CN105845948A - Preparation method for flower-shaped copper/copper oxide micro-nanocomposite and noble-metal-loaded catalyst for fuel cell - Google Patents
Preparation method for flower-shaped copper/copper oxide micro-nanocomposite and noble-metal-loaded catalyst for fuel cell Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a preparation method for a flower-shaped copper/copper oxide micro-nanocomposite and noble-metal-loaded catalyst for a fuel cell, and belongs to the synthesis technical field of a catalyst for fuel cells. The key point of the technical scheme comprises the steps of taking copper chloride as the copper source, taking glucose as the carbon source, taking hexadecyl trimethyl ammonium bromide as a surfactant and a structural guiding agent, and taking deionized water as a solvent, synthesizing the flower-shaped copper/copper oxide micro-nanocomposite through a hydrothermal reaction; and then enabling the flower-shaped copper/copper oxide micro-nanocomposite to be functionalized and to react with a noble-metal precursor under the effect of a reducing agent to obtain the target product. According to the preparation method, the copper oxide is taken as the transitional metal oxide, so that the activity of the noble metal catalyst can be improved through a promoted catalytic effect, the usage of noble metals can be reduced, and the cost of the catalyst for the fuel cell can be lowered; in the carrier, elemental copper and copper oxide form the composite material; due to the addition of copper, the electron conduction performance of the material is effectively reinforced; and the problem of bad conductivity of the transitional metal oxide is solved.
Description
Technical field
The invention belongs to the synthesis technical field of fuel-cell catalyst, be specifically related to the preparation method of a kind of flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is as clean energy resource, and fuel is renewable, wide material sources, deposit safety and environmental friendliness.In Proton Exchange Membrane Fuel Cells, catalyst is core component, is also to determine battery cost and the critical material of performance.The carrier that fuel-cell catalyst is conventional has carbon black (XC-72), CNT (MWCNTs) and mesoporous carbon carrier etc..Carbon black is one of catalyst carrier of being widely used at present, but its corrosion resistance is more weak, poor stability；Carbon nano tube surface is inert, lacks active sites, and noble metal granule is difficult to adhere at its surface uniform deposition；The porosity characteristic of mesoporous carbon makes partial catalyst metal nanoparticle may be covered by duct, causes the utilization rate of catalyst to reduce.Therefore, develop a kind of novel carriers that can improve catalyst activity to become fuel-cell catalyst synthesis technical field and have one of major issue to be solved.
In recent years, emerge in an endless stream as the research of direct alcohol fuel cell (DAFC) catalyst carrier and promoter about transition metal oxide.Main reason is that: on the one hand transition metal oxide can pass through promoting catalysis, improve the activity of noble metal catalyst, reduce the consumption of noble metal, and then reduce the cost of fuel-cell catalyst；On the other hand transition metal oxide can improve the electrochemical stability of catalyst, extends catalytic life.But the most not about the relevant report of flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst preparation method.
Summary of the invention
Present invention solves the technical problem that the preparation method that there is provided a kind of flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, be effectively increased the performance of fuel-cell catalyst.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, the preparation method of a kind of flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterised in that concretely comprise the following steps:
(1) with copper chloride for copper source, glucose is carbon source, and cetyl trimethylammonium bromide is surfactant and structure directing agent, and deionized water is solvent, in 150-200 DEG C of hydro-thermal reaction 9-48h, product is dried to obtain after deionized water and absolute ethanol washing black powder product；
(2) the black powder product that step (1) obtains is placed in tube furnace in 800 DEG C of calcining 3h, then take out sample dispersion and be heated to reflux 1-5h in the aqueous slkali that molar concentration is 0.5-3mol/L, question response cools down after terminating and is washed with deionized to neutrality, obtains flower-shaped copper/copper oxide complexes carrier after drying；
(3) flower-shaped copper/copper oxide complexes carrier step (2) obtained and sodium citrate ultrasonic disperse are in water-alcohol solution, add noble metal precursor body and to regulate the pH of reaction system be 10, washing and be dried to obtain flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst after being subsequently adding reducing agent reduction, wherein noble metal precursor body is H2PtCl6、Na2PdCl4、RuCl3Or RhCl3In one or more, reducing agent is KBH4、NaBH4, ascorbic acid, hydrazine hydrate, H2Or CO.
Further preferably, described copper chloride is 1:10-10:1 with the mass ratio of glucose, and copper chloride is 1:20-20:1 with the mass ratio of cetyl trimethylammonium bromide.
Further preferably, described aqueous slkali is potassium hydroxide solution, sodium hydroxide solution or ammonia spirit.
Further preferably, the pattern of described flower-shaped copper/copper oxide complexes carrier is the radial flower type structure of multidimensional, its a size of 1-5 μm.
Further preferably, described noble metal active component is Pt, Pd, PtPd, PtRu, PtRh, PdRu or PdRh.
Further preferably, in described water-alcohol solution, water is 1:1 with the volume ratio of alcohol, and alcohol is specially methanol, ethanol or propanol.
The present invention compared with prior art has the advantages that
1, the present invention has synthesized flower-shaped copper/copper oxide Micron-nano composites first as fuel-cell catalyst carrier, and this synthetic method is simple to operate, and yield is higher；
2, the flower-shaped copper/copper oxide Micron-nano composites of present invention synthesis has flower-shaped special construction, this special construction serves advantageous effect to the uniform load of noble metal catalyst, prevent the reunion of noble metal nano particles, be therefore effectively increased the catalysis activity of catalyst；
3, the flower-shaped copper/copper oxide Micron-nano composites of present invention synthesis has bigger specific surface area, and electric conductivity is strong simultaneously, is conducive to mass transfer in the electrolytic solution to conduct with electric current；
4, the present invention synthesis flower-shaped copper/copper oxide Micron-nano composites in copper oxide as transition metal oxide, the oxy radical on its surface has effectively slackened the carbon monoxide class material poisoning effect to catalyst, in flower-shaped copper/copper oxide Micron-nano composites, copper improves the electric conductivity of this carrier, and serve surface modified good action, it is effectively increased catalyst degree of scatter and then enhances electro-chemical activity.
Accompanying drawing explanation
Fig. 1 is the SEM figure of flower-shaped copper/copper oxide complexes carrier that the embodiment of the present invention 1 prepares；
Fig. 2 is the XRD figure spectrum of flower-shaped copper/copper oxide complexes carrier that the embodiment of the present invention 1 prepares；
Fig. 3 is the electrochemistry cyclic voltammetry curve comparison of the Pt catalyst that the embodiment of the present invention 1 prepares with comparative example 1, comparative example 2.
Detailed description of the invention
Being described in further details the foregoing of the present invention by the following examples, but this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, all technology realized based on foregoing of the present invention belong to the scope of the present invention.
Embodiment 1
Take 3g copper chloride, 1g glucose and 1g cetyl trimethylammonium bromide and be dissolved in wiring solution-forming in 30mL deionized water, then in 160 DEG C of hydro-thermal reactions 36h, and by product through deionized water and absolute ethanol washing several times, obtain black powder product after drying；Prepared black powder product is placed in tube-type atmosphere furnace and calcines 3h in 800 DEG C, then take appropriate amount of sample to be scattered in boiling water bath in the sodium hydroxide solution that molar concentration is 2mol/L and be heated to reflux 3h, by its surface-functionalized process, question response is washed with deionized after cooling to neutrality after terminating, and obtains the most flower-shaped copper of black powder sample/copper oxide complexes carrier after drying；Take the flower-shaped copper of 40mg/copper oxide complexes carrier and 100mg sodium citrate ultrasonic disperse in water/alcohol mixeding liquid that volume ratio is 1:1, add 10mL noble metal precursor body H2PtCl6And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.The target product that the present embodiment prepares as shown in Figure 1 is flower-like structure, and pattern is homogeneous, and diameter is about 3 μm.
Embodiment 2
Take 2g copper chloride, 1g glucose and 1.5g cetyl trimethylammonium bromide and be dissolved in wiring solution-forming in 30mL deionized water, then in 180 DEG C of hydro-thermal reactions 24h, and by product through deionized water and absolute ethanol washing several times, obtain black powder product after drying；Prepared black powder product is placed in tube-type atmosphere furnace and calcines 3h in 800 DEG C, then take appropriate amount of sample to be scattered in boiling water bath in the sodium hydroxide solution that molar concentration is 3mol/L and be heated to reflux 2h, by its surface-functionalized process, question response is washed with deionized after cooling to neutrality after terminating, and obtains the most flower-shaped copper of black powder sample/copper oxide complexes carrier after drying；Take the flower-shaped copper of 40mg/copper oxide complexes carrier and 100mg sodium citrate ultrasonic disperse in water/alcohol mixeding liquid that volume ratio is 1:1, add 10mL noble metal precursor body H2PtCl6And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.The target product that the present embodiment prepares as shown in Figure 2 is copper/copper oxide composite structure, does not has impurity peaks to occur, diffraction maximum sharply illustrates that degree of crystallinity is preferable.
Embodiment 3
Take 20g copper chloride, 5g glucose and 1g cetyl trimethylammonium bromide and be dissolved in wiring solution-forming in 30mL deionized water, then in 200 DEG C of hydro-thermal reactions 18h, and by product through deionized water and absolute ethanol washing several times, obtain black powder product after drying；Prepared black powder product is placed in tube-type atmosphere furnace and calcines 3h in 800 DEG C, then take appropriate amount of sample being scattered in molar concentration is that in 2mol/L ammonia spirit, boiling water bath is heated to reflux 4h, by its surface-functionalized process, question response is washed with deionized after cooling to neutrality after terminating, and obtains the most flower-shaped copper of black powder sample/copper oxide complexes carrier after drying；Take the flower-shaped copper of 40mg/copper oxide complexes carrier and 100mg sodium citrate ultrasonic disperse in the water that volume ratio is 1:1/propanol mixed liquor, add 10mL noble metal precursor body Na2PdCl4And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.
Embodiment 4
Take 6g copper chloride, 1g glucose and 2g cetyl trimethylammonium bromide and be dissolved in wiring solution-forming in 30mL deionized water, then in 160 DEG C of hydro-thermal reactions 18h, and by product through deionized water and absolute ethanol washing several times, obtain black powder product after drying；Prepared black powder product is placed in tube-type atmosphere furnace and calcines 3h in 800 DEG C, then take appropriate amount of sample to be scattered in boiling water bath in the sodium hydroxide solution that molar concentration is 1mol/L and be heated to reflux 3h, by its surface-functionalized process, question response is washed with deionized after cooling to neutrality after terminating, and obtains the most flower-shaped copper of black powder sample/copper oxide complexes carrier after drying；Take the flower-shaped copper of 40mg/copper oxide complexes carrier and 100mg sodium citrate ultrasonic disperse in water/alcohol mixed solution that volume ratio is 1:1, add 5mL noble metal precursor body H2PtCl6With 5mL noble metal precursor body Na2PdCl4And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.
Embodiment 5
Take 5g copper chloride, 3g glucose and 5g cetyl trimethylammonium bromide and be dissolved in wiring solution-forming in 30mL deionized water, then in 150 DEG C of hydro-thermal reactions 48h, and by product through deionized water and absolute ethanol washing several times, obtain black powder product after drying；Prepared black powder product is placed in tube-type atmosphere furnace and calcines 3h in 800 DEG C, then take appropriate amount of sample to be scattered in boiling water bath in the sodium hydroxide solution that molar concentration is 0.5mol/L and be heated to reflux 1h, by its surface-functionalized process, question response is washed with deionized after cooling to neutrality after terminating, and obtains the most flower-shaped copper of black powder sample/copper oxide complexes carrier after drying；Take the flower-shaped copper of 40mg/copper oxide complexes carrier and 100mg sodium citrate ultrasonic disperse in the water that volume ratio is 1:1/methanol mixed solution, add 5mL noble metal precursor body H2PtCl6With 5mL noble metal precursor body RuCl3And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.
Comparative example 1
Illustrate as a example by multi-walled carbon nano-tubes (MWCNTs) carried noble metal Pt makees catalyst.Take 40mg carrier MWCNTs and 100mg sodium citrate ultrasonic disperse in water/ethanol solution that volume ratio is 1:1, add 10mL noble metal precursor body H2PtCl6And the pH regulating reaction system is 10, it is washed with deionized and puts in vacuum drying oven after being subsequently adding KBH4 reduction and be dried in 40 DEG C, finally obtain black objects product.
Comparative example 2
Illustrate as a example by XC-72 carried noble metal Pt makees catalyst.Take 40mg carrier XC-72 and 100mg sodium citrate ultrasonic disperse in water/ethanol solution that volume ratio is 1:1, add 10mL noble metal precursor body H2PtCl6And the pH regulating reaction system is 10, it is subsequently adding KBH4It is washed with deionized after reduction and puts in vacuum drying oven and be dried in 40 DEG C, finally obtain black objects product.
Embodiment 6
Take flower-shaped copper/copper oxide load platinum catalyst (Pt/F-Cu/CuO), the prepared Pt/MWCNTs catalyst of comparative example 1 and the prepared Pt/XC-72 catalyst of comparative example 2 that the embodiment 1 of equivalent (3mg) prepares respectively, it is dispersed in dispersant, add PEM (Nafion), it is coated in glassy carbon electrode surface after ultrasonic for mixed liquor, use composition three-electrode system, measured the electrocatalysis characteristic of this catalyst by electrochemical workstation.This catalyst is to the cyclic voltammetry curve of methanol, ethanol, ethylene glycol and glycerol as shown in Figure 3, our experiments show that, the electro-catalysis oxidation of alcohols performance of flower-shaped copper/copper oxide load platinum catalyst that embodiment 1 prepares is better than carbon nanotube carrier in comparative example (MWCNTs) and the prepared catalyst of carbon black-supported (XC-72).
The flower-shaped copper of the present invention/copper oxide composite micro-nano rice material support load unitary, binary noble metal make catalyst, it is adaptable to the catalysis oxidation of multiple little molecule acids and alcohols, and have good electro catalytic activity and stability.Drawn by comparative example, compared with traditional carbon black and carbon nanotube carrier, electro catalytic activity and the stability of the flower-shaped copper invented/copper oxide complexes carrier supported precious metal catalyst are more excellent, are a kind of fuel-cell catalysts with broad prospect of application.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage; skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; under the scope without departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements each fall within the scope of protection of the invention.
Claims (6)
1. the preparation method of flower-shaped copper/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterised in that concretely comprise the following steps:
(1) with copper chloride for copper source, glucose is carbon source, and cetyl trimethylammonium bromide is surfactant and structure directing agent, and deionized water is solvent, in 150-200 DEG C of hydro-thermal reaction 9-48h, product is dried to obtain after deionized water and absolute ethanol washing black powder product；
(2) the black powder product that step (1) obtains is placed in tube furnace in 800 DEG C of calcining 3h, then take out sample dispersion and be heated to reflux 1-5h in the aqueous slkali that molar concentration is 0.5-3mol/L, question response cools down after terminating and is washed with deionized to neutrality, obtains flower-shaped copper/copper oxide complexes carrier after drying；
(3) flower-shaped copper/copper oxide complexes carrier step (2) obtained and sodium citrate ultrasonic disperse are in water-alcohol solution, add noble metal precursor body and to regulate the pH of reaction system be 10, washing and be dried to obtain the flower-shaped copper of target product/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst after being subsequently adding reducing agent reduction, wherein noble metal precursor body is H2PtCl6、Na2PdCl4、RuCl3Or RhCl3In one or more, reducing agent is KBH4、NaBH4, ascorbic acid, hydrazine hydrate, H2Or CO.
The preparation method of flower-shaped copper the most according to claim 1/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterized in that: described copper chloride is 1:10-10:1 with the mass ratio of glucose, copper chloride is 1:20-20:1 with the mass ratio of cetyl trimethylammonium bromide.
The preparation method of flower-shaped copper the most according to claim 1/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterised in that: described aqueous slkali is potassium hydroxide solution, sodium hydroxide solution or ammonia spirit.
The preparation method of flower-shaped copper the most according to claim 1/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterized in that: the pattern of described flower-shaped copper/copper oxide complexes carrier is the radial flower type structure of multidimensional, its a size of 1-5 μm.
The preparation method of flower-shaped copper the most according to claim 1/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterised in that: described noble metal active component is Pt, Pd, PtPd, PtRu, PtRh, PdRu or PdRh.
The preparation method of flower-shaped copper the most according to claim 1/copper oxide Micron-nano composites carried noble metal fuel-cell catalyst, it is characterised in that: in described water-alcohol solution, water is 1:1 with the volume ratio of alcohol, and alcohol is specially methanol, ethanol or propanol.
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| CN108906049A (en) * | 2018-06-25 | 2018-11-30 | 山东京博石油化工有限公司 | The preparation method and photoelectrocatalysis of flower-shaped copper oxide restore CO2Method |
| CN114149023A (en) * | 2021-12-02 | 2022-03-08 | 南京工程学院 | High-value conversion and reuse method for tobacco waste |
| CN114436316A (en) * | 2020-11-03 | 2022-05-06 | 中国石油天然气集团有限公司 | Monodisperse flower-shaped copper oxide/carbon nano composite material and preparation method thereof |
| CN114984953A (en) * | 2022-06-09 | 2022-09-02 | 陕西科技大学 | Preparation method of Cu/CuO electrocatalytic material loaded on carbon substrate |
| CN115160605A (en) * | 2022-06-21 | 2022-10-11 | 沪本新材料科技（上海）有限公司 | Preparation method of mixed-valence copper ion antibacterial masterbatch |
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| CN115160605A (en) * | 2022-06-21 | 2022-10-11 | 沪本新材料科技（上海）有限公司 | Preparation method of mixed-valence copper ion antibacterial masterbatch |
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| CN115925054A (en) * | 2022-10-31 | 2023-04-07 | 南京工业大学 | Preparation method and application of membrane bubble phase synthesis carbon electrode composite material |
| CN115925054B (en) * | 2022-10-31 | 2023-12-19 | 南京工业大学 | Preparation method and application of membrane bubble phase synthetic carbon electrode composite material |
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