CN109994743A - 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

Info

Publication number
CN109994743A
CN109994743A CN201811504313.5A CN201811504313A CN109994743A CN 109994743 A CN109994743 A CN 109994743A CN 201811504313 A CN201811504313 A CN 201811504313A CN 109994743 A CN109994743 A CN 109994743A
Authority
CN
China
Prior art keywords
fuel cell
preparation
nano
cell anode
wire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811504313.5A
Other languages
Chinese (zh)
Other versions
CN109994743B (en
Inventor
张桥
袁小磊
张勇
曹暮寒
姜晓静
徐勇
吕奉磊
陈佳念
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201811504313.5A priority Critical patent/CN109994743B/en
Publication of CN109994743A publication Critical patent/CN109994743A/en
Application granted granted Critical
Publication of CN109994743B publication Critical patent/CN109994743B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof, the presoma palladium salt of default molar ratio and presoma bismuth salt are dissolved in the first polyol solvent by this method, obtain precursor solution；A certain amount of surfactant is dissolved in the second polyol solvent, reaction dissolvent is obtained；Then precursor solution is added into reaction dissolvent; obtain reaction solution; the reaction solution is heated under inert gas protection to 90~150 DEG C; after reacting 10~60min; clean the reaction solution; Pd base nano-wire first product is obtained, and electrochemical activation processing is carried out to the Pd base nano-wire first product under alkaline environment, obtains Pd-Bi (OH)3Nano-wire catalyst.Preparation process of the invention is simple, requires bismuth hydroxide (Bi (OH) that is low and preparing to production equipment3) the Pd nano-wire catalyst of modification has excellent oxidation of ethanol catalytic reaction activity and stability.

Description

A kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof
Technical field
The present invention relates to field of fuel cell technology more particularly to a kind of Direct Ethanol Fuel Cell anode catalyst and its Preparation method.
Background technique
Direct Ethanol Fuel Cell (DEFCs) is as a kind of very promising energy conversion equipment, efficiently with it Efficient energy conversion and potential application on portable mobile apparatus and be concerned.The course of work of DEFCs is mainly By yin-yang electrode catalyst come the conversion of catalysis ethanol fuel, however, due to its anode catalyst (such as Pd nanocatalyst) It is easy to be poisoned by intermediate, there is a problem of that oxidation of ethanol catalytic reaction activity is low, stability is poor, lead to existing DEFCs also It is not able to satisfy commercialized requirement.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of Direct Ethanol Fuel Cell anode catalyst and its Preparation method, the preparation method have simple process, require bismuth hydroxide (Bi (OH) that is low and preparing to production equipment3) repair The Pd nano-wire catalyst of decorations has excellent oxidation of ethanol catalytic reaction activity and stability.
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of Direct Ethanol Fuel Cell anode and urges The preparation method of agent, this method comprises:
Presoma palladium salt and presoma bismuth salt are dissolved in the first polyol solvent according to default molar ratio, obtain presoma Solution；
A certain amount of surfactant is dissolved in the second polyol solvent, reaction dissolvent is obtained；
The precursor solution is added into the reaction dissolvent, reaction solution is obtained；Under inert gas protection plus The heat reaction solution after reacting 10~60min, cleans the reaction solution, at the beginning of obtaining Pd base nano-wire to 90~150 DEG C Product；
Electrochemical activation processing is carried out to the Pd base nano-wire first product, obtains Pd-Bi (OH)3Nano-wire catalyst.
In reaction system of the invention, under the high temperature conditions, the alcohol OH in polyalcohol-Reproducibility is shown, since Pd has There is higher reduction potential, can preferentially be restored.However, reduction potential is lower for Bi, alcohol OH in addition-Compared with Weak reducing power, thus cause Bi can only be with oxide (bismuth oxide, Bi2O3) form be attached to the surface Pd.In subsequent electricity In chemical activation processing, bismuth oxide Bi2O3In alkaline environment, in insoluble Bi can be converted within the scope of certain voltage (OH)3, so as to obtain surface modification Bi (OH)3Pd-Bi (OH)3Nano-wire catalyst.
Further, in the precursor solution, the concentration of palladium ion is 0.005~0.05mol/L, the concentration of bismuth ion For 0.005~0.05mol/L.
Further, in the presoma palladium salt in palladium ion and presoma bismuth salt the molar ratio of bismuth ion be 1:(0.5~ 3)。
Further, the presoma palladium salt is the group of one or more of palladium acetylacetonate, chlorine palladium acid, palladium acetate It closes；The presoma bismuth salt is the combination of one or more of five water bismuth nitrates, new lauric acid/dodecanoic acid bismuth and acetylacetone,2,4-pentanedione bismuth.
Further, first polyol solvent and the second polyol solvent are ethylene glycol, diethylene glycol, the third three The combination of one or more of alcohol, pentaerythrite.
Further, the surfactant is polyvinylpyrrolidone, and the molecular weight of the polyvinylpyrrolidone is big In being equal to 40000g/mol, the concentration of polyvinylpyrrolidone is more than or equal to 0.0063mol/L in the reaction dissolvent.
Further, described that a certain amount of surfactant is dissolved in the second polyol solvent, obtain reaction dissolvent packet It includes:
Polyvinylpyrrolidone is mixed, and under vacuum conditions with second polyol solvent, controls revolving speed It is 20~60 DEG C for 300~1000r/min, temperature, stirs 10~30min, obtain the reaction dissolvent.
Further, the heating reaction solution includes: to 90~150 DEG C
It is 0.5~10 DEG C/min according to heating rate, heats the reaction solution to 90~150 DEG C.
Further, the electrochemical activation processing includes: that electrochemical cyclic voltammetry activation or chronoamperometry are living Change, electrolyte is 0.1~2mol/L NaOH or KOH solution, and potential range is -1.0~0.2V, and sweeping speed is 10~200mV/ s。
The second aspect of the present invention provides a kind of direct fuel alcohol fuel cell anode catalyst, which is to adopt The Pd-Bi (OH) being prepared with the preparation method of any one of the above Direct Ethanol Fuel Cell anode catalyst3Nano wire Catalyst, the Pd-Bi (OH)3Nano-wire catalyst has chain structure, the Pd-Bi (OH)3The surface of nano-wire catalyst There is Bi (OH)3Modification.
A kind of Direct Ethanol Fuel Cell anode catalyst of the invention and preparation method thereof, has the following beneficial effects:
Compared with prior art, the Pd-Bi of one-dimensional catenary structure is prepared using easy polyol process by the present invention (OH)3Nano-wire catalyst, the catalyst have bigger active surface area, after electrochemical activation is handled, activation Pd nanowire surface has more defects, so that the oxidation of ethanol catalytic reaction activity of the catalyst is higher.
In addition, by electrochemical activation treated catalyst, the Bi of Pd nanowire surface2O3It is converted into Bi (OH)3, And Bi (OH)3More readily facilitate the OH that water decomposition generates ADSORPTION STATE-, so as to the CO being effectively facilitated around Pd active site Quick oxidation removal so that preparation Pd-Bi (OH)3There is nano-wire catalyst excellent catalysis ethanol oxidation reaction to stablize Property.
In addition, the Bi (OH) of the method for the present invention modification3The Pd that is present in that also can be stable in long-term catalytic process receives Nanowire surface, therefore there is excellent structural stability, it is suitable for industrialized scale, economic value with higher.
Detailed description of the invention
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical solution of the present invention The attached drawing used is briefly described.It should be evident that drawings in the following description are only some embodiments of the invention, it is right For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings Its attached drawing.
Fig. 1 is the process signal of the preparation method of Direct Ethanol Fuel Cell anode catalyst provided in an embodiment of the present invention Figure；
Fig. 2 a and 2b are 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The transmission electron microscope of nano-wire catalyst Figure；
Fig. 3 is 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The transmission electron microscope diffraction pattern of nano-wire catalyst；
Fig. 4 is 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The X-ray diffractogram of nano-wire catalyst；
Fig. 5 is 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The x-ray photoelectron spectroscopy figure of nano-wire catalyst；
Fig. 6 is 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The second of nano-wire catalyst and business Pd/C catalyst Alcohol oxidation reaction catalytic activity cyclic voltammetry curve；
Fig. 7 is 1 resulting Pd-Bi (OH) of the embodiment of the present invention3The oxidation of ethanol catalytic reaction activity of nano-wire catalyst Chronoa mperometric plot；
Fig. 8 is that the oxidation of ethanol catalytic reaction activity chrono-amperometric of business Pd/C catalyst provided in an embodiment of the present invention is bent Line.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art without making creative work it is obtained it is all its His embodiment, shall fall within the protection scope of the present invention.
It is reacted to improve Pd nanocatalyst as oxidation of ethanol existing for Direct Ethanol Fuel Cell anode catalyst (EOR) problem that catalytic activity is low, stability is poor usually simply uses the surface area for increasing Pd nano particle in the prior art Mode improve the catalytic activity of catalyst, although this mode is capable of a degree of catalytic activity for improving catalyst, But since biggish surface area is easier CO absorption, thus more easily CO is poisoned and loses activity, i.e., stability is poor.This Outside, in the prior art there is also by Pd and Au, the metal phases such as Sn, Cu are combined to form bimetallic PdM nanometer alloy catalyst, this Method attempts to weaken CO absorption, but final effect is little by adjusting Pd band center；Another method be by Pd oxide or The compound characteristic to improve catalyst of person's hydroxide, although this method can be effectively improved CO poisoning, catalyst itself It is very unstable in catalytic process since it is compound.
In consideration of it, the embodiment of the present invention provides a kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof, with The prior art is compared, and the Pd-Bi (OH) of one-dimensional chain structure is prepared using easy polyol process by the present invention3Nano wire Catalyst, the catalyst have bigger active surface area, after electrochemical activation is handled, the Pd nanowire surface of activation With more defects, so that the oxidation of ethanol catalytic reaction activity of the catalyst is higher.
In addition, by electrochemical activation treated catalyst, the Bi of Pd nanowire surface2O3It is converted into Bi (OH)3, And Bi (OH)3More readily facilitate the OH that water decomposition generates ADSORPTION STATE-, so as to the CO being effectively facilitated around Pd active site Quick oxidation removal so that preparation Pd-Bi (OH)3There is nano-wire catalyst excellent catalysis ethanol oxidation reaction to stablize Property.
In addition, the Bi (OH) of the method for the present invention modification3The Pd that is present in that also can be stable in long-term catalytic process receives Nanowire surface, therefore there is excellent structural stability, it is suitable for industrialized scale, economic value with higher.
Illustrate Direct Ethanol Fuel Cell anode catalyst and its preparation of the invention using specific embodiment below Method.
Embodiment 1
A kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, as shown in Figure 1, this method specifically include it is following Step:
(1) molar ratio is dissolved in 5ml diethylene glycol solvent and is mixed for the palladium acetylacetonate of 1:1 and five water bismuth nitrates Afterwards, ultrasonic 30min, obtains precursor solution.
Wherein, in precursor solution, the concentration of palladium ion and bismuth ion is 0.013mol/L.
(2) by 1.65g (excessive 1%) polyvinylpyrrolidone and 40ml diethylene glycol solvent, by polyvinylpyrrolidone: Diethylene glycol solvent be 0.01mol:1L ratio mixed, then under vacuum conditions, control revolving speed be 1000r/min, Temperature is 50 DEG C, and stirring 10~30min dissolution obtains reaction dissolvent.
Wherein, the molecular weight of polyvinylpyrrolidone is 40000g/mol.
(3) precursor solution that above-mentioned steps (1) obtain is rapidly joined into step (2) resulting reaction dissolvent, is obtained To reaction solution.Under n 2 atmosphere, it is 10 DEG C/min according to heating rate, the temperature of reaction solution is increased to 100 DEG C, and 15min is reacted at this temperature, and then cooled reaction solution to room temperature cleans reaction solution and obtains black solid powder, the black Solid powder is Pd base nano-wire first product.
(4) the resulting black solid powder of step (3) is prepared into catalyst prepared Chinese ink, is then added drop-wise to glassy carbon electrode table Face naturally dry, is activated using electrochemical cyclic voltammetry, electrolyte be 1mol/L NaOH solution, potential range be -1V~ 0.2V (relative to saturated calomel electrode, SCE), sweeping speed is 50mV/S, and Pd-Bi (OH) can be obtained after electrochemical activation processing3 Nano-wire catalyst.
Pd-Bi (OH) obtained above3Nano-wire catalyst is observed by transmission electron microscope (TEM), is such as schemed Shown in 2a, resulting Pd-Bi (OH)3Nano wire is the nano wire of the one-dimensional catenary structure of morphological rules, further such as Fig. 2 b Shown, the nano wire of the one-dimensional catenary structure has apparent lattice fringe, and spacing of lattice 0.22nm corresponds to pure Pd's (111) face.Meanwhile the diffraction pattern (SEAD) with transmission electron microscope as shown in Figure 3 observes chain Pd-Bi (OH)3It receives Rice noodles, it can be found that it is polycrystalline structure.
By above-mentioned Pd-Bi (OH)3Nano-wire catalyst is scanned using X-ray diffractometer, as a result such as Fig. 4 institute Show, it can be seen that all XRD spectrum peaks correspond to the face-centered cubic phase (JCPDS, 87-0637) of Pd, wherein 2 θ of diffraction maximum= 38.8 °, 45.1 °, 65.8 °, 79.0 ° and 83.4 ° (111) that can be indexed as pure Pd, (200), (220), (311) and (222) face.
Further using x-ray photoelectron spectroscopy detection chain Pd-Bi (OH)3The component valence of Bi in nano-wire catalyst State, as shown in figure 5, occurring a pair of of peak figure spectrum at 159.0eV and 164.3eV, this can be attributed to Bi for Bi element (OH)3Presence therefore can prove above-mentioned to prepare Bi (OH)3The Pd nano wire of modification, as Pd-Bi (OH)3Nano wire Catalyst.
The test of (EOR) catalytic activity is reacted in oxidation of ethanol:
(1) preparation of catalysis electrode
By the Pd-Bi (OH) of above-mentioned preparation3Nano-wire catalyst and Vulcan XC-72 carbon (account for Pd catalyst 20%) It is dispersed in 1ml ethyl alcohol, (wherein, V in water and Nafion solutionEthyl alcohol/VWater/VNafion solution=1:1:0.06), then ultrasound 40min shape At uniform prepared Chinese ink.The amount control of Pd is based on depending on ICP test data in catalyst, and Pd load is maintained at 28ug/cm2.By 5uL Prepared Chinese ink drips on the glassy carbon electrode that area is 3mm, and then room temperature is dried for use.
(2) EOR is tested
In N2The 1mol/L NaOH+1mol/L C of saturation2H5With 50mv s in OH-1Sweep speed carries out EOR test.Containing 1mol/L C2H5In the 1mol/L NaOH solution of OH, at 0.8V (vs.RHE), the long-term of sample is prepared with timing Amperometric Determination Stability.In order to be compared, herein by business Pd/C (the Pd nano particle of 40wt% is supported on Vulcan XC-72 carbon, Sigma-Aldrich company) use same preparation step and test method.
1 resulting Pd-Bi (OH) of embodiment3The EOR performance of nano-wire catalyst works by using morning China CHI660e It stands, is tested in three pole battery systems.In three-electrode system, using saturated calomel electrode and Pt as reference electrode With to electrode.
Fig. 6 is the Pd-Bi (OH) of embodiment 13Nano-wire catalyst is in C containing 1mol/L2H5The 1mol/L NaOH solution of OH In, potential range -1V~0.2V (relative to saturated calomel electrode, SCE) sweeps the cyclic voltammetry curve that speed is 50mV/s.From Fig. 6 It can obtain, Pd-Bi (OH)3The EOR activity of nano-wire catalyst is 4.26A mg-1, and in contrast, the activity of business Pd/C is only There is 1.12A mg-1。
Fig. 7 is the Pd-Bi (OH) of embodiment 13Nano-wire catalyst is in C containing 1mol/L2H5The 1mol/L NaOH solution of OH In, under the conditions of current potential 0.2V (relative to saturated calomel electrode, SCE), every 50000s reactivating catalyst, the electrolyte renewed, The chronoa mperometric plot being repeated 3 times in total.As can be drawn from Figure 7, after 150000s stability test, Pd-Bi (OH)3Nano wire Catalyst still has more than 0.5Amg-1EOR activity.In contrast, business Pd/C, the electricity that renews primary with 20000s reactivation Liquid is solved, is tested by 60000s, EOR activity almost levels off to 0, that is, loses activity, as shown in Figure 8.
Embodiment 2
A kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, as shown in Figure 1, this method specifically include it is following Step:
(1) molar ratio is dissolved in 5ml diethylene glycol solvent and is mixed for the palladium acetylacetonate of 1:0.5 and five water bismuth nitrates After conjunction, ultrasonic 30min obtains precursor solution.
Wherein, in precursor solution, the concentration of palladium ion is 0.013mol/L, and the concentration of bismuth ion is 0.026mol/L.
(2) by 1.65g (excessive 1%) polyvinylpyrrolidone and 40ml diethylene glycol solvent, by polyvinylpyrrolidone: Diethylene glycol solvent be 0.01mol:1L ratio mixed, then under vacuum conditions, control revolving speed be 1000r/min, Temperature is 50 DEG C, and stirring 10~30min dissolution obtains reaction dissolvent.
Wherein, the molecular weight of polyvinylpyrrolidone is 40000g/mol.
(3) precursor solution that above-mentioned steps (1) obtain is rapidly joined into step (2) resulting reaction dissolvent, is obtained To reaction solution.Under n 2 atmosphere, it is 10 DEG C/min according to heating rate, the temperature of reaction solution is increased to 100 DEG C, and 15min is reacted at this temperature, and then cooled reaction solution to room temperature cleans reaction solution and obtains black solid powder, the black Solid powder is Pd base nano-wire first product.
(4) the resulting black solid powder of step (3) is prepared into catalyst prepared Chinese ink, is then added drop-wise to glassy carbon electrode table Face naturally dry, is activated using electrochemical cyclic voltammetry, electrolyte be 1mol/L NaOH solution, potential range be -1V~ 0.2V (relative to saturated calomel electrode, SCE), sweeping speed is 50mV/S, and Pd-Bi (OH) can be obtained after electrochemical activation processing3 Nano-wire catalyst.
Embodiment 3
A kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, as shown in Figure 1, this method specifically include it is following Step:
(1) molar ratio is dissolved in after being mixed in 5ml ethylene glycol solvent for the chlorine palladium acid of 1:1 and new lauric acid/dodecanoic acid bismuth, is surpassed Sound 30min, obtains precursor solution.
Wherein, in precursor solution, the concentration of palladium ion is 0.005mol/L, and the concentration of bismuth ion is 0.005mol/L.
(2) by polyvinylpyrrolidone and ethylene glycol solvent, by polyvinylpyrrolidone: ethylene glycol solvent is The ratio of 0.0063mol:1L is mixed, and then under vacuum conditions, control revolving speed is 300r/min, temperature is 60 DEG C, is stirred 10~30min dissolution is mixed, reaction dissolvent is obtained.
Wherein, the molecular weight of polyvinylpyrrolidone is 60000g/mol.
(3) precursor solution that above-mentioned steps (1) obtain is rapidly joined into step (2) resulting reaction dissolvent, is obtained To reaction solution.Under n 2 atmosphere, it is 2 DEG C/min according to heating rate, the temperature of reaction solution is increased to 90 DEG C, and at this At a temperature of react 60min, then cooled reaction solution to room temperature cleans reaction solution and obtains black solid powder, the black is solid Body powder is Pd base nano-wire first product.
(4) the resulting black solid powder of step (3) is prepared into catalyst prepared Chinese ink, is then added drop-wise to glassy carbon electrode table Face naturally dry, is activated using electrochemical cyclic voltammetry, electrolyte be 0.1mol/L KOH solution, potential range be -1V~ 0.2V (relative to saturated calomel electrode, SCE), sweeping speed is 100mV/S, and Pd-Bi (OH) can be obtained after electrochemical activation processing3 Nano-wire catalyst.
Embodiment 4
A kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, as shown in Figure 1, this method specifically include it is following Step:
(1) palladium acetate and acetylacetone,2,4-pentanedione bismuth that molar ratio is 1:3 are dissolved in after being mixed in 5ml glycerine solvent, are surpassed Sound 30min, obtains precursor solution.
Wherein, in precursor solution, the concentration of palladium ion is 0.005mol/L, and the concentration of bismuth ion is 0.015mol/L.
(2) by polyvinylpyrrolidone and glycerine solvent, by polyvinylpyrrolidone: glycerine solvent is 0.01mol: The ratio of 1L is mixed, and then under vacuum conditions, control revolving speed is 800r/min, temperature is 20 DEG C, stirs 10~30min Dissolution, obtains reaction dissolvent.
Wherein, the molecular weight of polyvinylpyrrolidone is 80000g/mol.
(3) precursor solution that above-mentioned steps (1) obtain is rapidly joined into step (2) resulting reaction dissolvent, is obtained To reaction solution.Under n 2 atmosphere, it is 5 DEG C/min according to heating rate, the temperature of reaction solution is increased to 150 DEG C, and 10min is reacted at this temperature, and then cooled reaction solution to room temperature cleans reaction solution and obtains black solid powder, the black Solid powder is Pd base nano-wire first product.
(4) the resulting black solid powder of step (3) is prepared into catalyst prepared Chinese ink, is then added drop-wise to glassy carbon electrode table Face naturally dry, is activated using electrochemical cyclic voltammetry, electrolyte be 2mol/L KOH solution, potential range be -1V~ 0.2V (relative to saturated calomel electrode, SCE), sweeping speed is 10mV/S, and Pd-Bi (OH) can be obtained after electrochemical activation processing3 Nano-wire catalyst.
Embodiment 5
A kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, as shown in Figure 1, this method specifically include it is following Step:
(1) molar ratio is dissolved in 5ml pentaerythrite solvent and is mixed for the palladium acetylacetonate of 1:1 and five water bismuth nitrates Afterwards, ultrasonic 30min, obtains precursor solution.
Wherein, in precursor solution, the concentration of palladium ion is 0.05mol/L, and the concentration of bismuth ion is 0.05mol/L.
(2) by polyvinylpyrrolidone and glycerine solvent, by polyvinylpyrrolidone: glycerine solvent is 0.01mol: The ratio of 1L is mixed, and then under vacuum conditions, control revolving speed is 1000r/min, temperature is 50 DEG C, and stirring 10~ 30min dissolution, obtains reaction dissolvent.
Wherein, the molecular weight of polyvinylpyrrolidone is 50000g/mol.
(3) precursor solution that above-mentioned steps (1) obtain is rapidly joined into step (2) resulting reaction dissolvent, is obtained To reaction solution.Under n 2 atmosphere, it is 0.5 DEG C/min according to heating rate, the temperature of reaction solution is increased to 100 DEG C, and 40min is reacted at such a temperature, and then cooled reaction solution to room temperature cleans reaction solution and obtains black solid powder, this is black Color solid powder is Pd base nano-wire first product.
(4) the resulting black solid powder of step (3) is prepared into catalyst prepared Chinese ink, is then added drop-wise to glassy carbon electrode table Face naturally dry, is activated using electrochemical cyclic voltammetry, electrolyte be 1mol/L KOH solution, potential range be -1V~ 0.2V (relative to saturated calomel electrode, SCE), sweeping speed is 200mV/S, and Pd-Bi (OH) can be obtained after electrochemical activation processing3 Nano-wire catalyst.
To sum up, Pd-Bi (OH) prepared by preparation method of the invention3Nano-wire catalyst has good oxidation of ethanol Catalytic reaction activity, i.e., EOR activity is good, and excellent in stability, preparation process is simple, it is at low cost, be convenient for industrial-scale production.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention. Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.

Claims (10)

1. a kind of preparation method of Direct Ethanol Fuel Cell anode catalyst, which is characterized in that the described method includes:
The presoma palladium salt of default molar ratio and presoma bismuth salt are dissolved in the first polyol solvent, precursor solution is obtained；
A certain amount of surfactant is dissolved in the second polyol solvent, reaction dissolvent is obtained；
The precursor solution is added into the reaction dissolvent, reaction solution is obtained；Institute is heated under inert gas protection Reaction solution is stated to 90~150 DEG C, after reacting 10~60min, the reaction solution is cleaned, obtains Pd base nano-wire first product；
Electrochemical activation processing is carried out to the Pd base nano-wire first product under alkaline environment, obtains Pd-Bi (OH)3Nano wire is urged Agent.
2. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described In precursor solution, the concentration of palladium ion is 0.005~0.05mol/L, and the concentration of bismuth ion is 0.005~0.05mol/L.
3. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described The molar ratio of presoma palladium salt and presoma bismuth salt is 1:(0.5~3).
4. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described Presoma palladium salt is the combination of one or more of palladium acetylacetonate, chlorine palladium acid, palladium acetate；The presoma bismuth salt is five water The combination of one or more of bismuth nitrate, new lauric acid/dodecanoic acid bismuth and acetylacetone,2,4-pentanedione bismuth.
5. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described First polyol solvent and the second polyol solvent are one of ethylene glycol, diethylene glycol, glycerine, pentaerythrite or several The combination of kind.
6. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described Surfactant is polyvinylpyrrolidone, and the molecular weight of the polyvinylpyrrolidone is more than or equal to 40000g/mol, described The concentration of polyvinylpyrrolidone is more than or equal to 0.0063mol/L in reaction dissolvent.
7. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 6, which is characterized in that described A certain amount of surfactant is dissolved in the second polyol solvent, obtaining reaction dissolvent includes:
Polyvinylpyrrolidone is mixed with second polyol solvent, and under vacuum conditions, control revolving speed is 300 ~1000r/min, temperature are 20~60 DEG C, stir 10~30min, obtain the reaction dissolvent.
8. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described The reaction solution, which is heated, to 90~150 DEG C includes:
It is 0.5~10 DEG C/min according to heating rate, heats the reaction solution to 90~150 DEG C.
9. the preparation method of Direct Ethanol Fuel Cell anode catalyst according to claim 1, which is characterized in that described Electrochemical activation processing includes: electrochemical cyclic voltammetry activation or chronoamperometry activation, and electrolyte is 0.1~2mol/L NaOH solution or KOH solution, potential range are -1.0~0.2V, and sweeping speed is 10~200mV/s.
10. a kind of Direct Ethanol Fuel Cell anode catalyst, which is characterized in that for using described in any one of claim 1~9 Direct Ethanol Fuel Cell anode catalyst the Pd-Bi (OH) that is prepared of preparation method3Nano-wire catalyst, it is described Pd-Bi(OH)3Nano-wire catalyst has chain structure, the Pd-Bi (OH)3The surface of nano-wire catalyst has Bi (OH)3It repairs Decorations.
CN201811504313.5A 2018-12-10 2018-12-10 Direct ethanol fuel cell anode catalyst and preparation method thereof Active CN109994743B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811504313.5A CN109994743B (en) 2018-12-10 2018-12-10 Direct ethanol fuel cell anode catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811504313.5A CN109994743B (en) 2018-12-10 2018-12-10 Direct ethanol fuel cell anode catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109994743A true CN109994743A (en) 2019-07-09
CN109994743B CN109994743B (en) 2022-04-05

Family

ID=67128618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811504313.5A Active CN109994743B (en) 2018-12-10 2018-12-10 Direct ethanol fuel cell anode catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109994743B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113178588A (en) * 2021-03-26 2021-07-27 南通大学 Preparation method of Pd-based porous nano catalyst with strong coupling structure
CN114959788A (en) * 2022-06-14 2022-08-30 安徽大学 Preparation of oxophilic metal doped network-shaped PdH/C and application thereof in ethanol electrocatalytic oxidation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6092239A (en) * 1983-10-24 1985-05-23 Kawaken Fine Chem Co Ltd Preparation of gluconic acid
CN103887529A (en) * 2012-12-21 2014-06-25 中国科学院大连化学物理研究所 M1 + M2/C catalyst and its preparation method
CN104226310A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Selective hydrogenation catalyst with core-shell structure and preparation method thereof
CN108274014A (en) * 2018-01-23 2018-07-13 南开大学 It is a kind of that there is multiple branched Nanoalloy and preparation method thereof
CN108736030A (en) * 2018-05-17 2018-11-02 福州大学 A kind of porous no C catalyst of used in proton exchange membrane fuel cell and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6092239A (en) * 1983-10-24 1985-05-23 Kawaken Fine Chem Co Ltd Preparation of gluconic acid
CN103887529A (en) * 2012-12-21 2014-06-25 中国科学院大连化学物理研究所 M1 + M2/C catalyst and its preparation method
CN104226310A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Selective hydrogenation catalyst with core-shell structure and preparation method thereof
CN108274014A (en) * 2018-01-23 2018-07-13 南开大学 It is a kind of that there is multiple branched Nanoalloy and preparation method thereof
CN108736030A (en) * 2018-05-17 2018-11-02 福州大学 A kind of porous no C catalyst of used in proton exchange membrane fuel cell and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
L. DEMARCONNAY 等: "Ethylene glycol electrooxidation in alkaline medium", 《SCIENCE DIRECT》 *
沈培康 等: "钯基醇氧化电催化剂的研究进展", 《电源技术》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113178588A (en) * 2021-03-26 2021-07-27 南通大学 Preparation method of Pd-based porous nano catalyst with strong coupling structure
CN114959788A (en) * 2022-06-14 2022-08-30 安徽大学 Preparation of oxophilic metal doped network-shaped PdH/C and application thereof in ethanol electrocatalytic oxidation
CN114959788B (en) * 2022-06-14 2024-01-30 安徽大学 Preparation of aerophilic metal doped network PdH/C and application thereof in electrocatalytic oxidation of ethanol

Also Published As

Publication number Publication date
CN109994743B (en) 2022-04-05

Similar Documents

Publication Publication Date Title
CN108736031B (en) Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof
CN105170169B (en) A kind of nitrogen-doped graphene iron-based nano-particles reinforcement type catalyst and preparation method thereof
CN104681823B (en) A kind of nitrogen-doped graphene and Co3O4 hollow nano-sphere composites and its preparation method and application
Kakaei et al. Fabrication of Pt–CeO2 nanoparticles supported sulfonated reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation
CN103495432A (en) Method for preparing efficient stable fuel cell catalyst
CN114293223B (en) Method for preparing superfine cerium dioxide supported metal monoatomic catalyst from cluster-based framework material
CN111266110B (en) Anode catalyst for water electrolysis hydrogen production by using transition metal doped titanium oxide as carrier and preparation method thereof
CN105289687A (en) Nitrogen-doped graphene-supported iron-based nanoparticle composite catalyst and preparation method thereof
CN109967094A (en) A kind of nano porous metal compound catalyst of monatomic platinum dopant, preparation method and application
CN102324531A (en) Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof
CN113277573B (en) PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof
CN109994743A (en) A kind of Direct Ethanol Fuel Cell anode catalyst and preparation method thereof
CN113481004A (en) Carbon dots and preparation method and application thereof
CN101773828A (en) Pt-TiO2/CNTs catalyst and preparation method thereof
CN110350213B (en) High-efficiency PtRu/C bifunctional fuel cell anode catalyst and preparation method thereof
CN109244485B (en) NiCo/TiO2Battery anode catalyst and preparation method thereof
CN107195917A (en) A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof
CN103706375A (en) Preparation method of PtFe/C catalyst used for proton exchange membrane fuel cell
CN112058301A (en) Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction
CN101306366A (en) Preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst
CN102814177B (en) Preparation method of catalyst for direct methanol fuel cell and direct methanol fuel cell
CN113731466B (en) MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, preparation and application thereof
CN106887602A (en) A kind of Ag-CuO/C catalyst and its preparation and application
CN110247061B (en) Carbon-supported bimetallic monatomic electrocatalyst and preparation and application thereof
KR20220027437A (en) A transition metal nitride-carbon catalyst composite, a method for manufacturing the same, a electrode catalyst for fuel cell comprising the transition metal nitride-carbon catalyst composite, a fuel cell comprising the electrode catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant