CN108315771A - 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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- CN108315771A CN108315771A CN201810141113.1A CN201810141113A CN108315771A CN 108315771 A CN108315771 A CN 108315771A CN 201810141113 A CN201810141113 A CN 201810141113A CN 108315771 A CN108315771 A CN 108315771A
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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 abstract 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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
- 239000000243 solution Substances 0.000 claims abstract description 14
- 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 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 238000004070 electrodeposition Methods 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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 11
- 239000008151 electrolyte solution Substances 0.000 abstract description 6
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 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
- -1 deionized water small molecule Chemical class 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
- 238000005516 engineering process Methods 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
- 238000010586 diagram 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
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- 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 preparation method of sub-nanometer size copper particle elctro-catalyst, this method includes that graphite is placed in sulfuric acid and nitric acid volume ratio is 3:1 in the mixed solvent, preserves to take out after 4 12h at room temperature and is placed in dialysis in deionized water and removes remaining acid, the graphite oxide foil expanded；Graphite oxide foil is placed in water heating kettle, and thiourea solution is added under the conditions of 120 180 DEG C, 4 12h of hydro-thermal reaction, 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 as reference electrode in electrolyte solution, 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 preparing technical field more particularly to a kind of sub-nanometer size copper particle elctro-catalysts
Electrochemical preparation method.
Background technology
Copper nano-particle achieves extensively in the reactions 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 nano-particle, and it is suitble to directly prepare nano-particle 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 to hundreds of receive
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.
Invention content
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 present invention is as follows：
A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst, includes the following steps：
(S1) it is 3 the graphite foil of required size to be placed in sulfuric acid and nitric acid volume ratio:1 in the mixed solvent, 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
It than electrode, is placed in the electrolyte mixed solution of soluble cupric salt and a concentration 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 sizes is obtained.
Further, in the step (S2) thiourea solution a concentration of 0.05-0.5mol/L.
Further, cupric salt solution is copper sulphate or copper chloride in the step (S3).
Specifically, cupric salt solution is concentration 1-10mmol/L in the step (S3).
Compared with prior art, the invention has the advantages that：
(1) present invention is by sulfuric acid and nitric acid volume ratio being 3 by graphite foil:Graphite oxide is obtained by the reaction in 1 solution
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 sizes can be obtained in difference, and solving existing in the prior art cannot prepare sub-nanometer particle
The problem of, be conducive to application of the electro-deposition techniques in catalytic field.
(2) present invention is 3 by the way that graphite foil is placed in sulfuric acid and nitric acid volume ratio:Expansion is obtained in 1 mixed solution to dredge
The porous graphite oxide foil of pine so that graphite oxide foil reacts more abundant with thiourea solution in water heating kettle, obtains nitrogen sulphur content
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.
Description of the drawings
Fig. 1 is the flowage structure schematic diagram of the present invention.
Fig. 2 is that the scanning electron of nitrogen sulfur doping graphite foil/sub-nanometer size copper particle composite construction prepared by the present invention is aobvious
Micro mirror photo.
Fig. 3 is sub-nanometer size copper particle transmission electron microscope photo prepared by the present invention.
Fig. 4 is the XPS scores of nitrogen sulfur doping graphite foil/sub-nanometer size copper particle composite construction prepared by the present invention and each
Element spectrogram.
Fig. 5 is sub-nanometer size copper particle, nitrogen sulfur doping graphite foil substrate and copper sheet electro-catalysis two prepared by the present invention
Aoxidize the linear sweep voltammetry curve of carbon reduction reaction.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and examples, and embodiments of the present invention include but 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) it is 3 the graphite foil of required size to be placed in sulfuric acid and nitric acid volume ratio:1 in the mixed solvent, 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, a concentration of 0.05-0.5mol/L thiourea solutions is added, 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 a concentration of 0.05- that electrolyte solution is concentration 1-10mmol/L copper sulphate or copper chloride
In the electrolyte mixed solution of 1mol/L sulfuric acid, and potentiostatic electrodeposition is carried out in the state that operating potential is 0.1-0.2V, sunk
The product time is 5-60s；
(S4) according to different operating potential and sedimentation time, the sub-nanometer copper particle of 0.5-2nm sizes is obtained.
It is as follows that case is embodied：
Embodiment 1
Graphite foil is cut into 1 × 2cm2Size, it is 3 to be placed in sulfuric acid and nitric acid volume ratio:In 1 mixed acid system, temperature
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 solutions are added, and hydro-thermal reaction 12h under the conditions of 180 DEG C after taking-up, is set
Residual of dialysing away in deionized water small molecule, obtains 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 sulphate, operating potential be 0.2V and carry out potentiostatic electrodeposition, and sedimentation time 30s is to get to 0.5-
The sub-nanometer size copper particle of 2nm sizes.
And as shown in Figure 2, nitrogen sulfur doping graphite foil construction does not change after acid copper particle, still keeps stone
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 sizes；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, it is 3 to be placed in sulfuric acid and nitric acid volume ratio:In 1 mixed acid system, temperature
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 solutions are added, and hydro-thermal reaction 12h under the conditions of 180 DEG C after taking-up, is set
Residual of dialysing away in deionized water small molecule, obtains 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 sulphate, operating potential be 0.15V and carry out potentiostatic electrodeposition, and sedimentation time 20s is to get to 0.5-2nm sizes
Sub-nanometer size copper particle.
Embodiment 3
Graphite foil is cut into 4 × 2cm2Size, it is 3 to be placed in sulfuric acid and nitric acid volume ratio:In 1 mixed acid system, temperature
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 solutions are added, and hydro-thermal reaction 6h under the conditions of 120 DEG C after taking-up, is placed in
Residual of dialysing away in deionized water small molecule, obtains 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, operating potential be 0.2V and carry out potentiostatic electrodeposition, and sedimentation time 60s is to get to the sub-nanometer ruler of 0.5-2nm sizes
Very little copper particle.
Embodiment 4
Graphite foil is cut into 1 × 0.5cm2Size, it is 3 to be placed in sulfuric acid and nitric acid volume ratio:In 1 mixed acid system, temperature
Degree is maintained at room temperature, is taken 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 solutions, hydro-thermal reaction 12h under the conditions of 150 DEG C, after taking-up,
It is placed in deionized water residual small molecule of dialysing away, obtains 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 sulphate, operating potential be 0.2V and carry out potentiostatic electrodeposition, and sedimentation time 60s is to get to 0.5-2nm sizes
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
The design principle of the present invention, and the non-creative variation worked and made is carried out on this basis, it should all belong to the present invention's
Within protection domain.
Claims (4)
1. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst, which is characterized in that include the following steps：
(S1) it is 3 the graphite foil of required size to be placed in sulfuric acid and nitric acid volume ratio:1 in the mixed solvent, 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 of soluble cupric salt and a concentration of 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 sizes is obtained.
2. a kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst according to claim 1, feature
It is, a concentration of 0.05-0.5mol/L of thiourea solution 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 sulphate or copper chloride 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 is concentration 1-10mmol/L in the step (S3).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109126793A (en) * | 2018-09-10 | 2019-01-04 | 中国工程物理研究院材料研究所 | A kind of electrochemical preparation method of monatomic copper elctro-catalyst |
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| CN1686645A (en) * | 2005-04-26 | 2005-10-26 | 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 |
| CN102978667A (en) * | 2012-10-25 | 2013-03-20 | 烟台大学 | Preparation method for nanometer copper powder through electro-deposition |
| CN103046088A (en) * | 2012-12-20 | 2013-04-17 | 华南理工大学 | Micro-nano composite porous copper surface structure and preparation method and device thereof |
| CN103785856A (en) * | 2014-02-26 | 2014-05-14 | 北京科技大学 | Composite material in which carbon spheres are loaded with copper nanoparticles and preparation method 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 |
| CN105817616A (en) * | 2016-05-30 | 2016-08-03 | 李�浩 | Copper nano-film loaded on substrate and preparation method and application thereof |
| CN107460503A (en) * | 2017-09-14 | 2017-12-12 | 西南科技大学 | The method that micro-nano copper powder is reclaimed from waste printed circuit board |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126793A (en) * | 2018-09-10 | 2019-01-04 | 中国工程物理研究院材料研究所 | A kind of electrochemical preparation method of monatomic copper elctro-catalyst |
| CN109126793B (en) * | 2018-09-10 | 2020-10-16 | 中国工程物理研究院材料研究所 | Electrochemical preparation method of monoatomic copper electrocatalyst |
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