CN102380400A - Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof - Google Patents

Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof Download PDF

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CN102380400A
CN102380400A CN2011102847589A CN201110284758A CN102380400A CN 102380400 A CN102380400 A CN 102380400A CN 2011102847589 A CN2011102847589 A CN 2011102847589A CN 201110284758 A CN201110284758 A CN 201110284758A CN 102380400 A CN102380400 A CN 102380400A
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CN102380400B (en
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段东红
武爱莲
刘世斌
卫国强
张忠林
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Taiyuan University of Technology
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Abstract

Disclosed are a core-shell structural anode catalyst for direct borohydride fuel cells and a preparation method thereof. The catalyst comprises Mcore-Aushell nano composite particles which utilize M as the core and utilizes Au as the shell, and the particle size of the Mcore-Aushell particles ranges from 10nm to 50nm. The preparation method includes steps: firstly, adding M-salt and a stabilizing agent into a solvent sequentially, introducing nitrogen gas into the solvent and then stirring and heating the solvent, introducing and stirring nitrogen gas again, dropping a reducing agent to realize reaction and obtain M-nano catalyst sol, and then obtaining M-nano particles after filtering and washing; secondly, dissolving the M-nano particles into solvent, adding stabilizing agent and introducing nitrogen gas into the solvent along with stirring, adding chloroauric acid-tetrahydrofuran solution, introducing nitrogen gas again, dropping reducing agent to realize reaction and prepare nano-catalyst sol, separating and washing the nano-catalyst sol, drying the nano-catalyst sol in vacuum, and finally preparing powdered Mcore-Aushell nano-particle catalyst by means of grinding. The core-shell structural anode catalyst for direct borohydride fuel cells has higher BH4 (tetrahydrobiopterin)-oxidation activity and is low in hydrogen evolution, and accordingly fuel utilization rate is improved.

Description

Direct borohydride fuel cell nucleocapsid structure anode catalyst and preparation method thereof
Technical field
What the present invention relates to is a kind of direct borohydride fuel cell eelctro-catalyst, and specifically a kind of nuclear shell structure nano compound particle belongs to electro-catalysis technology and energy technology field as the direct borohydride fuel cell anode material.
Background technology
(Direct Borohydride Fuel Cell DBFC) is a kind of use liquid alkali metal boron hydride ABH to direct borohydride fuel cell 4(A=Na, Li or K) is the TRT of fuel.Because alkali metal borohydride is a kind of hydrogeneous more and stable again hydride ion material that contains, its hydrogen storage ability is similar with methyl alcohol, but owing to carbon elements not than methyl alcohol more " cleaning "; The volume energy density of sodium borohydride liquid fuel (about 3000Ah/L) is greater than liquified hydrogen (about 2000Ah/L), and its weight energy density (about 5Ah/g) is much larger than metal hydride (about 0.7Ah/L); Compare with methyl alcohol, the boron hydride chemical property is stable, is easy to store supply, and is safe in utilization and nonflammable.So use the alkali metal borohydride aqueous solution to be expected to become the power supply that solves a low temperature decentralized fuel storage difficult problem, cheap as the direct borohydride fuel cell of fuel.
DBFC adds alkali metal borohydride in the corresponding alkali lye as liquid fuel, in the anode-side oxidation, discharges 8 electronics; Oxidant (oxygen, air or hydrogen peroxide) is fed in the identical alkali lye, reduce at cathode side.Its anodic oxidation reactions is:
BH 4 -?+?8OH -?=?BO 2 -?+?6H 2O?+?8e - （1）
Yet in the actual discharge process, BH 4 -On electrode, always there is hydrolysis in various degree:
Figure 783790DEST_PATH_IMAGE001
（2）
Because BH on the electrode 4 -Electro-oxidation reaction and BH 4 -Hydrolysis vie each other, so the combined reaction metering-type is written as:
BH 4 -?+?nOH -?=?BO 2 -?+?(n-2)H 2O?+?(4?-0.5n)H 2?+ne - (3)
Figure 970052DEST_PATH_IMAGE002
Expression is by each BH 4 -Ion is the actual apparent electron number that discharges on anode, and its size is relevant with electrode material and reaction condition, usually less than theoretical value 8, BH 4 -The electron number that in the DBFC anode oxidation process, produces is lower than 8, has not only reduced faradic efficiency, and the bubble hydrogen that discharges can hinder the migration of ion and reduce the performance of battery, and the operation of returning battery simultaneously brings certain potential safety hazard.
The anode electrocatalysis material of DBFC use at present mainly contains precious metals pt, Pd and Au, non-noble metal Ni, Cu and some hydrogen storage materials and alloy etc.In these electrode catalytic materialses, according to BH 4Release hydrogen whether in catalytic oxidation process is divided into electrode material " catalysis " and " on-catalytic " two types.BH 4Electrochemical oxidation reactions on " catalysis " materials such as Pt, Pd, Ni, Cu has advantages of high catalytic activity, but the catalytic activity of its hydrolysis is also very high, so faradic efficiency is lower; And BH 4On Au, these " on-catalytic " electrodes of Ag, though can obtain very high electron number n, but its oxidizing reaction rate is slow.Therefore, some researchers adopt method preparation " difunctional " catalyst of alloying, attempt to develop both to BH 4Electrochemical oxidation reactions is active high, simultaneously the anode catalyst of catalyzing hydrolysis not again.(Atwan M H such as document Atwan; Macdonald C L B, Northwood D O, Gyenge E L. J. Power Sources; 2006; 158 (1): 36-44) adopt the Bonneman colloid method to prepare carbon-supported nano Au, Au-Pt and Au-Pd catalyst, under the room temperature, three's catalytic activity is followed successively by Au-Pt>Au>Au-Pd, this is illustrated in the Pt that adds " catalysis " among the Au of " on-catalytic " can improve NaBH 4Oxidation activity.Though adopt the method for binary metal alloying can improve catalytic electrode material to NaBH 4Oxidation activity, but " catalysis " metal component contacts with electrolyte in the alloy electrode material, releasing hydrogen gas still, fuel availability is lower, so the performance of alloying electrode catalyst still can not satisfy the needs of direct borohydride fuel cell.
Summary of the invention
The objective of the invention is provides a kind of high performance nucleocapsid structure M that has for direct borohydride fuel cell Core-Au ShellNano-complex particle anode electrocatalyst and preparation method solve the existing problem that DMFC anode activity is low, the hydrolysis liberation of hydrogen is serious, fuel availability is low.
For realizing this purpose, the present invention realizes through following technical scheme:
The nuclear shell structure nano metallic has the performance of shell and inner nuclear material concurrently, can also produce compound collaborative multifunctional effect simultaneously.The present invention is a kernel through adopting " catalysis " metal, is the nucleocapsid structure M of shell with Au Core-Au ShellNano-complex particle can not only keep gold to BH as the direct borohydride fuel cell anode catalyst 4The characteristics that catalytic hydrolysis reaction speed is little, and can avoid " catalysis " material directly to contact with electrolyte, performance " catalysis " material is to BH 4The active high characteristics of catalytic oxidation.This bimetallic nuclear shell type nano meter particle; Interior nuclear element produces inductive effect to the d orbital electron of shell Au metal; Can effectively change the structure and the binding energy of shell metallic d orbital electron; The surface adsorption property of nucleocapsid structure catalysis material is changed, thereby improve the catalytic oxidation activity of surface crust Au.
Direct borohydride fuel cell anode catalyst of the present invention is that M, shell are the nucleocapsid structure M that Au forms by kernel Core-Au ShellNano-complex particle, the particle diameter 10 ~ 50nm of core-shell particles.
The preparation method of direct borohydride fuel cell anode catalyst of the present invention may further comprise the steps:
(1) preparation M particle: M-salt and stabilizing agent are added in the 100ml solvent successively, and stirring and logical nitrogen fully mixed it in 20 ~ 30 minutes, were heated to 50 ~ 80 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Reducing agent, adding reducing agent mole is 1.2 ~ 2.5 times of M element, rate of addition is 40 min -1, reaction 20 ~ 60 min prepare M nanocatalyst colloidal sol, and suction filtration with the distilled water washing, gets the M nano particle then;
(2) be dissolved in the M nano particle in above-mentioned (1) in the solvent again; Stir and add stabilizing agent down; The concentration of stabilizing agent is 0.5 ~ 5g/L, feeds nitrogen and also stirred 30 minutes, and be that to add concentration be the tetrahydrofuran solution of 0.3g/L gold chloride for the ratio of 0.5 ~ 2.0:1 according to M, Au atomic molar ratio again; Under 60 ~ 70 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 20 ~ 30 min -1Speed to drip concentration be 0.1 molL -1Reducing agent, the mol ratio of reducing agent and gold atom is 2.5:1, under 60 ~ 70 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 300 ~ 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered M Core-Au ShellThe core-shell structure nanometer particle catalyst.
Used M-salt is NiCl among the preparation method of above-mentioned catalyst with core-casing structure 26H 2O, CoCl 26H 2O, Cu (NO 3) 3H 2O, H 2PtCl 66H 2O, PdCl 22H 2O and Pd (NO 3) 22H 2A kind of among the O, the concentration of M-salt in solvent is 5 ~ 30mmol/L.
Used solvent is a kind of in ethylene glycol, water, oxolane, isopropyl alcohol and the ethanol among the preparation method of above-mentioned catalyst with core-casing structure.
Used stabilizing agent is a kind of in polyethylene arsenic pyrrolidone (PVP), four octyl group ammonium bromides, polyethylene glycol and the polyvinyl alcohol among the preparation method of above-mentioned catalyst with core-casing structure, and stabilizing agent concentration in solvent is 0.5 ~ 5g/L,
Reducing agent used among the preparation method of above-mentioned catalyst with core-casing structure is: a kind of in hydrazine hydrate, lithium triethylborohydride and the sodium borohydride, the pH value of its solution is with 1 molL -1NaOH solution is adjusted to 13.
Direct borohydride fuel cell nucleocapsid structure anode catalyst of the present invention adopts direct sodium borohydride-hydrogen peroxide fuel battery system to carry out anode catalyst performance evaluation.Nucleocapsid structure M Core-Au ShellThe preparation process of/C anode is: with the M of the present invention's preparation Core-Au ShellWith the XC-72 carbon dust be that the ratio of 1:4 takes by weighing 0.1g in mass ratio, add the 2mL deionized water, 3.5mL absolute ethyl alcohol and 20% PTFE 0.150g, ultrasonic agitation becomes the prepared Chinese ink shape after 30 minutes, with spraying method catalyst prepared Chinese ink evenly is coated in 1 * 1cm 2Nickel screen on, control metal carrying capacity be 4mg/cm 2, dry naturally then, at last the nickel screen that scribbles catalyst 60 oHot pressing is 2 minutes under C, the 5MPa, promptly makes M Core-Au Shell/ C anode.Negative electrode is the platinum guaze (100 order) of 1 * 1cm, and reference electrode is saturated Hg/Hg 2Cl 2Electrode (232 type).The cathode chamber of electro-chemical test groove and anode chamber's size are 3 * 4 * 5cm, with the NRE-212 cationic membrane catholyte and anolyte are separated, and the exposed area of film is 1.0cm 2The upper end, anode chamber has a blast pipe to link to each other with U type gas gauge, collects the volume that produces hydrogen under the different electric current density with drainage.The polarization experiment anolyte is 2mol/LNaOH+1 molL -1NaBH 4, catholyte is 2.0 molL -1HCl+4.5 molL -1H 2O 2Adopt U.S. Princeton VMP III potentiostat to measure the performance of monocell.
The made catalyst with core-casing structure of the present invention demonstrates good BH in direct borohydride fuel cell monocell system 4 -Anode electroxidation performance.
The present invention is used for direct borohydride fuel cell nucleocapsid structure anode catalyst compared with prior art, and the used direct borohydride fuel cell nucleocapsid structure anode catalyst of the present invention is to BH 4 -The active height of oxidation, liberation of hydrogen is few, can effectively improve the utilization rate of fuel.
Description of drawings
Fig. 1 is the Cu of the embodiment of the invention 1 preparation Core-Au ShellThe transmission electron microscope of core-shell structure nanometer particle catalyst (TEM) photo;
Among the figure: particle diameter is 30nm, and middle black part is divided into Cu nuclear nano particle, and outer light cloud form partly is the Au shell, about 6 nm of the thickness of shell;
Fig. 2 is the battery performance curve of anode for different catalysts;
Among the figure: 1 is the Cu of the embodiment of the invention 1 preparation Core-Au ShellThe core-shell structure nanometer particle catalyst;
2 is that Cu, Au atomic molar are than being the Cu-Au alloy catalyst of 1:1; 3 is the Au catalyst.
The specific embodiment
Describe through the embodiment specific embodiments of the invention below
Embodiment 1
(1) preparation of Cu nano particle: with Cu (NO 3) 3H 2O and polyethylene arsenic pyrrolidone (PVP) add in the 20 ml ethylene glycol successively, and making the concentration of Cu atom in ethylene glycol is 20 mmol/L, and the concentration of polyethylene arsenic pyrrolidone (PVP) in ethylene glycol is 3 g/L.Stirring and logical nitrogen 25 min fully mix it, are heated to 60 ℃ then, continue to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Hydrazine hydrate solution, the mole that adds hydrazine hydrate is 2 times of Cu element, rate of addition is 40 min -1, react 40 min, prepare Cu nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Cu nano particle then;
(2) the Cu nano particle in above-mentioned (1) is dissolved in the 20 ml ethylene glycol again; Stir and add polyethylene arsenic pyrrolidone (PVP) down; Making its concentration is 3 g/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Cu, Au atomic molar than the ratio for 1:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 60 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 20 min -1Speed to drip concentration be 0.1 molL -1Hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, under 60 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol, centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol; 50 ℃ of dryings of vacuum 18 hours, 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Cu-Au core-shell structure nanometer particle catalyst; Its TEM photo is as shown in Figure 1, and observing nucleocapsid structure Cu-Au average particle diameter by Fig. 1 is 30nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.92V, is 94% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 124 mW/cm 2, its performance is shown in curve among Fig. 21.Be effect more of the present invention; Be equipped with Cu-Au alloy catalyst or Au catalyst in order to the below legal system: polyethylene arsenic pyrrolidone (PVP) is added in the 20 ml ethylene glycol; Making its concentration is 3 g/L, and feeding nitrogen also stirred 30 minutes, is the ratio adding Cu (NO of 1:1 again according to Cu, Au mol ratio 3) 3H 2O and concentration are the tetrahydrofuran solution of 0.3g/L gold chloride, under 60 ℃ of temperature, constantly stir and continue to feed nitrogen, then with 20 min -1Speed to drip concentration be 0.1 molL -1Hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 4.5:1, under 60 ℃ of temperature, continues stirring reaction 2h; Make Nanoalloy Cu-Au catalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, ethanol, 50 ℃ of dryings of vacuum 18 hours; 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Cu-Au alloy nano particle catalyst.The preparation method of Au nano-particle catalyst is the same with the Cu-Au alloy catalyst, in the preparation process, only adds the tetrahydrofuran solution of gold chloride.With gained eelctro-catalyst Cu-Au alloy is anode catalyst; At room temperature directly sodium borohydride-the open-circuit voltage of hydrogen peroxide fuel battery monocell is respectively and is 1.34V; Peak use rate by the amounts of hydrogen computing fuel that records is 63%, and maximum power density is 62 mW/cm 2, its performance is shown in curve among Fig. 22.With gained eelctro-catalyst Au is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is respectively 1.18V, is 88% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 29 mW/cm 2, its performance is shown in curve among Fig. 23.Can know, be that the DBFC performance of anode is superior to also being superior to independent Au catalyst with the Cu-Au alloy catalyst of forming with nucleocapsid structure Cu-Au nanocatalyst.
Embodiment 2
(1) preparation of Ni nano particle: with NiCl 26H 2O and four octyl group ammonium bromides add in the 20ml water successively, and making the concentration of Ni atom in water is 10 mmol/L, and the concentration of four octyl group ammonium bromides in water is 1.5 g/L.Stirring and logical nitrogen fully mixed it in 20 minutes, were heated to 50 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Lithium triethylborohydride solution, adding lithium triethylborohydride mole is 1.5 times of Ni element, rate of addition is 40 min -1, react 40 min, prepare Ni nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Ni nano particle then;
(2) the M nano particle in above-mentioned (1) is dissolved in the 20 ml water again; Stir and add four octyl group ammonium bromides down; The concentration of four octyl group ammonium bromides is 1.5g/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Ni, Au atomic molar than the ratio for 0.5:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 70 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 30 min -1Speed to drip concentration be 0.1 molL -1Lithium triethylborohydride solution, the mol ratio of lithium triethylborohydride and gold atom is 2.5:1, under 70 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Ni-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Ni-Au average particle diameter is 40nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.85V, is 95% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 116mW/cm 2
Embodiment 3
(1) preparation Pt nano particle: with H 2PtCl 66H 2O and polyethylene glycol add in the 20ml oxolane successively, and making the concentration of Pt atom in oxolane is 30 mmol/L, and the concentration of polyethylene glycol in oxolane is 5 g/L.Stirring and logical nitrogen fully mixed it in 30 minutes, were heated to 80 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Sodium borohydride solution, adding sodium borohydride mole is 2.5 times of Pt element, rate of addition is 40 min -1, react 60 min, prepare Pt nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Pt nano particle then;
(2) the Pt nano particle in above-mentioned (1) is dissolved in the 20ml oxolane again; Stir and add polyethylene glycol down; The concentration of polyethylene glycol is 5g/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Pt, Au atomic molar than the ratio for 2.0:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 70 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 20 min -1Speed to drip concentration be 0.1 molL -1Sodium borohydride solution, the mol ratio of sodium borohydride and gold atom is 2.5:1, under 70 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 350 ℃ of heat treatment 3h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pt-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pt-Au average particle diameter is 20nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.90V, is 97% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 126 mW/cm 2
Embodiment 4
(1) preparation Co nano particle: with CoCl 26H 2O and polyvinyl alcohol add in the 20ml isopropyl alcohol successively, and making the concentration of Co atom in isopropyl alcohol is 20 mmol/L, and the concentration of polyvinyl alcohol in isopropyl alcohol is 0.5 g/L.Stirring and logical nitrogen fully mixed it in 20 minutes, were heated to 50 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Hydrazine hydrate solution, adding hydrazine hydrate mole is 1.2 times of Co element, rate of addition is 40 min -1, react 20 min, prepare M nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Co nano particle then;
(2) the Co nano particle in above-mentioned (1) is dissolved in the 20ml isopropyl alcohol again; Stir and add polyvinyl alcohol down; The concentration of polyvinyl alcohol is 0.5/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Co, Au atomic molar than the ratio for 1.5:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 65 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 25 min -1Speed to drip concentration be 0.1 molL -1Hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, under 65 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol alcohol, 50 ℃ of dryings of vacuum 18 hours; 300 ℃ of heat treatment 1.5 h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Co-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Co-Au average particle diameter is 50 nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.83V, is 93% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 108 mW/cm 2
Embodiment 5
(1) preparation of Pd nano particle: with PdCl 22H 2O and polyethylene arsenic pyrrolidone (PVP) add in the 20ml ethanol successively, and making the concentration of Pd atom in ethanol is 5 mmol/L, and the concentration of polyvinyl alcohol in ethanol is 1 g/L.Stirring and logical nitrogen fully mixed it in 30 minutes, were heated to 60 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Sodium borohydride solution, adding sodium borohydride mole is 2.5 times of Pd element, rate of addition is 40 min -1, react 30 min, prepare Pd nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Pd nano particle then;
(2) the Pd nano particle in above-mentioned (1) is dissolved in the 20ml ethanol again; Stir and add four octyl group ammonium bromides down; The concentration of four octyl group ammonium bromides is 4g/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Pd, Au atomic molar than the ratio for 0.5:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 60 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 20 min -1Speed to drip concentration be 0.1 molL -1Lithium triethylborohydride solution, the mol ratio of lithium triethylborohydride and gold atom is 2.5:1, under 60 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pd-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pd-Au average particle diameter is 10nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.87V, is 96% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 113 mW/cm 2
Embodiment 6
(1) preparation of Pd nanometer: with Pd (NO 3) 22H 2O and four octyl group ammonium bromides add in the 20ml ethylene glycol successively, and making the concentration of Pd atom in ethylene glycol is 5 mmol/L, and the concentration of polyvinyl alcohol in ethylene glycol is 2 g/L.Stirring and logical nitrogen fully mixed it in 30 minutes, were heated to 50 ℃ then, continued to feed nitrogen and constantly stirring, and dripping concentration is 0.3 molL -1Hydrazine hydrate solution, adding hydrazine hydrate mole is 1.8 times of Pd element, rate of addition is 40 min -1, react 50 min, prepare Pd nanocatalyst colloidal sol, suction filtration with the distilled water washing, gets the Pd nano particle then;
(2) the Pd nano particle in above-mentioned (1) is dissolved in the 20ml ethylene glycol again; Stir and add polyethylene arsenic pyrrolidone (PVP) down; Its concentration is 2g/L, and feeding nitrogen also stirred 30 minutes, and adding concentration according to Pd, Au atomic molar than the ratio for 1:1 again is the tetrahydrofuran solution of 0.3g/L gold chloride; Under 60 ℃ of temperature, constantly stir and the lasting nitrogen that feeds, then with 20 min -1Speed to drip concentration be 0.1 molL -1Hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, under 60 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pd-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pd-Au average particle diameter is 30 nm.
With the gained eelctro-catalyst is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.86V, is 97% by the peak use rate of the amounts of hydrogen computing fuel that records, and maximum power density is 114 mW/cm 2

Claims (9)

1. direct borohydride fuel cell nucleocapsid structure anode catalyst, said catalyst are to be that M, shell are the nucleocapsid structure M of Au by kernel Core-Au ShellNano-complex particle, the particle diameter 10 ~ 50nm of core-shell particles.
2. preparation method who implements the described a kind of direct borohydride fuel cell nucleocapsid structure anode catalyst of claim 1, said method follows these steps to carry out:
(1) preparation M particle: M-salt and stabilizing agent are added in the 20 ml solvents successively, and stirring and feeding nitrogen mixed it in 20 ~ 30 minutes, were heated to 50 ~ 80 ℃ then, continued to feed nitrogen and continuous stirring, and it is 0.3 molL that the back drips concentration -1Reducing agent, adding reducing agent mole is 1.2 ~ 2.5 times of M element, rate of addition is 40 min -1, reaction 20 ~ 60 min make M nanocatalyst colloidal sol, and suction filtration washs then, gets the M nano particle;
(2) be dissolved in the M nano particle in the above-mentioned steps (1) in the solvent again; Stirring down, adding concentration is the stabilizing agent of 0.5 ~ 5g/L; Feeding nitrogen also stirred 30 minutes; Again in M, Au atomic molar ratio be the ratio of 0.5 ~ 2.0:1 to add concentration be the tetrahydrofuran solution of 0.3g/L gold chloride, under 60 ~ 70 ℃ of temperature, stir and continue to feed nitrogen, then with 20 ~ 30 min -1Speed to drip concentration be 0.1 molL -1Reducing agent, the mol ratio of reducing agent and gold atom is 2.5:1, under 60 ~ 70 ℃ of temperature, continues stirring reaction 2h; Make nanocatalyst colloidal sol; Centrifugation then is with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours; 300 ~ 400 ℃ of heat treatment 1 ~ 3h in the tube furnace argon gas atmosphere, grinding can obtain Powdered M-Au core-shell structure nanometer particle catalyst.
3. method as claimed in claim 2, said M-salt is NiCl 26H 2O, CoCl 26H 2O, Cu (NO 3) 3H 2O, H 2PtCl 66H 2O, PdCl 22H 2O and Pd (NO 3) 22H 2A kind of among the O.
4. like the described method of claim 2, the concentration of said M-salt in solvent is 5 ~ 30mmol/L.
5. like the described method of claim 2, said solvent is a kind of in ethylene glycol, water, oxolane, isopropyl alcohol and the ethanol.
6. like the described method of claim 2, said stabilizing agent is a kind of in polyethylene arsenic pyrrolidone (PVP), four octyl group ammonium bromides, polyethylene glycol and the polyvinyl alcohol.
7. like claim 2 or 6 described methods, said stabilizing agent concentration in solvent is 0.5 ~ 5g/L.
8. method as claimed in claim 2, said reducing agent are a kind of in hydrazine hydrate, lithium triethylborohydride and the sodium borohydride.
9. method as claimed in claim 2, the pH value of said solution is with 1 molL -1NaOH solution is adjusted to 13.
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CN104218249A (en) * 2014-08-15 2014-12-17 太原理工大学 Preparation method of core-shell structured catalyst for direct hydroboron fuel cell anode
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