CN105244511A - Alloy electrocatalyst and preparation method thereof - Google Patents

Alloy electrocatalyst and preparation method thereof Download PDF

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CN105244511A
CN105244511A CN201510634767.4A CN201510634767A CN105244511A CN 105244511 A CN105244511 A CN 105244511A CN 201510634767 A CN201510634767 A CN 201510634767A CN 105244511 A CN105244511 A CN 105244511A
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amtio
catalyst
rgo
accounts
gross mass
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CN105244511B (en
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张慧
高艺之
陈高文
窦立广
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Beijing University of Chemical Technology
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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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • 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
    • 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
    • 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 invention discloses an alloy electrocatalyst and a preparation method thereof, and belongs to the technical field of fuel cell catalysts. Chemical components of the catalyst can be described as Pt<x>Ni<1>/amTiO<2>/rGO, wherein Pt accounts for 15.3wt.%-18.0wt.% of total mass of the catalyst; Ni accounts for 2.0wt.%-4.7wt.% of total mass of the catalyst; the total mass of the Pt and the Ni accounts for 20wt.% of total mass of the catalyst; an amTiO<2>/rGO compound accounts for 80wt.% of total mass of the catalyst; and amTiO<2> accounts for 20wt.% of total mass of the amTiO<2>/GO compound. The alloy electrocatalyst has the advantages that size reduction of PtNi alloy particles is promoted; and small sizes and high dispersion of the PtNi particles are beneficial to improvement of the catalytic performance of a synthesized catalyst in positive and negative catalytic reactions of a DMFC. With ethylene glycol as a solvent and a reducing agent, H<2>PtCl<6>, Ni(NO<3>)<2> and GO are simultaneously reduced to prepare the Pt<x>Ni<1>/amTiO<2>/rGO electrocatalyst by an ethylene glycol impregnation-reduction method, so that the technology is simple and the operation is easy.

Description

A kind of alloy eelctro-catalyst and preparation method thereof
Technical field
The invention belongs to fuel cell catalyst technical field, specifically provide a kind of alloy eelctro-catalyst and preparation method thereof, is a kind of Pt xni 1/ amTiO 2/ rGO alloy eelctro-catalyst and preparation method thereof and application.
Background technology
At present, main using precious metals pt sill as anode and cathod catalyst in the investigation and application of direct methanol fuel cell (DMFC), mainly because in all metallic catalysts, Pt shows the highest electro catalytic activity and excellent electro-catalysis efficiency.But, due to the high cost of catalyst, anode catalyst easily poisoning, cathod catalyst overpotential is high and carbon carrier is perishable with problems such as oxidations, researcher is devoted to formulate the anode electrocatalyst of high CO tolerance and the cathod catalyst of low overpotential with novel structure day by day.
Graphene (GNs) carries Pt nano material and attracted the attention of a large amount of researcher because having low Pt content and difunctional mechanism and ligand effect in DMFC.Thereupon, Pt bimetallic or the research supported on GNs of tri-metal nano structure day by day increase (document (1) Chem.Rev., 2014,114:5117-5160).So far, some PtM/GNs alloy materials containing other noble metals are applied in DMFC as eelctro-catalyst, such as PtPd/GNs, PtAu/GNs and PtRu/GNs etc.But the introducing of other noble metals still can make the cost of Pt base eelctro-catalyst remain high.Therefore, there is researcher that the non-noble metal j element such as Ni, Co and Cu are introduced Graphene as alloying element at present and support PtM composite material as DMFC catalyst, as PtNi/GNs, PtCo/GNs and PtCu/GNs etc.It should be noted that, advantage (111) active surface (document (2) Chem.Commun. existed in the PtNi alloy that Pt and non-noble metal Ni are formed, 2014,49:7486-7488) make it both can be used as the catalyst of anode methanol electro-oxidizing reaction (MOR), can be used as again the catalyst of Cathodic oxygen reduction (ORR).The people such as Hu adopt a simple stage reduction method, are reducing agent with hydrazine hydrate, redox graphene (GO), the PtCl while of under normal temperature 6 2-and Ni 2+final obtained PtNi total content is the Series P tNi alloy catalyst of 40wt.%, and carry PtNi alloy catalyst with Single Walled Carbon Nanotube (SWNTs) and XC-72 carbon and make performance comparison, discovery is that the catalyst of carrier has the most excellent MOR activity and stability (document (3) Appl.Catal.B:Environ. with Graphene, 2012,111:208-217), and compared with not containing the Pt-graphene/GC of Ni, Pt-Ni-graphene/GC has the catalytic activity significantly improved.But, directly Pt or PtM alloy particle is supported on redox graphene (rGO), in electrocatalytic reaction, still there is Pt to the oxidation of carbon carrier rGO and electrolyte to the etching problem of rGO.
Titanium dioxide has high chemical stability, high rigidity, corrosion resistance and nontoxicity.Therefore, in the selectable carrier material of direct methanol fuel cell catalyst, TiO 2attract large quantifier elimination interest.Existing researcher is by Pt and TiO 2jointly support and obtain Pt base ternary complex catalyst on Graphene.Zhao etc. adopt business anatase TiO 2(particle diameter 20nm), prepares Pt/graphene-TiO with simple one pot of hydro thermal method 2hybrid catalyst (20wt.%Pt), Pt average grain diameter is 2.28nm, and this catalyst provides mass activity 423.3Ag in MOR -1, be 1.46 and 1.64 times (document (4) J.PowerSources, 2015,279:210-217) of Pt/graphene and business 20wt.%Pt/C (E-TEK) respectively.But, at present with TiO 2the catalyst based middle TiO of Pt of grapheme modified preparation 2mostly be Anatase, not yet have with amorphous TiO so far 2modifying redox graphene is that carrier is prepared the PtNi alloy catalyst of the different Pt:Ni atomic ratio of low Pt content and is applied to the report of DMFC anode and cathode catalysis reaction.
Summary of the invention
The object of the present invention is to provide a kind of alloy eelctro-catalyst and preparation method thereof, a kind of Pt xni 1/ amTiO 2/ rGO (x (Pt:Ni atomic ratio)=1,2,3) alloy eelctro-catalyst and preparation method thereof.First prepare graphene oxide (GO) sol system, then adopt the sol-gel process of improvement that isopropyl titanate (TTIP) is obtained amorphous TiO in the hydrolysis of GO sol system situ and long-time (72h) standing and drying of room temperature 2modify GO compound amTiO 2/ GO (20wt.%TiO 2); Then, ethylene glycol immersion reduction method is adopted to prepare support type PtNi alloy catalyst Pt xni 1/ amTiO 2/ rGO, wherein PtNi total content is 20wt.%.Amorphous TiO in such catalyst 2be dispersed in rGO surface, one of its effect is to provide TiO 2the performance of-OH key promoting catalyst difunctional mechanism in electro-catalysis methanol oxidation; two of effect is the decentralization improving PtNi nano particle; three of effect is the effects to a certain extent rGO being played to insulation blocking, utilizes Ni and Pt to form alloy simultaneously and can change the geometric configuration of Pt and PtNi alloy particle and amTiO 2the CO tolerance catalysts ability of the cooperative effect between/rGO and then raising catalyst, adds Ni replacement part Pt and can reduce the content of Pt in catalyst and then improve the utilance of Pt.In addition, by Pt 3ni 1/ amTiO 2/ rGO catalyst application, in the anodic oxidation reactions of Cathodic oxygen reduction and ethanol and formic acid, finds that this catalyst has Pt/amTiO more catalyst based than simple Pt 2the catalytic performance that/rGO, Pt/rGO and Pt/C (JM) improve.
1, in the present invention, the chemical composition of catalyst can be described as Pt xni 1/ amTiO 2/ rGO::Pt accounts for 15.3 ~ 18.0wt.% of catalyst gross mass, and Ni accounts for 2.0 ~ 4.7wt.% of catalyst gross mass, and the 20wt.% of catalyst gross mass that Pt and Ni gross mass accounts for.AmTiO 2/ rGO compound accounts for catalyst gross mass 80wt.%, and amTiO 2account for amTiO 2the 20wt.% of/GO compound gross mass.
Pt of the present invention xni 1/ amTiO 2preparation method's concrete steps of/rGO alloy eelctro-catalyst are as follows:
Step 1: adopt the Hummers method (document (5) Chem.Mater., 1999,11:771-778) improved to prepare graphene oxide (GO) hydrosol, concentration is 16.4mg/mL.
Step 2: adopt the sol-gel process improved to prepare amTiO 2/ GO, by ultrasonic 4h under 40mL absolute ethyl alcohol, 7.8mL deionized water, 360 μ L glacial acetic acid and 12.2mLGO hydrosol mixed liquor room temperature, makes mixed liquor be uniformly dispersed, is designated as A liquid;
Ultrasonic 0.5h under the mixed liquor room temperature of put 30mL absolute ethyl alcohol and 186 μ L isopropyl titanates, makes mixed liquor be uniformly dispersed, is designated as B liquid;
B liquid is dropwise instilled after in A liquid, continue to stir 1h, obtain TiO 2-GO colloidal sol; By TiO 2-GO colloidal sol is uncovered to be statically placed in 25 DEG C of water-baths, and solvent naturally volatilizees after 72h and obtains sepia solid, is ground to powder, collects for subsequent use, be designated as amTiO 2/ GO; Wherein amTiO 2at amTiO 2theoretical Mass mark in/GO is 20wt.%.
Step 3: adopt ethylene glycol immersion reduction method for preparing Pt xni 1/ amTiO 2/ rGO, x (1 ~ 3) are Pt:Ni atomic ratio, and PtNi total content is 20wt.% catalyst; By 2.07 ~ 2.45mL0.019MH 2ptCl 6the aqueous solution, 0.45 ~ 1.16mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 6.77 ~ 7.10mL deionized water join in there-necked flask, and ultrasonic mixing 0.5h, takes amTiO subsequently 2/ GO compound 40mg joins in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture; Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains serial eelctro-catalyst Pt for filtration washing xni 1/ amTiO 2/ rGO, wherein, theoretical Pt:Ni atomic ratio x is respectively 1,2,3, and precious metals pt Theoretical Mass mark is in the catalyst 15.3 ~ 18.0wt.%, Ni is 2.0 ~ 4.7wt.%.
The present invention has following beneficial effect compared with the prior art:
(1) amorphous TiO is prepared with the sol-gel process improved in step 2 2even modification GO compound amTiO 2/ GO as the carrier of PtNi alloy catalyst, amorphous TiO 2ptNi alloy particle is had to the effect promoting dispersion, and then promote the reduction of PtNi alloy particle size, the small size of PtNi particle and high dispersive are conducive to the raising of synthesized catalyst catalytic performance in DMFC anode and cathode catalysis reaction.
(2) in step 3 with ethylene glycol be solvent and reducing agent, adopt ethylene glycol immersion reduction method to reduce H simultaneously 2ptCl 6, Ni (NO 3) 2pt is prepared with GO xni 1/ amTiO 2/ rGO eelctro-catalyst, this process is without the need to adding other reducing agents again, and technique simply, easily operates.
Accompanying drawing explanation
Fig. 1 is amTiO 2the high-resolution-ration transmission electric-lens figure of/GO.
Fig. 2 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2the X-ray diffraction spectrogram of/rGO (3) and Pt/rGO (4).
Fig. 3 is Pt 3ni 1/ amTiO 2the SEM figure of/rGO
Fig. 4 Pt 3ni 1/ amTiO 2the Mapping figure of Ti element in/rGO.
Fig. 5 Pt 3ni 1/ amTiO 2the Mapping figure of Ni element in/rGO.
Fig. 6 Pt 3ni 1/ amTiO 2the Mapping figure of Pt element in/rGO.
Fig. 7 is Pt 3ni 1/ amTiO 2(illustration is Pt to/rGO low power high-resolution-ration transmission electric-lens figure 3ni 1alloy grain size distribution).
Fig. 8 is Pt 3ni 1/ amTiO 2/ rGO high power high-resolution-ration transmission electric-lens figure.
Fig. 9 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2/ rGO (3), Pt/rGO (4) and Pt/C (JM) (5) catalyst are at H 2sO 4(0.5M) cyclic voltammetry curve in solution, wherein sweep speed is 50mV/s.
Figure 10 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2/ rGO (3), Pt/rGO (4) and Pt/C (JM) (5) catalyst are at H 2sO 4(0.5M)+CH 3cyclic voltammetry curve in OH (0.5M) mixed solution, wherein sweep speed is 50mV/s.
Figure 11 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2/ rGO (3), Pt/rGO (4) and Pt/C (JM) (5) the catalyst current-vs-time under fixed voltage 0.6V (I-t) curve.
Figure 12 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2what/rGO (3), Pt/rGO (4) and Pt/C (JM) (5) catalyst 200 enclosed CV curve just sweeps peak current density value attenuation curve, and wherein sweep speed is 50mV/s.
Figure 13 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2the CV curve of/rGO (3), Pt/rGO (4) and Pt/C (JM) (5).Electrolyte is all O 2saturated H 2sO 4(0.5M) solution, cathodic oxygen reduction test is carried out on PARSTAT2273 electrochemical analyser.
Figure 14 is Pt 3ni 1/ amTiO 2/ rGO (1), Pt 3ni 1/ rGO (2), Pt/amTiO 2/ rGO (3), Pt/rGO (4) and Pt/C (JM) (5) 1600rpmLSV curve.Electrolyte is all O 2saturated H 2sO 4(0.5M) solution, cathodic oxygen reduction test is carried out on PARSTAT2273 electrochemical analyser.
Figure 15 is Pt 3ni 1/ amTiO 2the LSV curve of/rGO under different rotating speeds, wherein (1)-(7) be respectively 400,625,900,1225,1600,2025,2500rpm.Electrolyte is all O 2saturated H 2sO 4(0.5M) solution, cathodic oxygen reduction test is carried out on PARSTAT2273 electrochemical analyser.
Figure 16 is Pt 3ni 1/ amTiO 2the K-L curve of/rGO under different potentials, wherein (1)-(7) be respectively 0.00,0.05,0.10,0.15,0.20,0.25,0.30V.Electrolyte is all O 2saturated H 2sO 4(0.5M) solution, cathodic oxygen reduction test is carried out on PARSTAT2273 electrochemical analyser.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Step one: prepare graphene oxide (GO) hydrosol, its concentration is 16.4mg/mL.
Step 2: adopt the sol-gel process improved to prepare amTiO 2/ GO, by ultrasonic 4h under the mixed liquor room temperature of 40mL absolute ethyl alcohol, 7.8mL deionized water, 360 μ L glacial acetic acid and the 12.2mLGO hydrosol (see step one), makes mixed liquor be uniformly dispersed, is designated as A liquid.Ultrasonic 0.5h under the mixed liquor room temperature of put 30mL absolute ethyl alcohol and 186 μ L isopropyl titanates, is designated as B liquid.Under 25 DEG C of magnetic agitation conditions, B liquid is dropwise instilled after in A liquid, continue to stir 1h, obtain TiO 2-GO colloidal sol; By TiO 2-GO colloidal sol is uncovered is statically placed in aging 72h in 25 DEG C of water-baths, obtains amTiO 2/ GO compound, is ground to powder, collects for subsequent use.Wherein amTiO 2at amTiO 2theoretical Mass mark in/GO is 20wt.%.
Step 3: adopt ethylene glycol immersion reduction method for preparing Pt 3ni 1/ amTiO 2/ rGO eelctro-catalyst, by 2.45mL0.019MH 2ptCl 6the aqueous solution, 0.45mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 7.10mL deionized water join in there-necked flask, and ultrasonic mixing 0.5h, takes amTiO subsequently 2/ GO compound 40mg joins in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture.Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains eelctro-catalyst Pt for filtration washing 3ni 1/ amTiO 2/ rGO, theoretical Pt:Ni atomic ratio x is 3, and wherein precious metals pt Theoretical Mass mark is in the catalyst 18.0wt.%, Ni be 2.0wt.%, PtNi gross mass mark is 20wt.%.
Embodiment 2
The present embodiment except following characteristics with embodiment 1:
By 2.35mL0.019MH 2ptCl 6the aqueous solution, 0.65mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 7.00mL deionized water join in there-necked flask, and ultrasonic mixing 0.5h, takes amTiO subsequently 2/ GO compound 40mg is placed in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture.Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains eelctro-catalyst Pt for filtration washing 2ni 1/ amTiO 2/ rGO, theoretical Pt:Ni atomic ratio x is 2, and wherein precious metals pt Theoretical Mass mark is in the catalyst 17.4wt.%, Ni be 2.6wt.%, PtNi gross mass mark is 20wt.%.
Embodiment 3
The present embodiment except following characteristics with embodiment 1:
By 2.07mL0.019MH 2ptCl 6the aqueous solution, 1.16mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 6.77mL deionized water join in there-necked flask, and ultrasonic mixing 0.5h, takes amTiO subsequently 2/ GO compound 40mg joins in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture.Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains eelctro-catalyst Pt for filtration washing 1ni 1/ amTiO 2/ rGO, theoretical Pt:Ni atomic ratio x is 1, and wherein precious metals pt Theoretical Mass mark is in the catalyst 15.3wt.%, Ni be 4.7wt.%, PtNi gross mass mark is 20wt.%.
Comparative example 1
The present embodiment except following characteristics with embodiment 1:
By 2.45mL0.019MH 2ptCl 6the aqueous solution, 0.45mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 7.00mL deionized water join in there-necked flask, ultrasonic mixing 0.5h, measure GO hydrosol 2.47mL subsequently and join in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture.Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains eelctro-catalyst Pt for filtration washing 3ni 1/ rGO, theoretical Pt:Ni atomic ratio x is 3, and wherein precious metals pt Theoretical Mass mark is in the catalyst 18.0wt.%, Ni be 2.0wt.%, PtNi gross mass mark is 20wt.%.
Comparative example 2
The present embodiment except following characteristics with embodiment 1:
Adopt ethylene glycol immersion reduction method for preparing Pt/amTiO 2/ rGO eelctro-catalyst, by 40mgamTiO 2/ GO (see step one) joins 40mL ethylene glycol, 7.35mL deionized water and 2.65mL0.019MH 2ptCl 6in the mixed liquor of the aqueous solution, ultrasonic immersing 0.5h obtains suspension; Gained suspension is put into the oil bath pan of 120 DEG C, stir 24h at condensing reflux condition lower magnetic force, obtain black suspension; Suspension filtered washing is separated to obtain black solid for several times; Again by black solid vacuumize 24h at 40 DEG C, collect after being ground to powder, be designated as Pt/amTiO 2/ rGO.Wherein precious metals pt Theoretical Mass mark is in the catalyst 20.0wt.%.
Comparative example 3
This comparative example except following characteristics with embodiment 1:
By 4.9mL deionized water, 2.65mL0.019MH 2ptCl 6the ultrasonic 0.5h of mixed liquor of the GO hydrosol in the aqueous solution, 40mL ethylene glycol and 2.45mL embodiment 1 obtains suspension; Gained suspension is put into the oil bath pan of 120 DEG C, stir 24h at condensing reflux condition lower magnetic force, obtain black suspension; Black suspension filtration washing is separated to obtain black solid for several times; Again by black solid vacuumize 24h at 40 DEG C, collect after being ground to powder, be designated as Pt/rGO.Wherein precious metals pt Theoretical Mass mark is in the catalyst 20.0wt.%.
The Series P t prepared according to the method described above xni 1/ amTiO 2/ rGO eelctro-catalyst with Pt nano particle for catalytic active component, Ni and amTiO 2for co catalysis composition, and amTiO 2rGO is played a protective role, slows down its oxide etch speed in Electrocatalytic Oxidation of Methanol reaction.Fig. 1 is amTiO 2, there is minute quantity and belong to anatase TiO in/GO high-resolution-ration transmission electric-lens figure 2lattice fringe, i.e. TiO 2exist with amorphous state.
Fig. 2 is the X-ray diffraction spectrogram of each embodiment sample, the characteristic diffraction peak all occurring belonging to face-centered cubic Pt can be seen in publishing picture, and Pt (111) crystallographic plane diffraction peak offsets 0.2 degree to high angle compared with pure Pt catalyst, prove that Pt and Ni forms alloy, and do not occur TiO in figure 2crystal characteristic diffraction maximum, illustrates TiO 2for amorphous state.
Fig. 3 is Pt 3ni 1/ amTiO 2the SEM figure of/rGO, Fig. 4 are Pt/amTiO 2the Mapping figure of Ti element in/rGO, Fig. 5 is Pt/amTiO 2the Mapping figure of Ni element in/rGO, Fig. 6 is Pt/amTiO 2the Mapping figure of Pt element in/rGO.By Fig. 4,5 and 6 known at Pt 3ni 1/ amTiO 2in/rGO, each element is all evenly distributed, and tests known Pt by Energy Dispersive X power spectrum 3ni 1/ amTiO 2in/rGO, precious metals pt content is 17.93wt.%, Ni content is 1.92wt.%.Fig. 7 is Pt 3ni 1/ amTiO 2/ rGO high-resolution-ration transmission electric-lens figure, known PtNi alloy nano particle is at amTiO 2/ rGO is upper dispersed.Average-size through statistics Pt nano particle (Fig. 7 illustration) is 2.45nm, is less than Pt 3ni 1pt nano-particles size (3.26nm) in/rGO.From Fig. 8 high power high-resolution-ration transmission electric-lens figure, occur belonging to Pt (111) crystal face lattice fringe, reduce to some extent compared with pure Pt catalyst crystal lattice striped (0.2271nm), prove that the alloying action of Ni makes the Lattice Contraction of Pt.
Anode electrochemical performance test:
CHI660D electrochemical workstation (Shanghai occasion China) is adopted to carry out organic molecule electro-oxidation reaction in room temperature (25 ± 2 DEG C) three-electrode system.Adopt platinum filament to be to electrode, saturated calomel electrode (SCE) is reference electrode, and the glass-carbon electrode being loaded with eelctro-catalyst is work electrode.Before carrying out electrochemical property test, first polishing is carried out to glass-carbon electrode, adopt 1.0 μm, 0.3 μm and 0.05 μm of Al respectively 2o 3powder and ultra-pure water mix to drip respectively carry out polishing to electrode on corresponding polishing cloths, then adopt the HNO of volume fraction 50% respectively 3solution, absolute ethyl alcohol and deionized water carry out ultrasonic cleaning to the glass-carbon electrode after polishing successively, and naturally dry under being placed in room temperature.Eelctro-catalyst slurries are all prepared according to the proportioning of 5mg catalyst fines, 450 μ L isopropyl alcohols, 50 μ LNafion solution (5wt.%, DuPont).Then, get 2.5 μ L eelctro-catalyst slurry drops in glassy carbon electrode surface, left at room temperature dries for subsequent use.In the present invention, all electrode potentials are all relative to saturated calomel electrode (vs.SCE).
Electrochemical cathode performance test:
Adopt on PARSTAT2273 electrochemical analyser and carry out cathodic oxygen reduction test.Adopt traditional standard three-electrode system, the glass carbon rotating disk electrode (r.d.e) (GCRDE, Pine company of the U.S.) of work electrode to be diameter be 5mm, be Pt silk to electrode, reference electrode is saturated calomel electrode (SCE).Adopt import Al 2o 3polishing fluid carries out polishing to GCRDE, adopts ultra-pure water that electrode clean is clean subsequently, dry in left at room temperature.Then, accurate weighing 5mg catalyst and 450 μ L isopropyl alcohols and 50 μ LNafion (5wt.%, Dupont) mix, ultrasonic disperse 30min obtains catalyst slurry, 5 μ L slurry drops are pipetted on GCRDE with micro-sampling pin, leave standstill under room temperature normal pressure, after solvent evaporation, carry out electro-chemical test.In the present invention, all electrode potentials are all relative to saturated calomel electrode (vs.SCE).
The electrochemically active specific surface area value (ECSA) calculated by Fig. 9 and Figure 10 just sweep peak current density (I f) known, Pt 3ni 1/ amTiO 2the MOR of/rGO is active in Pt 3ni 1/ rGO, Pt/rGO and Pt/C (JM), with the Pt/amTiO of high Pt content 2/ rGO is close, proves the Pt prepared by the present invention 3ni 1/ amTiO 2/ rGO catalyst has excellent electro catalytic activity, and Pt 3ni 1/ amTiO 2/ rGO just sweeps peak current density (I f) sweep peak current density (I with counter b) ratio (I f/ I b) far above Pt/amTiO 2/ rGO, Pt/rGO and Pt/C (JM), prove Pt 3ni 1/ amTiO 2the CO tolerance catalysts ability of/rGO significantly improves, owing to alloying action and the amTiO of Ni 2the existence of-OH key promotes the performance of difunctional mechanism.Figure 11 adopts current-vs-time method at H 2sO 4(0.5M)+CH 3the electrochemical stability of detecting catalyst electro-catalysis methanol oxidation in OH (0.5M) mixed solution, fixed potential is 0.6V, and the testing time is 3600s.As seen from the figure, Pt 3ni 1/ amTiO 2the current density value of/rGO is always higher than Pt 3ni 1/ rGO, Pt/rGO and Pt/C (JM), the current value of final 3600s is higher than high Pt content catalyst Pt/amTiO 2/ rGO, with CV multi-turn scans I fattenuation trend consistent (Figure 12), proves the Pt prepared by this patent 3ni 1/ amTiO 2/ rGO catalyst has more excellent electro-catalysis stability, and this may owing to the alloying action of Ni, amTiO 2the cooperative effect that may exist between the dispersed available protecting rGO on rGO surface and each point.
In Figure 13, Pt 3ni 1/ amTiO 2/ rGO is at O 2saturated H 2sO 4the hydrogen reduction peak current of the CV curve in solution, apparently higher than other catalyst, implies that this catalyst may have the oxygen reducing ability of raising.Figure 14 can be observed and Pt/amTiO 2/ rGO compares, Pt 3ni 1/ amTiO 2limiting current density (the 3.92mA/cm of/rGO 2) be significantly improved.Pt 3ni 1/ amTiO 2/ rGO take-off potential is 0.78V, with Pt/amTiO 2/ rGO and Pt/C (JM) compares and all shuffles, and proves that its ORR with raising is active.Figure 16 is Pt 3ni 1/ amTiO 2the K-L curve of/rGO under different potentials, wherein the K-L slope of curve under 0.3V current potential being substituted into and calculating ORR electron transfer number value in K-L equation is 4.2, shows Pt 3ni 1/ amTiO 2/ rGO is main with 4 electronic channel catalysis O in ORR course of reaction 2reduction, end product is water.
Meanwhile, we also studied Pt 3ni 1/ amTiO 2/ rGO, in electroxidation ethanol (EOR) and formic acid (FAOR) reaction, all shows higher catalytic oxidation active.Wherein, Pt 3ni 1/ amTiO 2the I of/rGO in EOR ffor 537mA/mg pt, be Pt 3ni 11.37 and 1.68 times of/rGO and Pt/C (JM), a little less than Pt/amTiO 2/ rGO; I in its FAOR fvalue is 738mA/mg pt, a little less than Pt/amTiO 2/ rGO is Pt 3ni 11.67 and 1.76 times of/rGO and Pt/C (JM).
The above is only the preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvement, and these improvement also should be considered as protection scope of the present invention.

Claims (2)

1. an alloy eelctro-catalyst, is characterized in that, chemical composition is described as Pt xni 1/ amTiO 2/ rGO:Pt accounts for 15.3 ~ 18.0wt.% of catalyst gross mass, and Ni accounts for 2.0 ~ 4.7wt.% of catalyst gross mass, and the 20wt.% of catalyst gross mass that Pt and Ni gross mass accounts for; AmTiO 2/ rGO compound accounts for catalyst gross mass 80wt.%, and amTiO 2account for amTiO 2the 20wt.% of/GO compound gross mass.
2. a preparation method for alloy eelctro-catalyst according to claim 1, its feature exists, and the technical parameter of processing step and control is as follows:
(1) adopt Hummers legal system for graphene oxide, i.e. the GO hydrosol, its concentration is 16.4mg/mL;
(2) sol-gel process improved is adopted to prepare amTiO 2/ GO, by ultrasonic 4h under 40mL absolute ethyl alcohol, 7.8mL deionized water, 360 μ L glacial acetic acid and 12.2mLGO hydrosol mixed liquor room temperature, makes mixed liquor be uniformly dispersed, is designated as A liquid;
Ultrasonic 0.5h under the mixed liquor room temperature of put 30mL absolute ethyl alcohol and 186 μ L isopropyl titanates, makes mixed liquor be uniformly dispersed, is designated as B liquid;
B liquid is dropwise instilled after in A liquid, continue to stir 1h, obtain TiO 2-GO colloidal sol; By TiO 2-GO colloidal sol is uncovered to be statically placed in 25 DEG C of water-baths, and solvent naturally volatilizees after 72h and obtains sepia solid, is ground to powder, collects for subsequent use, be designated as amTiO 2/ GO; Wherein amTiO 2at amTiO 2theoretical Mass mark in/GO is 20wt.%;
(3): adopt ethylene glycol immersion reduction method for preparing Pt xni 1/ amTiO 2/ rGO, x (1 ~ 3) are Pt:Ni atomic ratio, and PtNi total content is 20wt.% catalyst; By 2.07 ~ 2.45mL0.019MH 2ptCl 6the aqueous solution, 0.45 ~ 1.16mL0.034MNi (NO 3) 2the aqueous solution, 40mL ethylene glycol and 6.77 ~ 7.10mL deionized water join in there-necked flask, and ultrasonic mixing 0.5h, takes amTiO subsequently 2/ GO compound 40mg joins in there-necked flask, and ultrasonic process 1h, guarantees that compound is dispersed in Glycol Mixture; Subsequently by said mixture reductase 12 4h under 120 DEG C of condensing reflux magnetic agitation, for several times, the product obtained is vacuumize 24h at 40 DEG C, collects after being ground to powder, obtains serial eelctro-catalyst Pt for filtration washing xni 1/ amTiO 2/ rGO, wherein, theoretical Pt:Ni atomic ratio x is respectively 1,2,3, and precious metals pt Theoretical Mass mark is in the catalyst 15.3 ~ 18.0wt.%, Ni is 2.0 ~ 4.7wt.%, and the 20wt.% of catalyst gross mass that Pt and Ni gross mass accounts for.
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