CN107808964B - A method of using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry - Google Patents

A method of using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry Download PDF

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CN107808964B
CN107808964B CN201710990622.7A CN201710990622A CN107808964B CN 107808964 B CN107808964 B CN 107808964B CN 201710990622 A CN201710990622 A CN 201710990622A CN 107808964 B CN107808964 B CN 107808964B
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ptcofe
methanol
polygonal pattern
electrode
polygonal
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CN107808964A (en
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高道伟
吕一品
李书娜
陈国柱
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University of Jinan
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 present invention relates to a kind of polygonal pattern PtCoFe nanocatalysts and its methanol electrocatalysis characteristic to study.Using the polygonal pattern PtCoFe being prepared as catalyst; catalyst preparation is with chloroplatinic acid; cobalt chloride and ferric trichloride are raw material; using PVP as reducing agent and protective agent; the CTAB and NaBr of certain content is added; the higher polygonal pattern PtCoFe nanocatalyst of selectivity, the cleaning of preparation method green are prepared under hydrogen reducing atmosphere.The polygonal pattern PtCoFe alloy catalyst particle step atom obtained is more, and active site density is high, and methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3Cyclic voltammetry is carried out in OH electrolyte, is shown excellent electro catalytic activity in methanol electro-oxidizing-catalyzing experiment, is with a wide range of applications.

Description

It is a kind of using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry Method
Technical field
The present invention relates to electrochemical catalyst fields.Specifically, the present invention is using the polygonal pattern being prepared PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry.
Background technique
Precious metals pt nano-structured calalyst is widely used in industry due to its excellent catalytic performance and thermal stability Catalysis, bionic, the fields such as electro-catalysis.But due to some restraining factors in practical applications, such as easily poisoning, the service life it is short with And it is at high price, so that this excellent nanocatalyst can not further genralrlization and application.Research worker is in order to solve this A little problems substitute Pt frequently with by cheap 3d transition metal element part at present, form Pt base binary/multicomponent alloy and urge Agent, and controlled by condition, probe into its pattern, the relationship of composition and stable in catalytic performance.
In numerous transition metal elements, Co and Fe respectively as one of transition metal element more abundant on the earth, It is that Pt base bianry alloy preferably selects.The report for preparing PtCoFe alloy nano particle at present is less, and these methods are all Organic solvent macromolecular is as solvent, and most of PtCoFe alloy nano particle being synthesized is wrapped up by organic matter, active sites It cannot expose, can not be in contact with reactant.Therefore it designs and exploitation aqueous solution preparation PtCoFe alloy nano particle has weight The meaning wanted.A kind of method for preparing polygonal PtCoFe alloy nano particle that the present invention develops, substantially increases the step of Pt Atomicity increases the active site density of PtCoFe alloy.
Fuel cell is considered as the important power device of traditional internal combustion engine alternative in the near future.Proton exchange Another important feature of membrane cell is that it both can be using clean energy resource such as hydrogen etc. as fuel, also can be with reproducible small Molecular organic such as formic acid, ethyl alcohol, methanol etc. is fuel.According to before studies have shown that Pt catalyst is proton exchange membrane combustion Expect the best catalyst of catalytic performance in battery, but the high cost and utilization rate of Pt catalyst limits to a certain extent The application prospect of fuel cell, therefore prepare to be used to improve the catalyst for improving electrocatalysis characteristic and have become and be currently urgently badly in need of solving Certainly the problem of.
Summary of the invention
In view of the above technical problems, the present invention solves current Pt nano-structured calalyst and there is easily poisoning, and the service life is short, valence Lattice are high and the more low technical problem of catalyst activity of the prior art, prepare a kind of polygonal of high density active position Looks PtCoFe alloy nano catalyst improves the methanol electro-oxidizing performance of Pt nano-structured calalyst.
To achieve the above object, the present invention is achieved by the following technical solutions:
Methanol fuel cell electroxidation test method: anodic oxidation performance test uses conventional three-electrode system, It is carried out on CHI650D type electrochemical workstation, is a platinum filament to electrode using saturated calomel electrode as reference electrode, and worked Electrode is the glass-carbon electrode that diameter is 3mm, and a certain amount of polygonal pattern PtCoFe alloy nano catalyst suspension is taken to drip to glass carbon It is dry under infrared lamp on the surface of electrodes, then there is one end of sample to be separated by against UV ozone lamp working electrode drop 5mm irradiates 12h to remove the organic molecule of sample surfaces, and the 0.5wt% second of upper 1.5 μ L is then dripped on the surface of working electrode The diluted Nafion solution of alcohol, catalyst electrochemical activation area are tested with 0.5M H2SO4Solution is as electrolyte, before testing first The high-purity N of logical 30min2To electrolyte deoxygenation, cyclic voltammetry scan, the scanning range of setting are then carried out with 50mV/s rate It is -0.24~1.0V, it is N that superjacent is kept in experimentation2Atmosphere, methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3It is carried out in OH electrolyte, before cyclic voltammetry, leads to high-purity N2Purging 30min is used to remove the dissolved oxygen in electrolyte, The scanning range set determines that scanning speed is 50mV/s, current density is catalyzed with unit on working electrode as -0.2~1.0V Electric current on agent electrochemical activation area indicates that each working electrode is obtained with the circle of rate loop scan process 50 of 50mV/s Stable cyclic voltammetry curve, and a kind of experimental procedure of polygonal pattern PtCoFe alloy nano method for preparing catalyst is as follows:
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heating is reacted, after reaction by ethyl alcohol centrifuge washing, cold The processing steps such as dry are lyophilized, obtain polygonal PtCoFe alloy nano particle.
Preferably, the amount ranges of PVP K30 are 190-230mg, more preferably 210mg.
Preferably, the amount ranges of cetyl trimethylammonium bromide are 60mg.
Wherein: the dosage of NaBr and the dosage of cetyl trimethylammonium bromide are identical, the study found that Na+Ion and Br- The ratio of the ion guiding role marginal to PtCoFe crystal topology, only when the additional amount of CTAB and NaBr are equal In the case where for 60mg, polygonal PtCoFe alloy nano particle of the invention can be just obtained, unexpected technical effect is reached.
Preferably, the temperature range for heating reaction is 180-220 DEG C.
Further, it should be noted that the hydrogen atmosphere of 0.8MPa is also the polygonal PtCoFe of the synthesis present invention under primary condition The essential factor of alloy nano particle, since hydrogen has reproducibility, it is bis- that the present invention constitutes vapor phase hydrogen-liquid phase P VP Phase reduction system is used to synthesize PtCoFe alloy for the first time, constitutes a mutually matched entirety with other experiment parameters, collaboration exists Polygonal PtCoFe alloy of the invention can be just obtained together.
Beneficial effects of the present invention: methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3It is recycled in OH electrolyte Volt-ampere test, using the polygonal PtCoFe being prepared as catalyst, the polygonal PtCoFe alloy nano particle step atom of acquisition More, active site density is high, excellent electro catalytic activity is shown in methanol electro-oxidizing-catalyzing experiment, before having a wide range of applications Scape.And the present invention, with chloroplatinic acid, cobalt chloride and ferric trichloride are raw material, using PVP as reducing agent and protective agent, using specific The higher polygonal pattern PtCoFe alloy nanoparticle of selectivity is prepared in CTAB and NaBr additional amount under hydrogen reducing atmosphere Son, the cleaning of method green.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared；
Fig. 2 is the TEM map for the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared；
Fig. 3 is the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared and business Pt/C as methanol electro-oxidizing The cyclic voltammetry curve comparison diagram of catalyst；
Fig. 4 is the TEM map for the PtCoFe alloy nano particle that comparative example 1 is prepared；
Fig. 5 is the TEM map for the PtCoFe alloy nano particle that comparative example 2 is prepared.
Specific embodiment
Below by way of the implementation and possessed beneficial effect of specific embodiment the present invention will be described in detail technical solution, but not It can regard as any restriction to enforceable range of the invention.
Embodiment 1
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heats and is reacted at 200 DEG C, after reaction by ethyl alcohol from The processing steps such as heart washing, freeze-drying, obtain polygonal PtCoFe alloy nano particle (as shown in Figure 2), wherein polyethylene pyrrole The amount ranges of pyrrolidone K30 are 210mg, and the amount ranges of cetyl trimethylammonium bromide are 60mg, the dosage of NaBr with The dosage of cetyl trimethylammonium bromide is identical.
The test of methanol fuel cell electroxidation: anodic oxidation performance test uses conventional three-electrode system, It is carried out on CHI650D type electrochemical workstation.It is a platinum filament to electrode with saturated calomel electrode (SCE) for reference electrode, and Working electrode is the glass-carbon electrode (GC) that diameter is 3mm.A certain amount of catalyst suspension (holding metal quality is 4 μ g) is taken to drip to It is dry under infrared lamp on the surface of GC electrode, then there is one end of sample against the (transmitting of UV ozone lamp working electrode drop Wavelength is 185nm and 254nm, power 10W) it is separated by organic molecule (such as PVP) of the 5mm irradiation 12h to remove sample surfaces. Then the 0.5wt%Nafion solution (ethyl alcohol dilution) of upper 1.5 μ L is dripped on the surface of working electrode.Catalyst electrochemical activation face Product test is with 0.5M H2SO4Solution first leads to the high-purity N of 30min as electrolyte before experiment2To electrolyte deoxygenation, then with 50mV/s rate carries out cyclic voltammetric (CV) scanning, and the scanning range of setting is -0.24~1.0V.Solution is kept in experimentation Top is N2Atmosphere.Methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3It is carried out in OH electrolyte, before CV test, leads to height Pure N2Purging 30min is used to remove the dissolved oxygen in electrolyte, and the scanning range set determines scanning speed as -0.2~1.0V For 50mV/s.Current density is with unit catalyst electrochemical activation area (cm on working electrode2) on electric current indicate.Each work Make electrode and obtained stable CV curve is enclosed with the rate loop scan process 50 of 50mV/s.It prepared by embodiment 1 polygonal PtCoFe nanoparticle, its current density that peak is normalized on electrochemical surface area ECSA of just sweeping represent the sheet of catalyst Active size is levied, from figure 3, it can be seen that highest current density of the polygonal PtCoFe nanoparticle in methanol electro-oxidizing is 3.52mA cm-2, the methanol highest current density much higher than commercial Pt/C is 0.47mA cm-2。
Comparative example 1
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heats and is reacted at 200 DEG C, after reaction by ethyl alcohol from The processing steps such as heart washing, freeze-drying, wherein the amount ranges of PVP K30 are 210mg, cetyl three The amount ranges of methyl bromide ammonium are 60mg, and the dosage of NaBr is 70mg, obtain PtCoFe alloy nano particle (such as Fig. 4 institute Show), and test condition same as Example 1 is used, obtaining its highest current density in methanol electro-oxidizing is 1.86mA cm-2。
Comparative example 2
Measure 1.0mL chloroplatinic acid (19.3mmol/L) and, 4.0mL concentration for 1.66mmol/L cobalt chloride and 3.0mL it is dense Degree is the ferric chloride aqueous solutions of 1.66mmol/L in 30ml reaction kettle, is subsequently added into PVP K30 and 16 Alkyl trimethyl ammonium bromide CTAB and NaBr are stirred dissolution with magnetic stirring apparatus, are then passed through into reaction kettle Then 0.8MPa air is heated at 200 DEG C and is reacted, after reaction by ethyl alcohol centrifuge washing, freeze-drying etc. Manage step, wherein the amount ranges of PVP K30 are 210mg, the amount ranges of cetyl trimethylammonium bromide Dosage for 60mg, NaBr is 70mg, is obtained PtCoFe alloy nano particle (as shown in Figure 5), and using same as Example 1 Test condition, obtain its highest current density in methanol electro-oxidizing be 1.41mA cm-2。
Moreover, it relates to arrive multiple groups comparative example, it will not enumerate in view of length, be respectively relative to embodiment 1 Change one or more parametric variables, cannot get this hair in the case where changing one or more variable as the result is shown Bright polygonal pattern PtCoFe alloy nano particle, showing has collaboration between each technical characteristic of the technical solution of the application Effect, and methanol electro-oxidizing-catalyzing activity is respectively less than 2.0mA cm-2, far below the catalytic activity of the embodiment of the present invention 1, show this No matter the technical solution of application has reached unexpected technical effect for alloy pattern or catalytic activity.

Claims (3)

1. a kind of method using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry, specific steps are as follows:
Methanol electrochemical test method: anodic oxidation performance test is using conventional three-electrode system, in CHI650D type electrification It learns and is carried out on work station, be a platinum filament to electrode using saturated calomel electrode as reference electrode, and working electrode is that diameter is The glass-carbon electrode of 3mm takes a certain amount of polygonal pattern PtCoFe alloy nano catalyst suspension to drip on the surface of glass-carbon electrode It is dry under infrared lamp, then there is one end of sample to be separated by 5mm irradiation 12h against UV ozone lamp to remove working electrode drop The organic molecule of sample surfaces, the diluted Nafion of 0.5wt% ethyl alcohol for then dripping upper 1.5 μ L on the surface of working electrode are molten Liquid, catalyst electrochemical activation area are tested with 0.5M H2SO4Solution first leads to the high-purity N of 30min as electrolyte before experiment2 To electrolyte deoxygenation, cyclic voltammetry scan is then carried out with 50mV/s rate, the scanning range of setting is -0.24~1.0V, real It is N that superjacent is kept during testing2Atmosphere, methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3In OH electrolyte into It goes, before cyclic voltammetry, leads to high-purity N2Purging 30min is used to remove the dissolved oxygen in electrolyte, the scanning range of setting For -0.2~1.0V, determine that scanning speed is 50mV/s, current density is with unit catalyst electrochemical activation face on working electrode Electric current in product indicates that each working electrode encloses obtained stable cyclic voltammetric with the rate loop scan process 50 of 50mV/s Curve, it is characterised in that: the preparation method of the polygonal pattern PtCoFe alloy nano catalyst includes: to measure 1.0mL concentration For the chloroplatinic acid aqueous solution of 19.3mmol/L, the cobalt chloride and 3.0mL concentration that 4.0mL concentration is 1.66mmol/L are The ferric chloride aqueous solutions of 1.66mmol/L in 30ml reaction kettle, be subsequently added into 190-230mg PVP K30 and 60mg cetyl trimethylammonium bromide CTAB and 60mg NaBr, is stirred dissolution with magnetic stirring apparatus, then uses hydrogen It is discharged in reaction kettle after air, 0.8MPa hydrogen is passed through into reaction kettle, then heating is reacted, and passes through second after reaction Alcohol centrifuge washing, freeze-drying process step obtain polygonal PtCoFe alloy nanoparticle.
2. the side according to claim 1 using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry Method, it is characterised in that: the dosage of PVP K30 is 210mg.
3. according to claim 1 or 2 using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry Method, it is characterised in that: the temperature range that heating is reacted is 180-220 DEG C.
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