CN106582712A - Catalyst for hydrogen production through water electrolysis and preparation method thereof - Google Patents
Catalyst for hydrogen production through water electrolysis and preparation method thereof Download PDFInfo
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- CN106582712A CN106582712A CN201611167015.2A CN201611167015A CN106582712A CN 106582712 A CN106582712 A CN 106582712A CN 201611167015 A CN201611167015 A CN 201611167015A CN 106582712 A CN106582712 A CN 106582712A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000010949 copper Substances 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical group B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010277 boron hydride Inorganic materials 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229910001260 Pt alloy Inorganic materials 0.000 abstract description 3
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- SUDAKAMJKXJTSA-UHFFFAOYSA-N O.O.O.[N+](=O)(O)[O-].[Cu] Chemical compound O.O.O.[N+](=O)(O)[O-].[Cu] SUDAKAMJKXJTSA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/23—
-
- B01J35/393—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a catalyst for hydrogen production through water electrolysis. The catalyst is carbon-carrying nanometer copper platinum alloy. The catalyst provided by the invention has more active sites; the electrochemical catalysis efficiency is improved; meanwhile, copper is added, so that the carrying capacity of platinum is reduced; the cost is further reduced; due to the cooperated effect between metals, the platinum copper alloy can effectively reduce the overpotential of electrochemical reaction; the voltage of an electrolytic tank is reduced; the energy consumption cost is reduced. The invention also provides a preparation method of the catalyst.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more particularly to a kind of catalyst and its system of water electrolysis hydrogen production
Preparation Method.
Background technology
With the transition exploitation and utilization of fossil energy and increasingly increasing for Global Environmental Problems, the skill of new cleaning fuel
Art is developed and scale application increasingly obtains people's attention, such as solar energy, wind energy and tide energy.Wherein, hydrogen is available
Water being obtained, wide material sources.Meanwhile, the combustion heat value of hydrogen is high and combustion product is pollution-free.Therefore, hydrogen energy source has wide
DEVELOPMENT PROSPECT.
At present, the method for industrial hydrogen manufacturing mainly has water electrolysis hydrogen production, vaporizes by energy hydrogen manufacturing, biomass of fossil fuel
And biohydrogen, meanwhile, the accessory substance of the industry such as pyrolysis, fermentation, petrochemical industry can also obtain hydrogen.Water electrolysis hydrogen production is more to hold
Industrialized production method is easily realized, with electrolytic cell as reaction system, certain external voltage is applied in anode and cathode, negative electrode occurs
Evolving hydrogen reaction, realizes conversion of the electric energy to chemical energy, obtains the higher hydrogen of purity.
However, the high energy consumption in electrolytic process makes power cost become the subject matter of restriction electrochemistry hydrogen manufacturing development.Together
When, platinum reacts the price of one of cathod catalyst of full blast, its rare resource amount of storage and costliness as electrolysis water
Govern the application and development of electrochemistry hydrogen manufacturing.
The content of the invention
The present invention is directed to above-mentioned electrolysis water catalyst high cost, a kind of low deficiency of electrochemical efficiency, there is provided nanometer platinoid
The composite of alloy and carbon black is used as electrochemistry catalyst for preparing hydrogen and preparation method thereof.
A kind of catalyst of water electrolysis hydrogen production, the catalyst is carbon-supported nanometer Mock gold.
According to an embodiment of the present invention, platinum accounts for the 5%-15% of the alloy gross mass in the catalyst.
Another embodiment of the invention, the nanometer Mock gold accounts for more than the 80% of the catalyst quality.
Another embodiment of the invention, the crystallite dimension of the nanometer Mock gold is 2-20 nanometers.
A kind of preparation method of above-mentioned catalyst, comprises the steps：
S1：In mass ratio example weighs copper source compound, platinum source compound and stabilizer, respectively by copper source compound,
Platinum source compound and the stabilizer formation aqueous solution soluble in water；By the platinum source compound aqueous solution, the copper source compound aqueous solution
Precursor solution is mixed to get with the aqueous solution of stabilizer；
S2：Carbon-supported body is added in the precursor solution, it is dispersed；And
S3：Reducing agent is added in the solution of S2 steps formation, fully reaction.
According to an embodiment of the present invention, the platinum source compound is chloroplatinic acid hexahydrate.
Another embodiment of the invention, the stabilizer be water-soluble lemon acid and salt, polyvinylpyrrolidone,
In ethylenediamine tetra-acetic acid one or more.
Another embodiment of the invention, the carbon-supported body be carbon black, acetylene black, Ketjen black, carbon nano-fiber,
One or more in CNT.
Another embodiment of the invention, the reducing agent is a kind of in boron hydride, ascorbic acid, tartrate
Or it is several, the mole of the reducing agent is 3-6 times of metal molar amount.
Another embodiment of the invention, before S3 steps, also makes reduction reaction including persistently logical high pure nitrogen
Process is in high pure nitrogen protection step.
Relative to prior art, the Platinum Nanoparticles Cu alloy material for loading on the activated carbon of the preparation of the present invention is used as electrification
The catalyst of length of schooling hydrogen, because nano material specific surface area is larger, makes unit mass catalyst have more avtive spots, carries
High electrochemical catalytic efficiency.The addition of copper simultaneously reduces the carrying capacity of platinum, reduce further cost.Also, due between metal
Synergy, Mock gold can effectively reduce the overpotential of electrochemical reaction, reduce electrolytic cell voltage, reduce energy
Consumption cost.
Description of the drawings
Its example embodiment is described in detail by referring to accompanying drawing, above and other feature and advantage of the present invention will become
Become apparent from.
Fig. 1 is the X-ray diffraction result of the PtCu/C catalyst of the present invention；
Fig. 2 is the Pt of the present invention0.1Cu0.9/ C is the polarization curve of catalyst；
Fig. 3 is the polarization curve contrast of the different catalysts of the present invention；And
Fig. 4 is the different Pt of the present invention：Cu ratios (5：95、10：90、15：85) polarization curve of PtCu/C catalyst
Contrast.
Specific embodiment
The present invention is elaborated with reference to specific embodiment.
The carbon-supported Nanometer Copper platinum alloy catalyst of the present invention, reduces the carrying capacity of platinum in electrolysis water catalyst, improves platinum
Utilization rate is the effective means of reduces cost.
The catalyst of the present invention is the Nanometer Copper platinum alloy being supported on carbon-supported body, and the preparation method of catalyst includes
S1：Prepare precursor solution step；S2：Add carbon-supported body step；S3：Wet-chemical reduction step.However, people in the art
Member is appreciated that the preparation method of the present invention is not intended to be limited to above-mentioned 3 steps, in addition to above-mentioned 3 step, can also wrap
Include pre-filtration step for example described later, cleaning step, drying steps and pulverising step etc..
Hereinafter, above-mentioned operation S1～S3 and other operations are illustrated successively.
S1：Prepare precursor solution step
In mass ratio example weighs copper source compound, platinum source compound and stabilizer, respectively by copper source compound, platinum source chemical combination
Thing and the stabilizer formation aqueous solution soluble in water.By the water of the platinum source compound aqueous solution, the copper source compound aqueous solution and stabilizer
Solution is mixed to get precursor solution.
Copper source can be its water-soluble inorganic mantoquita chemical combination such as cupric nitrate trihydrate cupric nitrate trihydrate or copper chloride
Thing.Copper source compound is 1g with the mass volume ratio of water:10～20mL.
Platinum source can be chloroplatinic acid hexahydrate.Platinum source compound is 1g with the mass volume ratio of water:200～300mL.
Stabilizer can be one or more in water-soluble lemon acid and salt, polyvinylpyrrolidone, ethylenediamine tetra-acetic acid.
The mass volume ratio of stabilizer and water is 1g:10～20mL.
S2：Add carbon-supported body step
Carbon-supported body is added in precursor solution, it is dispersed.The mass volume ratio of carbon black and deionized water is 1g:
15000～17000mL.The ratio of the quality of carbon black and two kinds of metallic element quality sums is 1:3～4.
For the carbon-supported body of the present invention, as long as being typically used for the carbon-supported body of catalyst, it is not particularly limited, for example
Can be one or more in carbon black, acetylene black, Ketjen black, carbon nano-fiber, CNT.With carbon black in following examples
(VXC-72) as a example by, but it is not limited.
Dispersed can by the way of ultrasonic disperse, but be not limited, or other dispersing modes.
S3：Wet-chemical reduction step
Reducing agent is added in the solution of S2 steps formation, fully reaction.
Course of reaction can be carried out in ice bath, and reductant solution is added dropwise in reaction system.
Reducing agent can be one or more in boron hydride, ascorbic acid, tartrate.Concentration can be 0.05-
0.015mol·L-1.The mole of reducing agent is 3-6 times of metal molar amount.
Before reduction step is carried out, high pure nitrogen protection can be led to.Stirring is excluded after oxygen, is added dropwise over above-mentioned preparation
Reducing agent aqueous solution.The amount ratio for making the material of metallic element and reducing agent is 1:5～10, and in ice bath environment and nitrogen protective atmosphere
Enclose lower persistently stirring 8-10 hours.
In addition to above-mentioned steps, after reaction is stopped, solid particulate matter can be isolated using Vacuum filtration device.It is used in combination
After products therefrom is washed 6-8 time by deionized water, dry, grind stand-by.
Catalyst preparation
Embodiment 1
Weigh 1g chloroplatinic acid hexahydrates and be dissolved in 250mL deionized waters and be formulated as platinum acid chloride solution；Weigh 3g nitric acid
Copper trihydrate is dissolved in 250mL deionized waters and is formulated as copper nitrate solution；Weigh 18.75g two citric acid monohydrate trisodiums molten
Solution is formulated as sodium citrate solution in 250mL deionized waters；Sodium borohydride aqueous solution is prepared in ice bath environment, concentration is
0.15mol·L-1。
The VXC-72 carbon blacks of 30mg are weighed, by the way of ultrasonic disperse, in being dispersed in 500mL deionized waters.Measure respectively
Platinum acid chloride solution, 28.36mL copper nitrate solutions and the 40mL two citric acid monohydrate trisodiums solution of the above-mentioned preparations of 4.05mL are taken, is added
Wherein and it is stirred, mixing time is 2 hours.Above-mentioned mixed liquor is placed in ice bath environment and stirs and lead to nitrogen protection.Stir
After mixing 1 hour, the sodium borohydride aqueous solution of the above-mentioned preparations of 52mL is added dropwise over.Enclose lower lasting in ice bath environment and nitrogen protective atmosphere
Stirring 8-10 hours, stop reaction.And solid particulate matter is isolated using Vacuum filtration device.Deionized water is by products therefrom
After washing 6-8 time, dry, grind stand-by.The amount ratio of the material of as Pt and Cu is 1:9 PtCu/C catalyst
(Pt0.1Cu0.9/C)。
Embodiment 2
Method similarly to Example 1 is adopted to prepare the amount ratio of Pt and Cu materials for 0.5:9.5 PtCu/C catalyst
(Pt0.05Cu0.95/C)。
Embodiment 3
Method similarly to Example 1 is adopted to prepare the amount ratio of Pt and Cu materials for 1.5:8.5 PtCu/C catalyst
(Pt0.15Cu0.85/C)。
Electro-chemical test
Tested using monocell, carried out on CHI660d (Shanghai occasion China) electrochemical workstation.With the preparation of embodiment 1-3
Material be cathod catalyst, Ir is black for anode catalyst, and nafion115 films (Du Pont) are PEM, using direct-injection
Mode prepares membrane electrode.To be coated with supporting layer of the eastern beautiful Toray hydrophobics carbon paper of gas diffusion layers as membrane electrode.Anode and the moon
The work area of the electrode of pole is 5cm-2, and the load capacity of metallic catalyst is 1mgcm-2.It is compacted used in test process
Dynamic pump is with 3mLmin-1Flow velocity give anode water flowing, negative electrode then opens sky.Test temperature is 25 DEG C.
Characterization test result
To gained catalyst Pt0.1Cu0.9/ C sample carries out X-ray diffraction test, and its result is as shown in Figure 1.
Can observe wider peak type explanation metallic particles from figure to be evenly distributed in less grain size range
On carbon carrier.There is strong diffraction maximum in 2 θ=42.57 °, 48.97 ° and 70.99 °, correspond to respectively Cu metals (006), (404) and
(048) crystal face, wherein comparing with Cu base peaks, there occurs significantly negative shifting.Thus, sample main component is Mock gold.
The crystallite dimension that can calculate metallic particles according to Scherrer formula is 3.6nm.
Fig. 2 is Pt0.1Cu0.9The polarization curve of/C catalyst.Current density under different potentials see the table below 1.Can from table
Know, when catalyst has started peak when current potential is 1.6V, current density is raised with the rising of current potential.
The Pt of table 10.1Cu0.9The electrolysis data of/C catalyst
If Fig. 3 is respectively with prepared PtCu/C, Pt be black and Cu/C is tested as catalyst polarization curve.It is used
PtCu/C catalyst in Pt and Cu material amount ratio be 1:9, it can be seen that compared with Cu/C, PtCu/
C electrocatalysis characteristics have increased significantly.Compare and make catalyst with pure Pt, the PtCu/C of phase homogenous quantities equally shows more
Excellent performance.It is well known that Pt is compared to Cu, it is more suitable for making electrolysis water catalyst.PtCu/C catalysis prepared by the present invention
Agent, due to the interaction between platinoid, although the consumption of Pt is greatly lowered, has obtained catalytic effect more more preferable than pure Pt.
Fig. 4 is the polarization curve contrast of the PtCu/C of Pt and Cu different mol ratio examples.It can be seen that as Pt contains
The increase of amount, catalytic effect is in enhanced trend.However, Pt0.1Cu0.9/ C catalyst shows in relatively low potential range
More preferable chemical property, under the current potential of 1.5V, 1.6V and 1.7V, current density is respectively 10.58,22.59 and
34.31mA·cm-2.I.e. under relatively low current potential, higher current density is obtained, groove pressure, reducing energy consumption can have been reduced.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Know those skilled in the art and work as and various corresponding changes and deformation, but these corresponding changes and change can be made according to the present invention
Shape should all belong to the protection domain of appended claims of the invention.
Claims (10)
1. a kind of catalyst of water electrolysis hydrogen production, it is characterised in that the catalyst is carbon-supported nanometer Mock gold.
2. catalyst according to claim 1, it is characterised in that platinum accounts for the alloy gross mass in the catalyst
5%-15%.
3. catalyst according to claim 1, it is characterised in that the nanometer Mock gold accounts for the catalyst quality
More than 80%.
4. catalyst according to claim 1, it is characterised in that the crystallite dimension of the nanometer Mock gold is received for 2-20
Rice.
5. the preparation method of catalyst according to claim 1, it is characterised in that comprise the steps：
S1：In mass ratio example weighs copper source compound, platinum source compound and stabilizer, respectively by copper source compound, platinum source
Compound and the stabilizer formation aqueous solution soluble in water；By the platinum source compound aqueous solution, the copper source compound aqueous solution and steady
The aqueous solution for determining agent is mixed to get precursor solution；
S2：Carbon-supported body is added in the precursor solution, it is dispersed；And
S3：Reducing agent is added in the solution of S2 steps formation, fully reaction.
6. preparation method according to claim 5, it is characterised in that the platinum source compound is chloroplatinic acid hexahydrate.
7. preparation method according to claim 5, it is characterised in that the stabilizer is water-soluble lemon acid and salt, poly-
In vinylpyrrolidone, ethylenediamine tetra-acetic acid one or more.
8. preparation method according to claim 5, it is characterised in that the carbon-supported body is carbon black, acetylene black, section's qin
One or more in black, carbon nano-fiber, CNT.
9. preparation method according to claim 5, it is characterised in that the reducing agent is boron hydride, ascorbic acid, wine
In stone hydrochlorate one or more, the mole of the reducing agent is 3-6 times of metal molar amount.
10. preparation method according to claim 5, it is characterised in that before S3 steps, also including persistently leading to High Purity Nitrogen
Gas makes reduction reaction process be in high pure nitrogen protection step.
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