CN108315771B - A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst - Google Patents
A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst Download PDFInfo
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- CN108315771B CN108315771B CN201810141113.1A CN201810141113A CN108315771B CN 108315771 B CN108315771 B CN 108315771B CN 201810141113 A CN201810141113 A CN 201810141113A CN 108315771 B CN108315771 B CN 108315771B
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 54
- 239000011888 foil Substances 0.000 claims abstract description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000502 dialysis Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 150000003384 small molecules Chemical class 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 13
- 239000008151 electrolyte solution Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- 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
- B01J23/72—Copper
-
- B01J35/33—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of electrochemical preparing methods of sub-nanometer size copper particle elctro-catalyst, this method includes that graphite is placed in sulfuric acid and nitric acid volume ratio for the in the mixed solvent of 3:1, taking-up is placed in the remaining acid of dialysis removal, the graphite oxide foil expanded in deionized water after saving 4-12h at room temperature；Graphite oxide foil is placed in water heating kettle, and thiourea solution is added under the conditions of 120-180 DEG C, hydro-thermal reaction 4-12h, taking-up, which is placed in deionized water, gives remaining small molecule, obtains the graphite foil doped with nitrogen sulphur；Using doped with the graphite foil of nitrogen sulphur, as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is placed in electrolyte solution as reference electrode, and accesses the deposition that constant potential carries out the corresponding time, obtains various sizes of sub-nanometer copper particle.Through the above scheme, invention achieves the purposes that can get various sizes of sub-nanometer particle, have very high practical value and promotional value.
Description
Technical field
The present invention relates to nanocatalyst preparation technical field more particularly to a kind of sub-nanometer size copper particle elctro-catalysts
Electrochemical preparation method.
Background technique
Copper nano-particle achieves wide in the reaction such as organic reaction, light-catalyzed reaction, electrocatalytic reaction and gas phase reaction
General application.Since the catalytic activity and stability of copper catalyst are related with copper particle scale topography, extra small copper nanoparticle is prepared
Son has great importance.The method for commonly preparing extra small metal nanoparticle mainly have wet chemistry methods, reverse micelle method,
The methods of sputtering method, atomic layer deposition, however these methods require to be accurately controlled, there are complicated for operation or expensive ask
Topic, electro-deposition techniques have cheap, normal temperature and pressure operation, the feature that product purity is high, controllability is strong and environmental-friendly, extensively
In the general preparation applied to nanostructure or nanoparticle, and it is suitble to directly prepare nanoparticle on the electrode, and further
For electrocatalytic reaction；However, electro-deposition techniques generally are suitable for preparing the particle of larger nano-scale, such as tens received to several hundred
Rice, and be difficult to prepare the sub-nanometer sized particles of 1 ran or smaller cluster, electro-deposition techniques are then limited in this way to exist
The application of catalytic field.
Summary of the invention
The purpose of the present invention is to provide a kind of electrochemical preparing methods of sub-nanometer size copper particle elctro-catalyst, mainly
Solve the problems, such as that electro-deposition techniques existing in the prior art cannot prepare sub-nanometer size particle.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst, includes the following steps:
(S1) by the in the mixed solvent that the graphite foil of required size is placed in sulfuric acid and nitric acid volume ratio is 3:1, at room temperature
It is taken out after keeping 4-12h, is placed in dialysis in deionized water and removes remaining acid, the graphite oxide foil expanded；
(S2) graphite oxide foil is placed in water heating kettle, thiourea solution, and hydro-thermal reaction under the conditions of 120-180 DEG C is added
4-12h, taking-up, which is placed in deionized water, gives remaining small molecule, obtains the graphite foil of nitrogen sulfur doping；
(S3) using the graphite foil of nitrogen sulfur doping as working electrode, platinized platinum is used as to electrode, and silver/silver chloride electrode is as ginseng
Than electrode, it is placed in soluble cupric salt and concentration is in the electrolyte mixed solution of 0.05-1mol/L sulfuric acid, and in work electricity
Position carries out potentiostatic electrodeposition, sedimentation time 5-60s in the state of being 0.1-0.2V；
(S4) according to different operating potential and sedimentation time, the sub-nanometer copper particle of 0.5-2nm size is obtained.
Further, the concentration of thiourea solution is 0.05-0.5mol/L in the step (S2).
Further, cupric salt solution is copper-bath or copper chloride solution in the step (S3).
Specifically, cupric salt solution concentration is 1-10mmol/L in the step (S3).
Compared with prior art, the invention has the following advantages:
(1) present invention is by the way that by graphite foil, reaction obtains graphite oxide in the solution that sulfuric acid and nitric acid volume ratio are 3:1
Foil, and graphite oxide foil is placed in hot water to and is added thiourea solution reaction a few hours, the graphite foil of nitrogen sulfur doping is obtained, and
The potentiostatic electrodeposition that certain time is carried out in the state that operating potential is 0.1-0.2V, according to operating potential and sedimentation time
The sub-nanometer copper particle of 0.5-2nm size can be obtained in difference, and solving existing in the prior art cannot prepare sub-nanometer particle
The problem of, be conducive to electro-deposition techniques in the application of catalytic field.
(2) present invention is dredged by the way that graphite foil is placed in sulfuric acid and nitric acid volume ratio to obtain expansion in the mixed solution of 3:1
The porous graphite oxide foil of pine obtains nitrogen sulphur content so that graphite oxide foil reacts more abundant with thiourea solution in water heating kettle
The graphite foil that cloth uniformly adulterates.
(3) reaction condition of the invention is normal temperature and pressure, does not need special consersion unit, compared with the existing technology, this
The reaction condition of invention is low and easily controllable electrochemical deposition, easy to operate, and the price of reactant is relatively cheap, at low cost
Honest and clean achievable mass production.
Detailed description of the invention
Fig. 1 is flowage structure schematic diagram of the invention.
Fig. 2 is aobvious for nitrogen sulfur doping graphite foil prepared by the present invention/sub-nanometer size copper particle composite construction scanning electron
Micro mirror photo.
Fig. 3 is sub-nanometer size copper particle transmission electron microscope photo prepared by the present invention.
Fig. 4 is for nitrogen sulfur doping graphite foil prepared by the present invention/sub-nanometer size copper particle composite construction XPS score and respectively
Element spectrogram.
Fig. 5 is sub-nanometer size copper particle prepared by the present invention, nitrogen sulfur doping graphite foil substrate and copper sheet electro-catalysis two
Aoxidize the linear sweep voltammetry curve of carbon reduction reaction.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples, and embodiments of the present invention include but is not limited to
The following example.
As shown in Figures 1 to 5, a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst, including it is as follows
Step:
(S1) by the in the mixed solvent that the graphite foil of required size is placed in sulfuric acid and nitric acid volume ratio is 3:1, at room temperature
It is taken out after keeping 4-12h, is placed in dialysis in deionized water and removes remaining acid, the graphite oxide foil expanded；
(S2) graphite oxide foil is placed in water heating kettle, addition concentration is 0.05-0.5mol/L thiourea solution, and in 120-
Hydro-thermal reaction 4-12h under the conditions of 180 DEG C, taking-up, which is placed in deionized water, gives remaining small molecule, obtains nitrogen sulfur doping
Graphite foil；
(S3) using the graphite foil of nitrogen sulfur doping as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is as reference electricity
Pole is placed in soluble cupric salt and concentration that electrolyte solution is concentration 1-10mmol/L copper-bath or copper chloride solution
For in the electrolyte mixed solution of 0.05-1mol/L sulfuric acid, and constant potential is carried out in the state that operating potential is 0.1-0.2V
Deposition, sedimentation time 5-60s；
(S4) according to different operating potential and sedimentation time, the sub-nanometer copper particle of 0.5-2nm size is obtained.
It is as follows that case is embodied:
Embodiment 1
Graphite foil is cut into 1 × 2cm2Size, is placed in sulfuric acid and nitric acid volume ratio is temperature in the mixed acid system of 3:1
It is maintained at room temperature, is taken out after 12h, dialysis in deionized water is placed in and removes remaining acid, the graphite oxide foil expanded；By oxygen
Graphite foil is placed in water heating kettle, and 0.2mol/L thiourea solution is added, and hydro-thermal reaction 12h under the conditions of 180 DEG C after taking-up, is set
It dialyses away in deionized water and remains small molecule, obtain the graphite foil of nitrogen sulfur doping；The graphite foil of nitrogen sulphur will be adulterated as work
Make electrode, platinized platinum is used as to electrode, and silver/silver chloride electrode is used as reference electrode, electrolyte solution be 0.1mol/L sulfuric acid with
The mixed solution of 5mmol/L copper-bath, operating potential be 0.2V and carry out potentiostatic electrodeposition, and sedimentation time 30s is to get arriving
The sub-nanometer size copper particle of 0.5-2nm size.
And as shown in Figure 2, nitrogen sulfur doping graphite foil construction still keeps stone there is no variation after acid copper particle
The pleated structure on black surface, and surface does not have large scale metallic particles；From the figure 3, it may be seen that sub-nanometer size copper particle is uniformly distributed
On nitrogen thia graphite foil surface, size is distributed mainly between 0.5-2nm, and predominantly 1nm size；As shown in Figure 4, this is compound
Structure contains C, N, O, S and Cu element, and copper is 0 valence in sub-nanometer size copper particle, not oxidized；As shown in Figure 5, nitrogen sulfur doping
Graphite foil substrate does not have Carbon dioxide electrochemical reduction catalytic reaction activity；0.5-2nm size sub-nanometer size copper particle is urged
Change activity and is substantially better than copper sheet.
Embodiment 2
Graphite foil is cut into 5 × 5cm2Size, is placed in sulfuric acid and nitric acid volume ratio is temperature in the mixed acid system of 3:1
It is maintained at room temperature, is taken out after 12h, dialysis in deionized water is placed in and removes remaining acid, the graphite oxide foil expanded；By oxygen
Graphite foil is placed in water heating kettle, and 0.5mol/L thiourea solution is added, and hydro-thermal reaction 12h under the conditions of 180 DEG C after taking-up, is set
It dialyses away in deionized water and remains small molecule, obtain the graphite foil of nitrogen sulfur doping；The graphite foil of nitrogen sulphur will be adulterated as work
Make electrode, platinized platinum is used as to electrode, and silver/silver chloride electrode is used as reference electrode, electrolyte solution sulfuric acid containing 0.5mol/L with
10mmol/L copper-bath, operating potential be 0.15V and carry out potentiostatic electrodeposition, and sedimentation time 20s is to get arriving 0.5-2nm
The sub-nanometer size copper particle of size.
Embodiment 3
Graphite foil is cut into 4 × 2cm2Size, is placed in sulfuric acid and nitric acid volume ratio is temperature in the mixed acid system of 3:1
It is maintained at room temperature, is taken out after 6h, dialysis in deionized water is placed in and removes remaining acid, the graphite oxide foil expanded；By oxygen
Graphite foil is placed in water heating kettle, and 0.4mol/L thiourea solution is added, and hydro-thermal reaction 6h under the conditions of 120 DEG C after taking-up, is placed in
It dialyses away in deionized water and remains small molecule, obtain the graphite foil of nitrogen sulfur doping；The graphite foil of nitrogen sulphur will be adulterated as work
Electrode, platinized platinum are used as to electrode, and silver/silver chloride electrode is as reference electrode, electrolyte solution sulfuric acid containing 1mol/L and 5mmol/L
Copper chloride solution, operating potential is 0.2V and carries out potentiostatic electrodeposition, and sedimentation time 60s is to get the Ya Na for arriving 0.5-2nm size
Meter ruler cun copper particle.
Embodiment 4
Graphite foil is cut into 1 × 0.5cm2Size, is placed in sulfuric acid and nitric acid volume ratio is temperature in the mixed acid system of 3:1
Degree is maintained at room temperature, takes out after 4h, is placed in dialysis in deionized water and removes remaining acid, the graphite oxide foil expanded；It will
Graphite oxide foil is placed in water heating kettle, addition 0.1mol/L thiourea solution, hydro-thermal reaction 12h under the conditions of 150 DEG C, after taking-up,
It is placed in deionized water to dialyse away and remains small molecule, obtain the graphite foil of nitrogen sulfur doping；Using adulterate nitrogen sulphur graphite foil as
Working electrode, platinized platinum are used as to electrode, and silver/silver chloride electrode is used as reference electrode, electrolyte solution sulfuric acid containing 0.1mol/L with
1mmol/L copper-bath, operating potential is 0.2V and carries out potentiostatic electrodeposition, and sedimentation time 60s is to get big to 0.5-2nm
Small sub-nanometer size copper particle.
Above-described embodiment is merely a preferred embodiment of the present invention, and it is not intended to limit the protection scope of the present invention, as long as using
Design principle of the invention, and the non-creative variation worked and made is carried out on this basis, it should belong to of the invention
Within protection scope.
Claims (4)
1. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst, which comprises the steps of:
(S1) it by the in the mixed solvent that the graphite foil of required size is placed in sulfuric acid and nitric acid volume ratio is 3:1, keeps at room temperature
It is taken out after 4-12h, is placed in dialysis in deionized water and removes remaining acid, the graphite oxide foil expanded；
(S2) graphite oxide foil is placed in water heating kettle, thiourea solution, and hydro-thermal reaction 4- under the conditions of 120-180 DEG C is added
12h, taking-up, which is placed in deionized water, gives remaining small molecule, obtains the graphite foil of nitrogen sulfur doping；
(S3) using the graphite foil of nitrogen sulfur doping as working electrode, platinized platinum is used as to electrode, and silver/silver chloride electrode is as reference electricity
Pole is placed in the electrolyte mixed solution that soluble cupric salt and concentration are 0.05-1mol/L sulfuric acid, and be in operating potential
Potentiostatic electrodeposition, sedimentation time 5-60s are carried out in the state of 0.1-0.2V；
(S4) according to different operating potential and sedimentation time, the sub-nanometer copper particle of 0.5-2nm size is obtained.
2. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst according to claim 1, feature
It is, the concentration of thiourea solution is 0.05-0.5mol/L in the step (S2).
3. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst according to claim 2, feature
It is, cupric salt solution is copper-bath or copper chloride solution in the step (S3).
4. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst according to claim 3, feature
It is, cupric salt solution concentration is 1-10mmol/L in the step (S3).
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| CN1305618C (en) * | 2005-04-26 | 2007-03-21 | 黄德欢 | Method of preparing nano-bronze powder using electric deposition |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
| CN102978667B (en) * | 2012-10-25 | 2016-06-22 | 烟台大学 | A kind of method of preparing nano-bronze powder using electric deposition |
| CN103046088B (en) * | 2012-12-20 | 2015-08-26 | 华南理工大学 | A kind of micro-nano compound porous copper surface tissue and preparation method thereof and device |
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| CN105817616A (en) * | 2016-05-30 | 2016-08-03 | 李�浩 | Copper nano-film loaded on substrate and preparation method and application thereof |
| CN105568328A (en) * | 2016-01-05 | 2016-05-11 | 大连理工大学 | Nano-copper deposited film and preparation method and application thereof |
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