CN106532072A - Preparation method of copper phosphide composite material electrocatalyst - Google Patents

Preparation method of copper phosphide composite material electrocatalyst Download PDF

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Publication number
CN106532072A
CN106532072A CN201611163563.8A CN201611163563A CN106532072A CN 106532072 A CN106532072 A CN 106532072A CN 201611163563 A CN201611163563 A CN 201611163563A CN 106532072 A CN106532072 A CN 106532072A
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carbon
composite material
preparation
copper
phosphatization
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CN106532072B (en
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孙蓉
陈珍
符显珠
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention provides a preparation method of a copper phosphide composite material electrocatalyst. The method comprises the steps of adding a copper salt to a water solution of lauryl sodium sulfate, adding a palladium salt, sodium hydroxide and hydroxylamine hydrochloride, stirring at a room temperature to obtain a Cu(OH)2 composite material; and burning the Cu(OH)2 composite material and monohydrate sodium phosphate in an inert gas to obtain the copper phosphide composite material electrocatalyst. The catalytic efficiency of the copper phosphide composite material electrocatalyst is relatively high.

Description

The preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst
Technical field
The present invention relates to electro-catalysis technical field, more particularly to a kind of preparation for phosphatization carbon/carbon-copper composite material elctro-catalyst Method.
Background technology
With the worsening shortages of Fossil fuel, people are continuously increased to the demand of the energy so that research regenerative resource tool There is very important meaning.Glucose is a kind of most wide monosaccharide of distributed in nature, is widely distributed in organism.Glucose can For biological fuel cell, the renewable sources of energy can be obtained by the glucose in electrocatalytic oxidation biological fuel cell.Additionally, Jing is normal The content of internal glucose is determined for treatment diabetes are very important, and the measure of glucose is generally by electro-catalysis Oxidizing glucose.Therefore research can the glycoxidative elctro-catalyst of efficient catalytic Fructus Vitis viniferae have very important significance.
The content of the invention
In view of this, it is in order to overcome the defect and problem of prior art, of the invention to provide a kind of catalytic efficiency higher phosphorus Change the preparation method of carbon/carbon-copper composite material elctro-catalyst.
A kind of preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst, including：
Mantoquita is added in the aqueous solution of sodium lauryl sulphate, palladium salt, sodium hydroxide and oxammonium hydrochloride. is subsequently adding, It is stirred at room temperature, obtains Cu (OH)2Composite；
By the Cu (OH)2Composite and one hydration sodium hypophosphite calcine under an inert gas obtain phosphorized copper be combined Material elctro-catalyst.
Wherein in one embodiment, the mantoquita be copper chloride, copper nitrate or copper sulfate, the mantoquita and described 12 The mass ratio of alkyl sodium sulfate is 7:400-600.
Wherein in one embodiment, in the aqueous solution of the sodium lauryl sulphate, the sodium lauryl sulphate Concentration is 0.08～0.50mol L-1, the mantoquita is added to Cu after the aqueous solution of the sodium lauryl sulphate2+Concentration is 2-8mM。
Wherein in one embodiment, the concentration of the sodium hydroxide is 0.2-2.5M, and volume is 10-250mL；The salt The concentration of sour azanol is 0.1M-0.4M, and volume is 7-30mL.
Wherein in one embodiment, the mass ratio of the palladium salt, sodium hydroxide and oxammonium hydrochloride. is 1:100-300:20- 60, the mass ratio of the mantoquita and the palladium salt is 24:1-6.
Wherein in one embodiment, the palladium salt is Palladous chloride., palladium sulfate or Palladous nitrate..
Wherein in one embodiment, by the Cu (OH)2Composite and a hydration sodium hypophosphite are in tube furnace Calcine under noble gases, and calcining heat is 220～500 DEG C, calcination time is 1～5h.
Wherein in one embodiment, Cu (OH)2Composite and described one mass ratio for being hydrated sodium hypophosphite It is 1:5～50.
Wherein in one embodiment, Cu (OH)2Composite and described one mass ratio for being hydrated sodium hypophosphite It is 1:25.
Wherein in one embodiment, the noble gases are nitrogen.
In the preparation method of above-mentioned phosphatization carbon/carbon-copper composite material elctro-catalyst, there is height using elctro-catalyst prepared by the method Specific surface area and many avtive spots, so as to the catalysis activity of catalysis glucose is greatly improved, and whole experiment process is simple to operate, With short production cycle, stable chemical nature is glycoxidative to Fructus Vitis viniferae with very high catalysis activity and selectivity.
Description of the drawings
Fig. 1 is the preparation method flow chart of the phosphatization carbon/carbon-copper composite material elctro-catalyst of an embodiment；
Copper hydrate composites of the Fig. 2 for embodiment 3, the phosphatization carbon/carbon-copper composite material elctro-catalyst of embodiment 4, embodiment The cyclic voltammetry curve of 5 oxidation carbon/carbon-copper composite material.
Specific embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing Give the better embodiment of the present invention.The preferred embodiments of the present invention are these are only, the special of the present invention is not thereby limited Sharp scope, equivalent structure or equivalent flow conversion that every utilization description of the invention and accompanying drawing content are made, directly or Connect and be used in other related technical fields, be included within the scope of the present invention.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field for belonging to the present invention The implication that technical staff is generally understood that is identical.The term for being used in the description of the invention herein is intended merely to description tool The purpose of the embodiment of body, it is not intended that of the invention in limiting.Term as used herein " and/or " include one or more The arbitrary and all of combination of related Listed Items.
Fig. 1 is referred to, the preparation method of the phosphatization carbon/carbon-copper composite material elctro-catalyst of an embodiment comprises the steps：
S110, mantoquita is added in the aqueous solution of sodium lauryl sulphate, is subsequently adding palladium salt, sodium hydroxide and hydrochloric acid Azanol, is stirred at room temperature, and obtains Cu (OH)2Composite.
In one embodiment, in S110, in the aqueous solution of sodium lauryl sulphate, the concentration of sodium lauryl sulphate is 0.08～0.50mol L-1.Preferably, the concentration of sodium lauryl sulphate is 0.15mol L-1.Mantoquita is added to into 12 In operation in the aqueous solution of alkyl sodium sulfate, mantoquita is 7 with the mass ratio of sodium lauryl sulphate:400-600.In solution Cu2+Concentration is 2-8mM.
In one embodiment, in S110, in adding the operation of palladium salt, sodium hydroxide and oxammonium hydrochloride., the hydrogen-oxygen of addition The concentration for changing sodium is 0.2-2.5M, and volume is 10-250mL.The concentration of oxammonium hydrochloride. is 0.1M-0.4M, and volume is 7-30mL.
In one embodiment, in S110, mantoquita is copper chloride, copper nitrate or copper sulfate.
In one embodiment, in S110, palladium salt is Palladous chloride., palladium sulfate or Palladous nitrate..
In one embodiment, in S110, the mass ratio of palladium salt, sodium hydroxide and oxammonium hydrochloride. is 1:100-300:20- 60。
In one embodiment, in S110, the mass ratio of mantoquita and palladium salt is 24：1-6.
In one embodiment, in S110, the material after 2h or so will be stirred at room temperature and be centrifuged, then it is molten with ethanol Liquid cleaning is multiple, and vacuum drying oven obtains Cu (OH) after being dried2Composite.Wherein, in ethanol solution water and ethanol volume ratio For 1:1, the temperature that vacuum drying oven is dried is 50 DEG C, and drying time is 6h.
S120, by the Cu (OH)2Composite and a hydration sodium hypophosphite are calcined under an inert gas and obtain phosphatization Carbon/carbon-copper composite material elctro-catalyst.
In one embodiment, in S120, Cu (OH)2Composite and hydration sodium hypophosphite inertia in tube furnace The calcining heat calcined under gas is 220～500 DEG C.Preferably 250 DEG C.
In one embodiment, in S120, Cu (OH)2Composite is forged under an inert gas with a hydration sodium hypophosphite The calcination time of burning is 1～5h.Preferably 2h.
In one embodiment, in S120, Cu (OH)2Composite with described one hydration sodium hypophosphite mass ratio be 1:5～50.Preferably, Cu (OH)2Composite is 1 with the mass ratio of described one hydration sodium hypophosphite:25.
In one embodiment, in S120, noble gases are nitrogen.
Phosphatization carbon/carbon-copper composite material elctro-catalyst prepared by said method has high-specific surface area and many avtive spots, so as to pole The big catalysis activity for improving catalysis glucose, and whole experiment process is simple to operate, with short production cycle, stable chemical nature, it is right Fructus Vitis viniferae is glycoxidative with very high catalysis activity and selectivity.
Embodiment
Embodiment 1
By 7mL 0.1M CuCl2In adding the 150mL water containing 8.7g sodium lauryl sulphates, 5mg is subsequently adding PdCl2, 25mL 1M NaOH, 15mL 0.2M NH22h is stirred under OH HCl, room temperature, is centrifuged, with water and ethanol with volume ratio 1: 1 cleaning four times, 50 DEG C of vacuum drying ovens are dried 6h, that is, Copper hydrate composite is obtained；
By above-mentioned Copper hydrate composite and a hydration sodium hypophosphite with mass ratio 1:25 are put in tube furnace in nitrogen The lower 250 DEG C of calcinings 2h of gas, that is, be obtained phosphatization carbon/carbon-copper composite material elctro-catalyst.
Embodiment 2
Copper hydrate composite in embodiment 1 is put in in tube furnace 250 DEG C of calcining 2h under a nitrogen, that is, oxidation is obtained Carbon/carbon-copper composite material.
Embodiment 3
The Copper hydrate composite that embodiment 1 is prepared is with 4mg mL-1It is scattered in dehydrated alcohol, takes 14 μ L The glass-carbon electrode handled well is dropped in, 10 μ L 0.1%nafion of Deca again after drying, after drying, with which as working electrode, platinized platinum Electrode is that, to electrode, Ag/AgCl is reference electrode, contains 4mM glucoses by bottom liquid of 0.1M KOH, to sweep fast 50mV s-1Survey Which is tried to glucose catalytic performance, evaluation result is shown in accompanying drawing 2.
Embodiment 4
Phosphorized copper composite catalyst prepared by embodiment 1 is with 4mg mL-1It is scattered in dehydrated alcohol, evaluation side Method such as embodiment 3, evaluation result are shown in accompanying drawing 2.
Embodiment 5
Embodiment 2 is prepared into oxidation carbon/carbon-copper composite material with 4mg mL-1It is scattered in dehydrated alcohol, evaluation methodology is as implemented Example 3, evaluation result are shown in accompanying drawing 2.
According to Fig. 2 evaluation results, phosphatization carbon/carbon-copper composite material elctro-catalyst is more preferable to glucose catalytic performance.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the guarantor of the present invention Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.

Claims (10)

1. a kind of preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst, it is characterised in that include：
Mantoquita is added in the aqueous solution of sodium lauryl sulphate, palladium salt, sodium hydroxide and oxammonium hydrochloride. is subsequently adding, in room Temperature is lower to be stirred, and obtains Cu (OH)2Composite；
By the Cu (OH)2Composite and a hydration sodium hypophosphite are calcined under an inert gas and obtain phosphatization carbon/carbon-copper composite material Elctro-catalyst.
2. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that the mantoquita For copper chloride, copper nitrate or copper sulfate, the mantoquita is 7 with the mass ratio of the sodium lauryl sulphate:400-600.
3. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that described 12 In the aqueous solution of alkyl sodium sulfate, the concentration of the sodium lauryl sulphate is 0.08～0.50mol L-1, the mantoquita addition The Cu to after the aqueous solution of the sodium lauryl sulphate2+Concentration is 2-8mM.
4. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that the hydrogen-oxygen The concentration for changing sodium is 0.2-2.5M, and volume is 10-250mL；The concentration of the oxammonium hydrochloride. is 0.1M-0.4M, and volume is 7- 30mL。
5. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that the palladium The mass ratio of salt, sodium hydroxide and oxammonium hydrochloride. is 1:100-300:The mass ratio of 20-60, the mantoquita and the palladium salt is 24:1-6。
6. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that the palladium salt For Palladous chloride., palladium sulfate or Palladous nitrate..
7. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that by the Cu (OH)2Composite and a hydration sodium hypophosphite are calcined under noble gases in tube furnace, and calcining heat is 220～500 DEG C, calcination time is 1～5h.
8. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that the Cu (OH)2Composite is 1 with the mass ratio of described one hydration sodium hypophosphite:5～50.
9. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 8, it is characterised in that the Cu (OH)2Composite is 1 with the mass ratio of described one hydration sodium hypophosphite:25.
10. the preparation method of phosphatization carbon/carbon-copper composite material elctro-catalyst according to claim 1, it is characterised in that described lazy Property gas be nitrogen.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108483404A (en) * 2018-04-20 2018-09-04 中国科学技术大学 A kind of preparation method of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2031685A1 (en) * 2007-08-31 2009-03-04 Samsung SDI Co., Ltd. Cathode Catalyst, Method for Preparing the Same, Membrane-Electrode Assembly and Fuel Cell System Including the Same
CN105552394A (en) * 2015-12-09 2016-05-04 郑州轻工业学院 Method for solid phase reaction one-step preparation of reduced graphene oxide/palladium composite nanometer electrocatalyst
CN105772041A (en) * 2014-12-25 2016-07-20 中国科学院理化技术研究所 Photocatalysis hydrogen production promoter, photocatalysis system and hydrogen production method
CN105944743A (en) * 2016-05-17 2016-09-21 天津大学 Preparation method of Ni-P nano-particles having eggshell structure and applied to catalytic hydrogen production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2031685A1 (en) * 2007-08-31 2009-03-04 Samsung SDI Co., Ltd. Cathode Catalyst, Method for Preparing the Same, Membrane-Electrode Assembly and Fuel Cell System Including the Same
CN105772041A (en) * 2014-12-25 2016-07-20 中国科学院理化技术研究所 Photocatalysis hydrogen production promoter, photocatalysis system and hydrogen production method
CN105552394A (en) * 2015-12-09 2016-05-04 郑州轻工业学院 Method for solid phase reaction one-step preparation of reduced graphene oxide/palladium composite nanometer electrocatalyst
CN105944743A (en) * 2016-05-17 2016-09-21 天津大学 Preparation method of Ni-P nano-particles having eggshell structure and applied to catalytic hydrogen production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108483404A (en) * 2018-04-20 2018-09-04 中国科学技术大学 A kind of preparation method of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet

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