CN107808964A - A kind of method using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry - Google Patents

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

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CN107808964A
CN107808964A CN201710990622.7A CN201710990622A CN107808964A CN 107808964 A CN107808964 A CN 107808964A CN 201710990622 A CN201710990622 A CN 201710990622A CN 107808964 A CN107808964 A CN 107808964A
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ptcofe
methanol
polygonal pattern
nanocatalysts
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CN107808964B (en
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高道伟
吕品
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; add the CTAB and NaBr of certain content; the higher polygonal pattern PtCoFe nanocatalysts of selectivity, preparation method green cleaning are prepared under hydrogen reducing atmosphere.The polygonal pattern PtCoFe alloy catalysts 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, excellent electro catalytic activity is shown in methanol electro-oxidizing-catalyzing experiment, is with a wide range of applications.

Description

It is a kind of using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry Method
Technical field
The present invention relates to electrochemical catalyst field.Specifically, the present invention is using the polygonal pattern being prepared PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry.
Background technology
Precious metals pt nano-structured calalyst is widely used in work due to its excellent catalytic performance and heat endurance Industry is catalyzed, bionic, the field such as electro-catalysis.But due to some restraining factors in actual applications, such as easily poisoning, life-span Short and price is high so that this excellent nanocatalyst can not further genralrlization and application.Research worker is understanding Certainly these problems, substitute Pt, formation Pt bases binary/polynary frequently with by cheap 3d transition metals part at present Alloy catalyst, and controlled by condition, probe into its pattern, composition and the relation of stable in catalytic performance.
In numerous transition metals, Co and Fe respectively as on the earth compared with one of transition metal of horn of plenty, It is that Pt base bianry alloys preferably select.It is less that the report of PtCoFe alloy nano particles is prepared at present, and these methods are all Organic solvent macromolecular is wrapped up as most of solvent, the PtCoFe alloy nano particles being synthesized by organic matter, active sites It can not expose, can not be in contact with reactant.Therefore design and the exploitation aqueous solution prepares PtCoFe alloy nano particles and has weight The meaning wanted.A kind of method for preparing polygonal PtCoFe alloy nano particles that the present invention develops, substantially increase Pt step Atomicity, add the active site density of PtCoFe alloys.
Fuel cell is considered as the important power set of traditional internal combustion engine alternative in the near future.Proton is handed over Change another important feature of membrane cell and be that it both can be using clean energy resource such as hydrogen etc. as fuel, also can be with renewable Small organic molecule such as formic acid, ethanol, methanol etc. be fuel.Shown according to research before, Pt catalyst is proton exchange The best catalyst of catalytic performance in membrane cell, but the high cost of Pt catalyst and utilization rate are to a certain extent The application prospect of fuel cell is limited, therefore prepares the catalyst that electrocatalysis characteristic is improved for improving as current urgent Cut urgent problem.
The content of the invention
For above-mentioned technical problem, the present invention solves current Pt nano-structured calalysts and is poisoned in the presence of easy, short life, Price is high and the more low technical problem of the catalyst activity of prior art, prepares a kind of the more of high density active position Angular looks PtCoFe alloy nano catalyst, improve the methanol electro-oxidizing performance of Pt nano-structured calalysts.
To achieve the above object, the present invention is achieved by the following technical solutions：
Methanol fuel cell electroxidation method of testing：Anodic oxidation performance test uses conventional three-electrode system, Carried out on CHI650D type electrochemical workstations, be a platinum filament to electrode using saturated calomel electrode as reference electrode, and worked Electrode is a diameter of 3mm glass-carbon electrode, takes a certain amount of polygonal pattern PtCoFe alloy nano catalyst suspensions to drip to glass carbon Dried on the surface of electrodes under infrared lamp, working electrode drop is then had into one end of sample against UV ozone lamp phase 12h is irradiated to remove the organic molecule of sample surfaces every 5mm, then the 1.5 μ L in the drop of the surface of working electrode The Nafion solution of 0.5wt% ethanol dilution, catalyst electrochemical activation area are tested with 0.5M H2SO4Solution is as electrolysis Matter, 30min high-purity N is first led to before experiment2To electrolyte deoxygenation, cyclic voltammetry scan, setting are then carried out with 50mV/s speed Scanning range be -0.24~1.0V, it is N that superjacent is kept in experimentation2Atmosphere, methanol electro-oxidizing test be 0.5M H2SO4+2M CH3Carried out in OH electrolyte, before cyclic voltammetry, lead to high-purity N2Purging 30min is used for removing electricity The dissolved oxygen in matter is solved, the scanning range set is -0.2~1.0V, and it is 50mV/s to determine sweep speed, and current density is with work Make the electric current on electrode on unit catalyst electrochemical activation area and represent that each working electrode is with 50mV/s rate loop The cyclic voltammetry curve for the stabilization that the circle of scan process 50 obtains, and a kind of polygonal pattern PtCoFe alloy nano catalyst preparations The experimental procedure of method is as follows：
1.0mL chloroplatinic acids (19.3mmol/L) are measured, 4.0mL concentration is 1.66mmol/L cobalt chloride and 3.0mL concentration For 1.66mmol/L ferric chloride aqueous solutionses in 30ml reactors, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, dissolving is stirred with magnetic stirring apparatus, then with empty in hydrogen discharge reactor After gas, 0.8MPa hydrogen is passed through into reactor, then heating is reacted, reaction terminate after by ethanol centrifuge washing, cold The processing step such as dry is freezed, obtains polygonal PtCoFe alloy nano particles.
Preferably, the amount ranges of PVP K30 are 190-230mg, more preferably 210mg.
Preferably, the amount ranges of cetyl trimethylammonium bromide are 60mg.
Wherein：NaBr dosage is identical with the dosage of cetyl trimethylammonium bromide, and research is found, Na+Ion and Br- The guide effect marginal to PtCoFe crystal topologies of the ratio of ion, the only addition as CTAB and NaBr In the case of being 60mg, the polygonal PtCoFe alloy nano particles of the present invention can be just obtained, reach unexpected technology effect Fruit.
Preferably, the temperature range of heating response is 180-220 DEG C.
Further, it should be noted that 0.8MPa hydrogen atmosphere is also the polygonal PtCoFe of the synthesis present invention under primary condition The essential factor of alloy nano particle, because hydrogen has reproducibility, it is double that the present invention forms vapor phase hydrogen-liquid phase P VP Phase reduction system, it is used for synthesizing PtCoFe alloys first, the entirety of a mutual cooperation, collaboration is formed with other experiment parameters The polygonal PtCoFe alloys of the present invention can be just obtained together.
Beneficial effects of the present invention：Methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3Followed in OH electrolyte Ring volt-ampere is tested, and using the polygonal PtCoFe being prepared as catalyst, the polygonal PtCoFe alloy nano particles step of acquisition is former Son is more, and active site density is high, shows excellent electro catalytic activity in methanol electro-oxidizing-catalyzing experiment, widely should have Use prospect.And the present invention, with chloroplatinic acid, cobalt chloride and ferric trichloride are raw material, using PVP as reducing agent and protective agent, using spy Fixed CTAB and NaBr additions, the higher polygonal pattern PtCoFe alloys of selectivity are prepared under hydrogen reducing atmosphere Nano-particle, method green cleaning.
Brief description of the drawings
Fig. 1 is the XRD spectrum for the polygonal PtCoFe alloy nano particles that embodiment 1 is prepared；
Fig. 2 is the TEM collection of illustrative plates for the polygonal PtCoFe alloy nano particles that embodiment 1 is prepared；
Fig. 3 is the polygonal PtCoFe alloy nano particles 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 collection of illustrative plates for the PtCoFe alloy nano particles that comparative example 1 is prepared；
Fig. 5 is the TEM collection of illustrative plates for the PtCoFe alloy nano particles that comparative example 2 is prepared.
Embodiment
The implementation of technical solution of the present invention and possessed beneficial effect are described in detail below by way of specific embodiment, but It cannot be assumed that for the present invention can practical range any restriction.
Embodiment 1
1.0mL chloroplatinic acids (19.3mmol/L) are measured, 4.0mL concentration is 1.66mmol/L cobalt chloride and 3.0mL concentration For 1.66mmol/L ferric chloride aqueous solutionses in 30ml reactors, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, dissolving is stirred with magnetic stirring apparatus, then with empty in hydrogen discharge reactor After gas, 0.8MPa hydrogen is passed through into reactor, then heats and is reacted at 200 DEG C, reaction terminate after by ethanol from The processing steps such as heart washing, freeze-drying, obtain polygonal PtCoFe alloy nano particles (as shown in Figure 2), wherein, polyethylene Pyrrolidones K30 amount ranges are 210mg, and the amount ranges of cetyl trimethylammonium bromide are 60mg, NaBr dosage It is identical with the dosage of cetyl trimethylammonium bromide.
Methanol fuel cell electroxidation is tested：Anodic oxidation performance test uses conventional three-electrode system, Carried out on CHI650D type electrochemical workstations.It is a platinum filament to electrode with saturated calomel electrode (SCE) for reference electrode, And working electrode is a diameter of 3mm glass-carbon electrode (GC).Take a certain amount of catalyst suspension (holding metal quality is 4 μ g) Drip on the surface of GC electrodes and to be dried under infrared lamp, working electrode drop is then had to one end of sample against UV ozone lamp (launch wavelength is 185nm and 254nm, power 10W) is separated by 5mm and irradiates 12h to remove the organic molecule of sample surfaces (such as PVP).Then 1.5 μ L 0.5wt%Nafion solution (ethanol dilution) is dripped on the surface of working electrode.Catalyst electricity Chemical activation area is tested with 0.5M H2SO4Solution is as electrolyte, first logical 30min high-purity N before experiment2Electrolyte is removed Oxygen, cyclic voltammetric (CV) scanning is then carried out with 50mV/s speed, the scanning range of setting is -0.24~1.0V.Experimentation Middle holding superjacent is N2Atmosphere.Methanol electro-oxidizing test is in 0.5M H2SO4+2M CH3Carried out in OH electrolyte, CV is surveyed Before examination, lead to high-purity N2Purging 30min is used for removing dissolved oxygen in electrolyte, the scanning range set as -0.2~1.0V, It is 50mV/s to determine sweep speed.Current density is with unit catalyst electrochemical activation area (cm on working electrode2) on electricity Flow table is shown.Each working electrode encloses the CV curves of obtained stabilization with 50mV/s rate loop scan process 50.For reality Apply example 1 and prepare polygonal PtCoFe nano-particles, its current density generation just swept peak and be normalized on electrochemical surface area ECSA The table size of the latent active of catalyst, from figure 3, it can be seen that polygonal PtCoFe nano-particles are in methanol electro-oxidizing Highest current density is 3.52mA cm-2, the methanol highest current density far above commercial Pt/C is 0.47mA cm-2。
Comparative example 1
1.0mL chloroplatinic acids (19.3mmol/L) are measured, 4.0mL concentration is 1.66mmol/L cobalt chloride and 3.0mL concentration For 1.66mmol/L ferric chloride aqueous solutionses in 30ml reactors, be subsequently added into PVP K30 and hexadecane Base trimethylammonium bromide CTAB and NaBr, dissolving is stirred with magnetic stirring apparatus, then with empty in hydrogen discharge reactor After gas, 0.8MPa hydrogen is passed through into reactor, then heats and is reacted at 200 DEG C, reaction terminate after by ethanol 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 NaBr dosage is 70mg, obtain PtCoFe alloy nano particles (such as Fig. 5 institutes 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 acids (19.3mmol/L) and, 4.0mL concentration be 1.66mmol/L cobalt chloride and 3.0mL it is dense The ferric chloride aqueous solutionses for 1.66mmol/L are spent in 30ml reactors, are subsequently added into PVP K30 and 16 Alkyl trimethyl ammonium bromide CTAB and NaBr, dissolving is stirred with magnetic stirring apparatus, is then passed through into reactor 0.8MPa air, then heat and reacted at 200 DEG C, react after terminating by ethanol centrifuge washing, freeze-drying etc. Step is managed, wherein, the amount ranges of PVP K30 are 210mg, the dosage model of cetyl trimethylammonium bromide Enclose for 60mg, NaBr dosage is 70mg, obtains PtCoFe alloy nano particles (as shown in Figure 5), and using and embodiment 1 Identical test condition, it is 1.41mA cm to obtain its highest current density in methanol electro-oxidizing-2。
Moreover, it relates to arrive multigroup comparative example, in view of length will not enumerate, embodiment 1 is respectively relative to Change one or more parametric variables, be as a result shown in the case of changing one or more variable and cannot get this The polygonal pattern PtCoFe alloy nano particles of invention, showing between each technical characteristic of technical scheme of the application has Synergy, 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 no matter the technical scheme of the application has reached unexpected technology effect for alloy pattern or catalytic activity Fruit.

Claims (5)

1. a kind of method using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry, concretely comprise the following steps：
Methanol electrochemical test method：Anodic oxidation performance test is using conventional three-electrode system, in CHI650D types electrification Learn and carried out on work station, be a platinum filament to electrode using saturated calomel electrode as reference electrode, and working electrode is a diameter of 3mm glass-carbon electrode, a certain amount of polygonal pattern PtCoFe alloy nano catalyst suspensions are taken to drip on the surface of glass-carbon electrode Dried under infrared lamp, one end that working electrode drop is then had to sample is separated by 5mm irradiation 12h to remove against UV ozone lamp The organic molecule of sample surfaces, then the Nafion of 1.5 μ L 0.5wt% ethanol dilution is molten in the drop of the surface of working electrode Liquid, catalyst electrochemical activation area are tested with 0.5M H2SO4Solution is as electrolyte, first logical 30min high-purity N before experiment2 To electrolyte deoxygenation, cyclic voltammetry scan is then carried out with 50mV/s speed, 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 CH3Enter in OH electrolyte OK, before cyclic voltammetry, high-purity N is led to2Purging 30min is used for removing the dissolved oxygen in electrolyte, the scanning range of setting For -0.2~1.0V, it is 50mV/s to determine sweep speed, and current density is with unit catalyst electrochemical activation face on working electrode Electric current in product represents that each working electrode encloses the cyclic voltammetric of obtained stabilization with 50mV/s rate loop scan process 50 Curve, it is characterised in that：The preparation method of the porous PtCoFe alloy nanos catalyst includes：Measuring 1.0mL concentration is 19.3mmol/L chloroplatinic acid aqueous solution, the cobalt chloride and 3.0mL concentration that 4.0mL concentration is 1.66mmol/L are 1.66mmol/L Ferric chloride aqueous solutionses in 30ml reactors, be subsequently added into PVP K30 and cetyl trimethyl bromination Ammonium CTAB and NaBr, dissolving is stirred with magnetic stirring apparatus, is then discharged with hydrogen in reactor after air, to reactor In be passed through 0.8MPa hydrogen, then heating reacted, reaction terminate after by the processing such as ethanol centrifuge washing, freeze-drying step Suddenly, polygonal PtCoFe alloy nano particles are obtained.
A kind of 2. side using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry described in claim 1 Method, it is characterised in that：The amount ranges of PVP K30 are 190-230mg, preferably 210mg.
3. one kind described in claim 1-2 is used to use polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry Method, it is characterised in that：The amount ranges of cetyl trimethylammonium bromide are 50-70mg, preferably 60mg.
A kind of 4. side using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry described in claim 1-3 Method, it is characterised in that：NaBr dosage is identical with the dosage of cetyl trimethylammonium bromide.
A kind of 5. side using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry described in claim 1-4 Method, it is characterised in that：The temperature range of heating response is 180-220 DEG C.
CN201710990622.7A 2017-10-23 2017-10-23 A method of using polygonal pattern PtCoFe nanocatalyst catalysis oxidation methanol electrochemistry Expired - Fee Related CN107808964B (en)

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CN110048133A (en) * 2019-04-29 2019-07-23 济南大学 A kind of preparation method of cross cube Pt-Cu-Mn alloy nanoparticle

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CN110048133A (en) * 2019-04-29 2019-07-23 济南大学 A kind of preparation method of cross cube Pt-Cu-Mn alloy nanoparticle

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