanol Fuel Cell is less than corresponding unitary to the take-off potential of oxidation of ethanol, and binary catalyst is worth and improves 1~2 times for 0.14V, stability ratio Pt/GN, and the peak current density of catalysis ethanol oxidation can reach 9~11mAcm‑2.Preparation method of the present invention is simple and easy to do, is easy to commercial Application.Prepared PtSn-ZrO2/ GN composite catalysts reduce the load capacity of platinum, and catalyst cost is made to be greatly lowered.

Description

A kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof
Technical field
The present invention relates to the anode catalyst of catalysis ethanol oxidation and its preparations, and in particular to a kind of PtSn-ZrO2/ GN is urged Agent and preparation method, and the catalyst is used for Direct Ethanol Fuel Cell anode catalyst.
Background technology
Direct Ethanol Fuel Cell (DEFC) has the advantages that energy density is high, low toxicity, easily stored and transport, electronic It has broad application prospects in terms of automobile, Mobile portable equipment.Currently, elctro-catalyst is still using platinum as chief component, quilt Fuel cell optimum catalyst is considered, however, the higher cost of platinum-based electrocatalyst limits the extensive use of fuel cell. Therefore, low load platinum is researched and developed, high performance catalyst is the key technology for pushing fuel cell development.Recent studies have found that working as Pt Other metallic elements are added in base catalyst such as：When the metals such as Ni, Sn, Pd, Co, Cu, such double base or multicomponent catalyst are not The dosage that Pt metals in catalyst can only be reduced reduces cost, can also be because of the synergistic effect between other metallic elements and Pt Change adsorption capacity of the surfaces Pt for ethyl alcohol and Ethanol Oxidation intermediate state, to improve catalysis ethanol oxidation efficiency. Then the emerging catalyst such as Pt alloys, core-shell catalyst causes the extensive concern of people.PtSn is generally acknowledged to urging at present Change the best binary catalyst of oxidation of ethanol performance, but the binary catalyst can inhibit ethyl alcohol C-C keys to be broken, and be unfavorable for ethyl alcohol Oxidation generates CO2, to reduce the catalytic activity of catalyst.There is scholar with regard to this study found that platinum base is added in metal oxide In catalyst, the carrying capacity of platinum in catalyst can be not only reduced, but also can play and improve catalyst stability and catalytic activity Effect.Due to ZrO2There are more Lacking oxygens during cost of material is low and structure, to have higher oxygen storage capacity, It is a kind of preferred additive.
Document：Huanqiao Song et al.,Promotion of carbon nanotube-supported Pt catalyst for methanol and ethanol electro-oxidation by ZrO2in acidic media.Applied Catalysis A:In General, 2009 3641-7., Song et al. is prepared for a kind of Pt-ZrO2/ CNT catalyst, by the study found that ZrO2The C-C keys that can promote Pt fracture ethyl alcohol, COads (ads tables are generated while scission of link Show adsorbate), due to ZrO2Excellent Oxygen storage capacity, COads is reacted with oxygenated species generates CO2, COads is promoted from Pt tables Face removes, and so that it is released more active sites and carrys out further Oxidation of Alcohol.The catalyst improves Pt to a certain extent CO tolerance catalysts ability improve the utilization rate of Pt, but distance also still has some gaps using Pt to greatest extent.
Document：Dao-Jun Guo et al.,Synthesis of sulfated ZrO2/MWCNT composites as new supports of Pt catalysts for direct methanol fuel cell application.Applied Catalysis B:In Environment, 2,009 89 597-601., ZrO2It is acidified with sulfuric acid On back loading to multi-walled carbon nanotube (MWCNT), ZrO2Pt loads are obtained Pt-ZrO by/MWCNT up as carrier2/MWCNT Elctro-catalyst.By the study found that acidification rear catalyst specific surface area bigger, increase the utilization rate of Pt；Also make simultaneously ZrO2Hydrophily enhancing, be more advantageous in this way and decompose water and generate OH, therefore COads is more easy to be oxidized to CO2.The ZrO of acidification2Also Good proton conduction can be played, the utilization rate for improving Pt is more conducive to, finally greatly strengthens the work of catalyst Property, promote the oxidation reaction of alcohols.
Invention content
The purpose of the present invention is to provide a kind of low platinum carrying capacity and the high ethanol oxidation catalysts and its preparation of catalytic activity Method, and the catalyst is used as Direct Ethanol Fuel Cell anode catalyst.
Direct Ethanol Fuel Cell anode catalyst provided by the invention, is expressed as：PtSn-ZrO2/ GN is with graphene (GN) it is carrier, ZrO2The catalyst that PtSn is active component is adulterated, wherein PtSn is alloy part type, wherein ZrO2Uniformly mix It is miscellaneous in PtSn/GN；The catalyst is used as Direct Ethanol Fuel Cell anode catalyst, the oxidation of ethanol of the catalyst originates Current potential reaches 0.1-0.2V, and stability ratio Pt/GN catalyst improves 1-2 times, and the peak current density of catalysis ethanol oxidation reaches To 9~11mAcm-2。
The anode-catalyzed preparation method of Direct Ethanol Fuel Cell provided by the invention, specific preparation process are as follows：
A. by Zr (NO3)4·5H2100ml suspension A are prepared in O and graphite oxide (GO) dispersion in deionized water, wherein The molar concentration of zirconium nitrate is 0.08-0.27mol/L, and the molar concentration of graphite oxide is 1.03-1.74g/L；According to suspension A Volume ratio with sodium borohydride aqueous solution is 1：10g/L sodium borohydride aqueous solutions are added dropwise in 0.15-0.30, stir 1-2h, filter, and use 80% ethanol solution washing, it is dry, obtain the ZrO of prereduction2/ GN powder；
B. ZrO step A obtained2/ GN powder ultrasonics, which are scattered in ethylene glycol solution, is made into suspension B, wherein containing admittedly Amount is 10-20g/L, ultrasonic disperse 10-20min；Then at 120-160 DEG C, 3-6 hour is reacted, is filtered, it is molten with 80% ethyl alcohol Liquid washs, dry, obtains ZrO2/ GN powder, then under nitrogen atmosphere, temperature is 550-700 DEG C of calcining 1h；
C. by platinum acid chloride solution and SnCl2·2H2O is according to Pt:Sn molar ratios 1-4:1 mixed preparing solution C, then by solution C With ethylene glycol by volume 1:50-70 is mixed, and pH=9-12 is adjusted with the ethylene glycol solution of sodium hydroxide；In 120-160 DEG C, instead Answer 2-4h；A concentration of 1-4mol L of the ethylene glycol solution of the sodium hydroxide-1。
D. the ZrO that will be prepared by step B2/ GN powder pours into ethylene glycol and prepares suspension D, and wherein solid content is 5- 15g/L, ultrasonic disperse 15-30min；It is 1 according still further to the volume ratio of suspension D and solution C:Suspension D is added drop-wise to step by 2-5 In the reaction solution of C, in 120-160 DEG C of the reaction was continued 3-6h, filter, three times with deionized water and ethyl alcohol alternating washing sample, Vacuum drying obtains PtSn-ZrO2/ GN composite catalysts.
Fig. 1 is ZrO prepared by embodiment 12/ GN and PtSn-ZrO2The XRD spectra of/GN.In a, two curves of b, 2 θ= Corresponding gentle peak is the characteristic diffraction peak of carrier graphene at 26 °.By curve b and standard card (PDF card 04-0802) contrast, in 2 θ=39.8 °, the feature for being face-centred cubic structure Pt corresponding to 46.2 °, 67.4 ° and 81.3 ° Diffraction maximum, corresponding crystal face are respectively (111), (200), (220), (311).Curve b is PtSn-ZrO2/ GN catalyst The characteristic diffraction peak of XRD spectra, curve b metals Sn or its oxide does not occur, illustrates that Sn is in the form of unbodied In the presence of.It can be seen from the figure that each characteristic peak appearance is apparent in composite construction, well-formed.
Fig. 2 (a) is the electron microscopic picture of PtSn/GN catalyst prepared by embodiment 2.It can be seen from the figure that PtSn nanometers Particle has been evenly distributed on the surface of graphene, but subregion, which is observed that agglomeration, average grain diameter, is 2.48nm.Fig. 2 (b) is PtSn-ZrO prepared by embodiment 22The composite construction catalyst of/GN.It is observed that catalyst in figure Particle is evenly dispersed on carrier, illustrates ZrO2It can inhibit Pt nanoparticle agglomerates, and its average grain diameter is 2.4nm.
The characterization of chemical property is carried out to fuel-cell catalyst with cyclic voltammetry curve method and linear voltammetric scan method, As a result it sees figures 3 and 4, from Fig. 3,4：PtSn-ZrO2The catalytic activity of/GN will be significantly higher than PtSn/GN, just sweep direction (representing oxidation of ethanol) peak current density reaches 10.53mA cm-2, and it is doped with ZrO2Catalyst there is minimum starting electricity Position, illustrates in ZrO2In the presence of, since there are more Lacking oxygens for it, increase the concentration of partial oxygen.In catalysis ethanol In oxidation process, ZrO2As O mainly for source is answered, species CO among oxidation of ethanol is promotedadsOxidation and removal.
Advantageous effect：PtSn-ZrO prepared by the present invention2/ GN composite catalysts not only reduce the load capacity of platinum, drop Low catalyst cost, meanwhile, the ZrO of doping2Oxygen can not only be adsorbed by Lacking oxygen, it can also play promotion as Sn Water decomposition generates OHadsSpecies, OHadsWith COadsInteraction generates CO2, be conducive to COadsIt removes, is released more from the surfaces Pt More active sites.To improve the catalytic activity of catalyst.The take-off potential of its catalysis ethanol oxidation is 0.14V, the just side of sweeping It can reach 10.53mAcm to peak current density-2.Used preparation method is simple and easy to do, is easy to commercial Application.
Description of the drawings
Fig. 1 is ZrO prepared by embodiment 12/ GN and PtSn-ZrO2The XRD spectra of/GN.Wherein a is ZrO2The XRD of/GN Curve, b PtSn-ZrO2The XRD curves of/GN.
Fig. 2 is PtSn/GN and PtSn-ZrO prepared by embodiment 22The transmission electron microscope photo of/GN.A is the saturating of PtSn/GN Penetrate electromicroscopic photograph, b PtSn-ZrO2The transmission electron microscope photo of/GN.
Fig. 3 is PtSn/GN and PtSn-ZrO prepared by embodiment 32The cyclic voltammetry curve of/GN.A is following for PtSn/GN Ring volt-ampere curve, b PtSn-ZrO2The cyclic voltammetry curve of/GN.
Fig. 4 is the PtSn/GN and PtSn-ZrO of preparation prepared by embodiment 22The polarization curve of/GN.A is PtSn/GN's Polarization curve, b PtSn-ZrO2The polarization curve of/GN.
Specific implementation mode
Embodiment 1
A. 22.57g zirconium nitrates and 200mg graphite oxides (GO) dispersion are prepared into 100ml suspension A in deionized water, 10g/L sodium borohydride aqueous solution 15ml are added dropwise, after stirring 1h, filters, is washed with 80% ethanol solution, it is dry, obtain pre- go back Former ZrO2/ GN powder；
B. sample 1g ultrasonic disperses made from step A are prepared into suspension B, ultrasonic disperse in 100ml ethylene glycol solutions 10min reacts 5 hours by suspension B at 130 DEG C, filters, is washed with 80% ethanol solution, dry, obtains ZrO2/ GN powder.Again under nitrogen atmosphere, 1h is calcined when temperature is 550 DEG C；
C. the platinum acid chloride solution 1.1ml and stannous chloride 14.4mg for taking a concentration of 3g/100ml, according to Pt:Sn molar ratios 1: 1 mixed preparing solution C, solution C are mixed with 66ml ethylene glycol.With 1mol L-1The ethylene glycol solution of sodium hydroxide adjusts pH= 10；In 120 DEG C, 4h is reacted；
D. the 80mgZrO that will be prepared by step B2/ GN powder, which is added in 16ml ethylene glycol, prepares suspension D, ultrasound Disperse 15min.Suspension D is added drop-wise in the reaction solution of step C to the reaction was continued dropwise again, the dripping quantity of suspension D is 33ml, reaction temperature are 120 DEG C, reaction time 5h, are filtered, and distinguish washing sample three times with deionized water and ethyl alcohol, vacuum It is dried to obtain PtSn-ZrO2/ GN composite catalysts.
PtSn/GN catalyst is prepared according to step C, step D equally formula and method to be used for and above-mentioned PtSn-ZrO2/ GN composite catalysts carry out contrast test, do not include step A and step B, the difference is that needing the 80mgZrO in step D2/GN Change 80mg graphite oxides (GO) into.The result is shown in Figure 1.
Embodiment 2
A. 8.03mg zirconium nitrates and 200mg graphite oxides (GO) dispersion are prepared into 100ml suspension A in deionized water, 10g/L sodium borohydride aqueous solution 25ml are added dropwise, after stirring 1.5h, filters, is washed with 80% ethanol solution, it is dry, it obtains pre- The ZrO of reduction2/ GN powder；
B. sample 1.5g ultrasonic disperses made from step A are prepared into suspension B, ultrasound point in 100ml ethylene glycol solutions 15min is dissipated, by suspension B at 140 DEG C, 4 hours is reacted, filters, washed with 80% ethanol solution, it is dry, it obtains ZrO2/ GN powder.Again under nitrogen atmosphere, 1h is calcined when temperature is 600 DEG C；
C. take the platinum acid chloride solution 1.26ml and stannous chloride 11.0mg of a concentration of 3g/100ml according to Pt:Sn molar ratios 1.5:1 mixed preparing solution C, solution C are mixed with 75.6ml ethylene glycol.With 2mol L-1Sodium hydroxide and ethylene glycol solution are adjusted PH=11；In 130 DEG C, 3h is reacted；
D. the 80mg ZrO that will be prepared by step B2/ GN powder pours into 8ml ethylene glycol and prepares suspension D, ultrasound point Dissipate 20min.Suspension D is added drop-wise in the reaction solution of step B to the reaction was continued dropwise again, the dripping quantity of suspension D is 25.2ml, reaction temperature are 130 DEG C, reaction time 4h, are filtered, and distinguish washing sample three times with deionized water and ethyl alcohol, very Sky is dried to obtain PtSn-ZrO2/ GN composite catalysts.
PtSn/GN catalyst is prepared according to step C, step D equally formula and method to be used for and above-mentioned PtSn-ZrO2/ GN composite catalysts carry out contrast test, do not include step A and step B, the difference is that needing the 80mgZrO in step D2/GN Change 80mg graphite oxides (GO) into.As a result see Fig. 3.
Respectively by PtSn/GN, PtSn-ZrO of above-mentioned preparation2/ GN carries out chemical property comparison using cyclic voltammetry Test pretreatment of glassy carbon electrode：Respectively by 5mg PtSn/GN and PtSn-ZrO2/ GN 5ml isopropanols, 19.9ml deionized waters With 0.1ml 5%Nafion solution wiring solution-formings, the ultrasound 2h in ultrasonic cleaner, makes catalyst be dispersed in later In mixed solution；20 μ l catalyst solutions are pipetted in glassy carbon electrode surface with liquid-transfering gun, are dried at room temperature.
Test carries out in three-electrode system, makees working electrode (d=with glass-carbon electrode of the above-mentioned surface containing catalyst 5mm), reference electrode is Ag/AgCl electrodes, is platinum filament to electrode, with the HClO of 0.1mol/L4The ethanol solution of+1mol/L is done Electrolyte.
As seen from Figure 3, PtSn-ZrO2The catalytic activity of/GN will be significantly higher than PtSn/GN, PtSn-ZrO2The just side of sweeping of/GN Reach 10.53mAcm to peak current density-2, and the peak current density of PtSn/GN is 4.25mAcm-2
Embodiment 3
A. 6.28g zirconium nitrates and 200mg graphite oxides (GO) dispersion are prepared into suspension A in deionized water, are added dropwise 10g/L sodium borohydride aqueous solution 30ml after stirring 2h, are filtered, are washed with 80% ethanol solution, dry, obtain prereduction ZrO2/ GN powder；
B. sample 2g ultrasonic disperses made from step A are prepared into suspension B, ultrasonic disperse in 100ml ethylene glycol solutions 20min reacts 3 hours by suspension B at 160 DEG C, filters, is washed with 80% ethanol solution, dry, obtains ZrO2/GN Powder.Again under nitrogen atmosphere, 1h is calcined when temperature is 650 DEG C；
C. take the platinum acid chloride solution 1.36ml and stannous chloride 8.9mg of a concentration of 3g/100ml according to Pt:Sn molar ratios 2:1 Mixed preparing solution C, solution C are mixed with 81.6ml ethylene glycol.With 3mol L-1Sodium hydroxide and ethylene glycol solution adjust pH= 12；In 160 DEG C, 2h is reacted；
D. the 80mg ZrO that will be prepared by step B2/ GN powder pours into 5.3ml ethylene glycol and prepares suspension D, ultrasound Disperse 30min.Suspension D is added drop-wise in the reaction solution of step B to the reaction was continued dropwise again, the dripping quantity of suspension D is 20.4ml, reaction temperature are 160 DEG C, reaction time 3h, are filtered, and distinguish washing sample three times with deionized water and ethyl alcohol, very Sky is dried to obtain PtSn-ZrO2/ GN composite catalysts.
PtSn/GN catalyst is prepared according to step C, step D equally formula and method to be used for and above-mentioned PtSn-ZrO2/ GN composite catalysts carry out contrast test, do not include step A and step B, the difference is that needing the 80mgZrO in step D2/GN Change 80mg graphite oxides (GO) into.As a result see Fig. 4.
Using linear voltammetric scan method to respectively by PtSn/GN, PtSn-ZrO of above-mentioned preparation2/ GN carries out electrochemistry It can contrast test
The same cyclic voltammetry of pretreatment of glassy carbon electrode.
Test carries out in three-electrode system, makees working electrode (d=with glass-carbon electrode of the above-mentioned surface containing catalyst 5mm), reference electrode is Ag/AgCl electrodes, is platinum filament to electrode, in the HClO of 0.1mol/L4In the ethanol solution of+1mol/L Carry out linear voltammetric scan test.Sweep speed is 5mV/s, the ranging from -0.2-0.8V of test voltage, the rotating speed of rotating circular disk For 1600 rpm/min.Test result is shown in Fig. 4
PtSn-ZrO as seen from Figure 42/ GN bears relative to the oxidation of ethanol take-off potential of PtSn/GN and has moved 60mV. PtSn- ZrO2The peak current density of/GN curves is significantly higher than PtSn/GN.It is doped with ZrO2Catalyst there is apparent high peak current Density illustrates the concentration that partial oxygen is increased in the presence of scandium oxide.In catalysis ethanol oxidation process, zirconium oxide is made It is oxygen mainly for source is answered, promotes species CO among oxidation of ethanoladsOxidation.

Claims (1)

1. a kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, is as follows：
A. by Zr (NO3)4·5H2100ml suspension A, wherein nitric acid are prepared in O and graphite oxide (GO) dispersion in deionized water The molar concentration of zirconium is 0.08-0.27mol/L, a concentration of 2g/L of graphite oxide；According to suspension A and sodium borohydride aqueous solution Volume ratio be 1：10g/L sodium borohydride aqueous solutions are added dropwise in 0.15-0.30, stir 1-2h, filter, are washed with 80% ethanol solution It washs, it is dry, obtain the ZrO of prereduction2/ GN powder；
B. ZrO step A obtained2/ GN powder ultrasonics, which are scattered in ethylene glycol solution, is made into suspension B, and wherein solid content is 10-20g/L, ultrasonic disperse 10-20min；Then at 120-160 DEG C, 3-6 hour is reacted, filters, is washed with 80% ethanol solution It washs, it is dry, obtain ZrO2/ GN powder, then under nitrogen atmosphere, temperature is 550-700 DEG C of calcining 1h；
C. by platinum acid chloride solution and SnCl2·2H2O is according to Pt:Sn molar ratios 1-4:1 mixed preparing solution C, then by solution C and second Glycol by volume 1:50-70 is mixed, and pH=9-12 is adjusted with the ethylene glycol solution of sodium hydroxide；In 120-160 DEG C, 2- is reacted 4h；A concentration of 1-4mol L of the ethylene glycol solution of the sodium hydroxide-1；
D. the ZrO that will be prepared by step B2/ GN powder pours into ethylene glycol and prepares suspension D, and wherein solid content is 5-15g/L, Ultrasonic disperse 15-30min；It is 1 according still further to the volume ratio of suspension D and solution C:Suspension D is added drop-wise to the anti-of step C by 2-5 It answers in solution, in 120-160 DEG C of the reaction was continued 3-6h, filters, three times with deionized water and ethyl alcohol alternating washing sample, vacuum is dry It is dry to obtain PtSn-ZrO2/ GN composite catalysts；The catalyst is the ZrO using graphene as carrier2It is active component to adulterate PtSn Catalyst, wherein PtSn are alloy part type, ZrO2Uniform Doped is in PtSn/GN；The catalyst is fired as direct ethyl alcohol Expect that cell anode catalyst, oxidation of ethanol take-off potential reach 0.1-0.2V, stability ratio Pt/GN catalyst improves 1- 2 times, the peak current density of catalysis ethanol oxidation reaches 9~11mAcm-2。
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Inventor after: Jiang Qian

Inventor after: Zhu Hong

Inventor after: Han Kefei

Inventor after: Wang Zhongming

Inventor before: Yu Suping

Inventor before: Jiang Qian

Inventor before: Zhu Hong

Inventor before: Han Kefei

Inventor before: Wang Zhongming

CB03 Change of inventor or designer information