CN106363165A - Flaky copper particles, preparation method thereof, catalyst and electrode - Google Patents
Flaky copper particles, preparation method thereof, catalyst and electrode Download PDFInfo
- Publication number
- CN106363165A CN106363165A CN201610801199.7A CN201610801199A CN106363165A CN 106363165 A CN106363165 A CN 106363165A CN 201610801199 A CN201610801199 A CN 201610801199A CN 106363165 A CN106363165 A CN 106363165A
- Authority
- CN
- China
- Prior art keywords
- sheet
- copper
- granule
- preparation
- copper granule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 137
- 239000010949 copper Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005642 Oleic acid Substances 0.000 claims abstract description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims description 116
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- GOKQOZYJEDDDOC-UHFFFAOYSA-N C(=O)OC.C1=CC=CC=C1 Chemical group C(=O)OC.C1=CC=CC=C1 GOKQOZYJEDDDOC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 5
- 230000008569 process Effects 0.000 abstract description 4
- 150000001879 copper Chemical class 0.000 abstract 3
- 150000001299 aldehydes Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- 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
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
Abstract
The invention discloses flaky copper particles, a preparation method thereof, a catalyst and an electrode. The preparation method comprises the following steps: dissolving copper salt in a mixed solvent in which the volume ratio of oleic acid to ethanol is 1:0.25-1, and adding a surfactant and a reducing agent to obtain a mixed solution in which the content of the copper salt is 1 g/L-10 g/L; and loading the mixed solution in which the content of the copper salt is 1 g/L-10 g/L in a high pressure reactor, and reacting for 8-15 hours under the condition that the temperature is 170-200 DEG C so as to obtain the flaky copper particles of which the average value of the thicknesses is below 500 nm, the average value of absolute deviation of the thicknesses is below 50 nm, the average value of the maximum sizes of planes is 5,000-20,000 nm, and the average value of absolute deviation of the maximum sizes of the planes is below 1,500 nm. The method is simple in process, and the obtained flaky copper particles are uniform in size, regular in shape and good in monodispersity.
Description
Technical field
The present invention relates to a kind of sheet of copper granule and preparation method thereof, catalyst, electrode.
Background technology
Copper be widely studied as a kind of transition metal, because of its good performance, abundant reserves, cheap price and
Application.For example, copper granule can be used as sewage disposal device sparking electrode, catalytic reaction catalyst, and high conductivity and high intensity are received
Rice copper material etc..The difference of the pattern of copper granule, size and structure makes its performance different.Such as, the larger copper granule of surface area is fitted
Catalyst is made in conjunction, and regular shape, and the more smooth copper granule in surface is suitable as sewage disposal device sparking electrode.At present, make
Standby regular shape, the more smooth sheet of copper granule in surface is one of hot research direction.
The method that prior art prepares sheet of copper granule mainly has: template, electrolysis, solution phase chemical reduction, machinery
Polishing, hydro-thermal method etc..Such as, (Chen Mingwei, Zhu Yongping, Zhang Weigang, with peg600 as template liquid phase reduction for non-patent literature 1
Method prepares flake copper [j], 2008,8 (5): 1003-1007) disclosing using copper sulphate pentahydrate is copper source, and peg600 is template
Agent, sodium hypophosphite prepares 10-40 μm of particle diameter, thick 1.5-2.5 μm of flake copper for reducing agent.For another example non-patent literature 2 (Cao
Dawn state, Wu Bailin, chemical reduction method prepares the research [j] of electrically-conducting paint ultrafine flake copper powder, 2004,34 (6)) disclose with
Copper sulphate pentahydrate is raw material, and ascorbic acid is reducing agent, and ammonia is chelating agent, is prepared for the sheet of copper that particle diameter distribution is 1-10 μm
Powder.
During realizing the present invention, inventor find prior art at least there is problems in that
Some complex process of prior art, the sheet of copper particle size heterogeneity of preparation.
Content of the invention
In order to solve the inhomogenous problem of sheet of copper particle size of prior art preparation, the embodiment of the present invention provides a kind of
Sheet of copper granule and preparation method thereof.Described technical scheme is as follows:
In a first aspect, the embodiment of the present invention provides a kind of sheet of copper granule, the meansigma methodss of the thickness of described sheet of copper granule
For below 500nm, the absolute deviation meansigma methodss of described thickness are below 50nm, and the plane of described sheet of copper granule is maximum sized
Meansigma methodss are 5000nm～20000nm, and the maximum sized absolute deviation meansigma methodss of described plane are below 1500nm.
Specifically, the plane of described sheet of copper granule is circular or hexagon.
Specifically, the variance of the thickness of described sheet of copper granule is less than 500.
Specifically, the variance of the planar dimension of described sheet of copper granule is less than 50.
Specifically, the content of the impurity of described sheet of copper granule is less than 0.1%.
Specifically, described sheet of copper granule does not contain Red copper oxide and copper oxide.
Second aspect, the embodiment of the present invention provides a kind of deposit comprising sheet of copper granule, and this deposit comprises:
More than the 90% sheet of copper granule described in embodiment of the present invention first aspect, and
Copper granule beyond less than the 10% sheet of copper granule described in embodiment of the present invention first aspect.
The third aspect, the embodiment of the present invention provides a kind of preparation method of sheet of copper granule.Including:
It is in the mixed solvent of 1:0.25～1 that mantoquita is dissolved in Oleic acid and the volume ratio of ethanol, adds surfactant,
Add reducing agent, obtain the mixed solution that mantoquita content is 1g/l～10g/l；
The mixed solution that described mantoquita content is 1g/l～10g/l loads autoclave, in 170～200 DEG C of bar
React under part, obtain the mixed solution containing sheet of copper granule.
Preferably, described mantoquita is inorganic mantoquita.
Preferably, described inorganic mantoquita is copper nitrate, copper sulfate, Schweinfurt green or copper chloride.
Preferably, described mixed solvent is the mixed solvent that the volume ratio of Oleic acid and ethanol is 1:0.25～0.5.
Preferably, described surfactant is essence of Niobe.
Preferably, the content of described essence of Niobe is 3%～11%.
Preferably, described reducing agent is aldehydes reducing agent.
Preferably, described aldehydes reducing agent is long-chain aldehydes.
Preferably, described long-chain aldehydes is 1- octanal.
Preferably, described autoclave is flange form autoclave.
Preferably, the response time of described reaction is 8-15 hour.
Fourth aspect, the embodiment of the present invention provides a kind of catalyst, comprises the piece described in embodiment of the present invention first aspect
Shape copper granule.
5th aspect, the embodiment of the present invention provides a kind of electrode, comprises the lamellar described in embodiment of the present invention first aspect
Copper granule.
Technical scheme provided in an embodiment of the present invention has the benefit that
The embodiment of the present invention prepares a kind of sheet of copper granule, using a step hydrothermal synthesis method, using Oleic acid and ethanol as molten
Agent, inorganic mantoquita is dissolved in solvent, using essence of Niobe as surfactant, 1- octanal as reducing agent, 170～
200 DEG C are reacted 8～15 hours, then obtain copper granule through sucking filtration, washing, centrifugation and vacuum drying；The method process is simple,
The sheet of copper granule obtaining is that monodispersity is good, the granule of regular shape, size uniformity, and its plane is circular or six sides
Shape, the meansigma methodss of the thickness of described sheet of copper granule are below 500nm, the absolute deviation meansigma methodss of described thickness be 50nm with
Under.The maximum sized meansigma methodss of plane of described sheet of copper granule are 5000nm～20000nm, and described plane is maximum sized absolutely
It is below 1500nm to deviation average；And this sheet of copper granule does not comprise copper oxide and Red copper oxide, the content of its impurity
For less than 0.1%.
Brief description
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, will make to required in embodiment description below
Accompanying drawing be briefly described it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the scanning electron microscope diagram of multiple sheet of copper granules that the embodiment of the present invention 1 provides；
Fig. 2 is the scanning electron microscope diagram of the single sheet of copper granule that the embodiment of the present invention 1 provides；
Fig. 3 is the scanning electron microscope diagram of the single sheet of copper grain thickness that the embodiment of the present invention 1 provides；
Fig. 4 is the ratio scattergram with thickness for the sheet of copper granule plane full-size of the embodiment of the present invention 1 offer；
Fig. 5 is the X-ray diffraction pattern of the sheet of copper granule that the embodiment of the present invention 1 provides；
Fig. 6 is the energy spectrum diagram of the sheet of copper granule that the embodiment of the present invention 1 provides.
Specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail.
In a first aspect, the embodiment of the present invention provides a kind of sheet of copper granule, the meansigma methodss of the thickness of this sheet of copper granule are
Below 500nm, the absolute deviation meansigma methodss of described thickness are below 50nm, and the plane of this sheet of copper granule is maximum sized average
It is worth for 5000nm～20000nm, its plane maximum sized absolute deviation meansigma methodss are below 1500nm.Wherein, plane is maximum
Size refers to the greatest length of an end points of plane to another end points.
In above-mentioned first aspect, although the meansigma methodss of the thickness of this sheet of copper granule do not have the restriction of lower limit, as super
Cross 0nm, as one, can be 10～500nm, it is also possible to be preferably below 490nm or below 480nm or 460nm
Below or below 440nm or below 420nm or below 400nm or below 380nm or below 360nm or below 340nm,
Or below 320nm or below 300nm, can also be preferably more than 20nm or more than 30nm or more than 40nm or 50nm with
Upper or more than 60nm or more than 70nm or more than 80nm or more than 90nm or more than 100nm or more than 110nm or
More than 120nm, more preferably 130～290nm, more preferably 150～250nm.
Although the absolute deviation meansigma methodss of the thickness of this sheet of copper granule do not have the restriction of lower limit, as one, Ke Yiwei
0-50nm, it is also possible to be preferably below 40nm or below 30nm or below 20nm, more preferably 1-19nm, excellent further
Elect 5-10nm as.
The maximum sized meansigma methodss of plane of this sheet of copper granule are 5000nm～20000nm, can also be preferably
5500nm～18000nm or 6000nm～17000nm or 6500nm～16000nm or 7000nm～15000nm, more preferably
For 7500nm～14000nm, more preferably 8000nm～13000nm.
Although the plane of this sheet of copper granule maximum sized absolute deviation meansigma methodss do not have the restriction of lower limit, as one
Example, can be 100-1500nm, it is also possible to be preferably below 1400nm or below 1300nm or below 1200nm or
Below 1100nm, can also be preferably more than 200nm or more than 300nm or more than 400nm or more than 500nm or 600nm
More than, more preferably 700-1000nm, more preferably 800-920nm.
Specifically, the plane of this sheet of copper granule is circular or hexagon.
Specifically, the variance of the thickness of this sheet of copper granule is less than 500.Wherein, the side of the thickness of this sheet of copper granule
Difference, as one, can be 10～500, it is also possible to be preferably less than 400 or less than 300 or less than 200, more preferably
100-200, more preferably 110-150.
Specifically, the variance of the planar dimension of this sheet of copper granule is less than 50.Wherein, the plane meter of this sheet of copper granule
Very little variance, as one, can be 0～50, it is also possible to be preferably less than 40 or less than 30 or less than 20, or 10 with
Under, more preferably 0-9, more preferably 1-8.
Specifically, the content of the impurity of this sheet of copper granule is less than 0.1%.More preferably less than 0.05%, more preferably
For less than 0.02%.
Specifically, this sheet of copper granule does not contain Red copper oxide and copper oxide.
Second aspect, the embodiment of the present invention provides a kind of deposit comprising sheet of copper granule, and this deposit comprises:
Sheet of copper granule in more than 90% embodiment of the present invention first aspect, and
The copper granule beyond sheet of copper granule in less than 10% embodiment of the present invention first aspect.
The third aspect, the embodiment of the present invention provides a kind of preparation method of sheet of copper granule.Including:
It is oil in the mixed solvent of 1:0.25～1 that 0.015g～0.15g mantoquita is dissolved in Oleic acid and the volume ratio of ethanol
The mixed solvent of acid and ethanol is 15ml, adds the surfactant of 0.5～2.0ml, adds the reducing agent of 1ml, obtains mantoquita
Content is the mixed solution of 1g/l～10g/l；
Wherein, Oleic acid and ethanol with volume ratio as 1:0.25～1 arbitrary proportion mixing, when ethanol content is less than 20%
When, mixed and disorderly little particle can be formed, when ethanol content is more than 50%, the copper granule of cube structure can be formed.Mantoquita content is
Sheet of copper granule could be formed during 1g/l～10g/l；
The mixed solution that described mantoquita content is 1g/l～10g/l loads autoclave, in 170～200 DEG C of bar
React under part, obtain the mixed solution containing sheet of copper granule.
In the above-mentioned third aspect, mantoquita content is 0.015g～0.15g or 0.02g～0.14g or 0.03g
～0.13g or 0.04g～0.12g, more preferably 0.05g～0.1g.
Mantoquita content is 1g/l～10g/l or 2g/l～9g/l, more preferably 2.78g/l～3.03g/l, more
It is preferably 2.94g/l～3.03g/l.
Preferably, mantoquita is inorganic mantoquita.
Preferably, inorganic mantoquita is copper nitrate, copper sulfate, Schweinfurt green or copper chloride.
Preferably, mixed solvent is the mixed solvent that the volume ratio of Oleic acid and ethanol is 1:0.25～0.5.
Preferably, surfactant is essence of Niobe.
Preferably, the content of essence of Niobe is 3%～11%, and the content of essence of Niobe is could when 3%～11%
Form sheet of copper granule.
Preferably, reducing agent is aldehydes reducing agent.
Preferably, aldehydes reducing agent is long-chain aldehydes.
Preferably, long-chain aldehydes is 1- octanal.
Preferably, autoclave is flange form autoclave.
Preferably, the response time of reaction is 8-15 hour.
Fourth aspect, the embodiment of the present invention provides a kind of catalyst, comprises the piece described in embodiment of the present invention first aspect
Shape copper granule.
5th aspect, the embodiment of the present invention provides a kind of electrode, comprises the lamellar described in embodiment of the present invention first aspect
Copper granule.
Chemical reagent used in the embodiment of the present invention:
Ethanol: chemistry is pure, producer is Beijing chemical reagents corporation；
Oleic acid: chemistry is pure, producer is Shantou, Guangdong city Xi Long chemical plant；
Copper nitrate: chemistry is pure, producer is Beijing chemical reagents corporation；
Copper sulfate: chemistry is pure, producer is Beijing chemical reagents corporation；
Copper chloride: chemistry is pure, producer is Beijing chemical reagents corporation；
1- octanal: chemistry is pure, producer is Beijing chemical reagents corporation；
Essence of Niobe: analysis is pure, producer is Aladdin Reagent Company.
Instrument used in the embodiment of the present invention:
Flange form autoclave: customization, inner bag is politef, and shell is rustless steel；
Tgl-16c type centrifuge, anke instrument company；
Kq-300gvdv type ultrasonic machine, Kunshan Ultrasonic Instruments Co., Ltd.；
Shz- type vacuum filtration machine, Tianjin Stettlen Instrument Ltd.；
Dz-1bc type vacuum drying oven, Tianjin Stettlen Instrument Ltd.；
Sirion 200 type scanning electron microscope, Dutch fei company
X-ray diffraction instrument, x ' pert pro mrd, Dutch PANalytical company.
Embodiment 1
10ml Oleic acid and 5ml ethanol are mixed to get mixed solvent, 0.05g copper nitrate are dissolved in this mixed solvent,
Add 1ml essence of Niobe, add 1ml 1- octanal, and be stirred, obtain the mixing that nitric acid copper content is 2.94g/l molten
Liquid；This mixed solution is loaded in flange form autoclave, reaction temperature is 180 DEG C, the response time is 10 hours；Take out anti-
The product that should obtain, vacuum filtration this product of machine sucking filtration of the microporous filter membrane being 0.22 μm with filter membrane；Sucking filtration is obtained
To filter cake add 10ml ethanol in be cleaned by ultrasonic, repeatedly clean twice；The centrifuge being 5000 revs/min with rotating speed
Separation cleaning fluid and copper granule, filter after centrifugation and discard the supernatant；The copper granule that centrifugation is obtained is put in vacuum drying oven
Dry.
Embodiment 2
The preparation method of sheet of copper granule that the present embodiment provides is with the difference of embodiment 1: by 0.05g sulphuric acid
Copper dissolution is in the mixed solvent of Oleic acid and ethanol.
Embodiment 3
The preparation method of sheet of copper granule that the present embodiment provides is with the difference of embodiment 1: by 12ml Oleic acid
It is mixed to get mixed solvent with 3ml ethanol.
Embodiment 4
The preparation method of sheet of copper granule that the present embodiment provides is with the difference of embodiment 1: adds 0.5ml benzene
Methyl formate；Obtain the mixed solution that nitric acid copper content is 3.03g/l.
Embodiment 5
The preparation method of sheet of copper granule that the present embodiment provides is with the difference of embodiment 1: adds 2ml benzene first
Sour methyl ester；Obtain the mixed solution that nitric acid copper content is 2.78g/l.
Embodiment 6
The present embodiment utilizes scanning electron microscope sem (scanning electron microscope) to by this
The sheet of copper particulate samples of bright embodiment 1 preparation are characterized, and can intuitively be reflected by the scanning electron microscope diagram of sample
Go out architectural feature and pattern of sheet of copper granule etc..
Fig. 1 is the scanning electron microscope diagram of multiple sheet of copper granules, Fig. 2 and Fig. 3 is the scanning of single sheet of copper granule
Electron microscope picture, can be seen that the surface topography rule of the sheet of copper granule preparing by the present embodiment 1 from above-mentioned in figure
Then, its plane is circular or hexagon.
Laggard to the plane full-size and thickness measure of 50 sheet of copper particulate samples that the embodiment of the present invention 1 provides
Row statistical analysiss, the plane full-size obtaining lamellar structure is 6000-10000nm, and thickness is 150-250nm.Plane is maximum
Size average is 8000nm, and plane maximum sized absolute deviation meansigma methodss are 920nm, and the maximum sized variance of plane is
1.52, thickness average value is 189nm, and the absolute deviation meansigma methodss of thickness are 8.85nm, and the variance of thickness is 144.2, illustrate logical
Cross that the sheet of copper particle size that the embodiment of the present invention 1 prepares is homogeneous, monodispersity is preferable.And as shown in figure 4, Fig. 4 is
Sheet of copper granule plane full-size and the ratio scattergram of thickness that the embodiment of the present invention 1 provides, this sheet of copper particulate samples
The ratio of plane full-size and its thickness be 30～55, and have 79% the plane full-size of copper granule and thickness ratio
Fall in 35～45 intervals, equally illustrate that the dimension scale of this sheet of copper granule is more unified.
Embodiment 8
The present embodiment is prepared to by the embodiment of the present invention 1 using x-ray diffraction instrument xrd (x-ray diffraction)
Sheet of copper particulate samples characterized, crystal structure of sheet of copper granule etc. can be obtained by the X-ray diffraction pattern of sample
Information.
Fig. 5 is the X-ray diffraction pattern of sheet of copper granule, and from Fig. 5 and pdf2002 data base, 02-1225 file is permissible
Draw, the diffraction maximum of in figure is from left to right the diffraction maximum of the crystal faces such as copper (111), (200), (220) respectively, and sheet of copper is described
Granule is copper crystal, and the content of its impurity is less than 0.1%.
Embodiment 9
The present embodiment utilizes energy disperse spectroscopy eds (the energy dispersive in scanning electron microscope
Spectroscopy) the sheet of copper particulate samples prepared by the embodiment of the present invention 1 are characterized, by the energy spectrum diagram of sample
The information such as the element that sheet of copper granule contains can be obtained.
Fig. 6 is the energy spectrum diagram of sheet of copper granule, from fig. 6, it can be seen that the peak of in figure copper is main peaks, copper
Peak is very strong, and the peak of oxygen element is very weak, and element silicon peak and carbon peak are impurity peaks, may be introduced by conducting adhesive cloth and si piece,
Illustrate that sheet of copper granule does not contain copper oxide or Red copper oxide, the content of its impurity is less than 0.1%.
For embodiment 2～5, detected using the mensuration mode similar to embodiment 6～9, it was found that every knot
Fruit is approximate with embodiment 1.
Technical scheme provided in an embodiment of the present invention has the benefit that
The embodiment of the present invention prepares a kind of sheet of copper granule, using a step hydrothermal synthesis method, using Oleic acid and ethanol as molten
Agent, inorganic mantoquita is dissolved in solvent, using essence of Niobe as surfactant, 1- octanal as reducing agent, 170～
200 DEG C are reacted 8～15 hours, then obtain copper granule through sucking filtration, washing, centrifugation and vacuum drying；The method process is simple,
The sheet of copper granule obtaining is that monodispersity is good, the granule of regular shape, size uniformity, and its plane is circular or six sides
Shape, the meansigma methodss of the thickness of described sheet of copper granule are below 500nm, the absolute deviation meansigma methodss of described thickness be 50nm with
Under.The maximum sized meansigma methodss of plane of described sheet of copper granule are 5000nm～20000nm, and described plane is maximum sized absolutely
It is below 1500nm to deviation average；And this sheet of copper granule does not comprise copper oxide and Red copper oxide, the content of its impurity
For less than 0.1%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (20)
1. a kind of sheet of copper granule is it is characterised in that the meansigma methodss of the thickness of described sheet of copper granule are below 500nm, described
The absolute deviation meansigma methodss of thickness are below 50nm, the maximum sized meansigma methodss of plane of described sheet of copper granule be 5000nm～
20000nm, the maximum sized absolute deviation meansigma methodss of described plane are below 1500nm.
2. sheet of copper granule according to claim 1 is it is characterised in that its plane is circular or hexagon.
3. sheet of copper granule according to claim 1 and 2 is it is characterised in that the variance of the thickness of described sheet of copper granule
For less than 500.
4. sheet of copper granule according to claim 3 is it is characterised in that the variance of the planar dimension of described sheet of copper granule
For less than 50.
5. sheet of copper granule according to claim 1 is it is characterised in that the content of impurity is less than 0.1%.
6. sheet of copper granule according to claim 1 is not it is characterised in that it contains Red copper oxide and copper oxide.
7. a kind of deposit comprising sheet of copper granule is it is characterised in that described deposit comprises:
Sheet of copper granule any one of more than 90% claim 1～6, and
The copper granule beyond sheet of copper granule any one of 10% claims below 1～6.
8. a kind of preparation method of sheet of copper granule is it is characterised in that methods described includes:
It is in the mixed solvent of 1:0.25～1 that mantoquita is dissolved in Oleic acid and the volume ratio of ethanol, adds surfactant, adds
Reducing agent, obtains the mixed solution that mantoquita content is 1g/l～10g/l；
The mixed solution that described mantoquita content is 1g/l～10g/l loads autoclave, under conditions of 170～200 DEG C
Reaction, obtains the mixed solution containing sheet of copper granule.
9. the preparation method of sheet of copper granule according to claim 8 is it is characterised in that described mantoquita is inorganic mantoquita.
10. the preparation method of sheet of copper granule according to claim 9 is it is characterised in that described inorganic mantoquita is nitric acid
Copper, copper sulfate, Schweinfurt green or copper chloride.
The preparation method of 11. sheet of copper granules according to claim 8 is it is characterised in that described mixed solvent is Oleic acid
Volume ratio with ethanol is the mixed solvent of 1:0.25～0.5.
The preparation method of 12. sheet of copper granules according to claim 8 is it is characterised in that described surfactant is benzene
Methyl formate.
13. preparation methoies of sheet of copper granule according to claim 12 are it is characterised in that containing of described essence of Niobe
Measure as 3%～11%.
The preparation method of 14. sheet of copper granules according to claim 8 it is characterised in that described reducing agent be aldehydes also
Former dose.
The preparation method of 15. sheet of copper granules according to claim 14 is it is characterised in that described aldehydes reducing agent is length
Chain aldehydes.
The preparation method of 16. sheet of copper granules according to claim 15 is it is characterised in that described long-chain aldehydes is that 1- is pungent
Aldehyde.
The preparation method of 17. sheet of copper granules according to claim 8 is it is characterised in that described autoclave is method
Blue formula autoclave.
The preparation method of 18. sheet of copper granules according to claim 8 is it is characterised in that the response time of described reaction
For 8-15 hour.
A kind of 19. catalyst, comprise the sheet of copper granule any one of claim 1～6.
A kind of 20. electrodes, comprise the sheet of copper granule any one of claim 1～6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610801199.7A CN106363165B (en) | 2016-09-05 | 2016-09-05 | A kind of sheet of copper particle and preparation method thereof, catalyst, electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610801199.7A CN106363165B (en) | 2016-09-05 | 2016-09-05 | A kind of sheet of copper particle and preparation method thereof, catalyst, electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106363165A true CN106363165A (en) | 2017-02-01 |
| CN106363165B CN106363165B (en) | 2019-02-15 |
Family
ID=57899269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610801199.7A Active CN106363165B (en) | 2016-09-05 | 2016-09-05 | A kind of sheet of copper particle and preparation method thereof, catalyst, electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106363165B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586953A (en) * | 2018-06-12 | 2019-12-20 | 本田技研工业株式会社 | High yield preparation of two-dimensional copper nanosheets |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642680A (en) * | 2002-11-22 | 2005-07-20 | 三井金属矿业株式会社 | Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder |
| CN1792520A (en) * | 2005-12-16 | 2006-06-28 | 华南理工大学 | Sheet crystal cupper powder and liquid phase chemical preparation process thereof |
| CN1950162A (en) * | 2004-04-28 | 2007-04-18 | 三井金属矿业株式会社 | Flaky copper powder, process for producing the same, and conductive paste |
| CN1962136A (en) * | 2006-11-21 | 2007-05-16 | 华南理工大学 | Laminar crystallized copper powder and preparation method thereof |
| JP2007169770A (en) * | 2005-12-26 | 2007-07-05 | Mitsui Mining & Smelting Co Ltd | Copper powder, copper particle and method for producing the copper particle |
| JP2010138494A (en) * | 2010-02-10 | 2010-06-24 | Mitsui Mining & Smelting Co Ltd | Method for producing flake copper powder |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| JP2015147990A (en) * | 2014-02-07 | 2015-08-20 | 日立化成株式会社 | Electrode, method of producing electrode, electrochemical reduction method and method of producing electrochemical reduction product |
| CN105451917A (en) * | 2013-06-14 | 2016-03-30 | Lg化学株式会社 | Metal nanoplate, method for manufacturing same, and conductive ink composition and conductive film comprising metal nanoplate |
-
2016
- 2016-09-05 CN CN201610801199.7A patent/CN106363165B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642680A (en) * | 2002-11-22 | 2005-07-20 | 三井金属矿业株式会社 | Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder |
| CN1950162A (en) * | 2004-04-28 | 2007-04-18 | 三井金属矿业株式会社 | Flaky copper powder, process for producing the same, and conductive paste |
| CN1792520A (en) * | 2005-12-16 | 2006-06-28 | 华南理工大学 | Sheet crystal cupper powder and liquid phase chemical preparation process thereof |
| JP2007169770A (en) * | 2005-12-26 | 2007-07-05 | Mitsui Mining & Smelting Co Ltd | Copper powder, copper particle and method for producing the copper particle |
| CN1962136A (en) * | 2006-11-21 | 2007-05-16 | 华南理工大学 | Laminar crystallized copper powder and preparation method thereof |
| JP2010138494A (en) * | 2010-02-10 | 2010-06-24 | Mitsui Mining & Smelting Co Ltd | Method for producing flake copper powder |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| CN105451917A (en) * | 2013-06-14 | 2016-03-30 | Lg化学株式会社 | Metal nanoplate, method for manufacturing same, and conductive ink composition and conductive film comprising metal nanoplate |
| JP2015147990A (en) * | 2014-02-07 | 2015-08-20 | 日立化成株式会社 | Electrode, method of producing electrode, electrochemical reduction method and method of producing electrochemical reduction product |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586953A (en) * | 2018-06-12 | 2019-12-20 | 本田技研工业株式会社 | High yield preparation of two-dimensional copper nanosheets |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106363165B (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105170155B (en) | Changed red mud, its method of modifying and the catalyst suitable for DCL/Direct coal liquefaction | |
| CN105617871B (en) | The preparation and its application in emulsion separation of a kind of super infiltration cobaltosic oxide nano pin perforated membrane | |
| CN103103510A (en) | Silver-plated copper nanowire and preparation method thereof | |
| CN104045076A (en) | Graphene oxide quantum dot preparation method | |
| CN113398771A (en) | Multi-component bacterial cellulose composite filter membrane and preparation method and application thereof | |
| CN102849774A (en) | Method for preparing nanometer cerium oxide by hydrothermal method | |
| CN107673390B (en) | A kind of preparation method of exquisite spherical nano yttrium oxide | |
| CN103991909A (en) | Preparation method for amorphous iron oxyhydroxide with high sulfur capacity | |
| CN106673049B (en) | A kind of preparation method of porous graduation ball active oxidation copper powder | |
| CN106363165A (en) | Flaky copper particles, preparation method thereof, catalyst and electrode | |
| CN103878386A (en) | Method for preparing fluorescent silver nano-clusters | |
| CN109529903B (en) | Method for preparing nickel-nitrogen co-doped carbon material by using hydrotalcite as template | |
| CN101182040A (en) | Method for producing ultra-fine tungsten oxide | |
| CN103203469B (en) | Preparation method of Ag-Ag2O hetero-structure silver material | |
| Mao et al. | Template-free synthesis of VO x hierarchical hollow spheres | |
| CN102262942A (en) | Method for preparing conductive silver paste | |
| CN105879896A (en) | Preparation method of Cu3B2O6/g-C3N4 (cupric borate/graphitic carbon nitride) heterojunction photocatalyst and method for degrading methylene blue dye wastewater | |
| CN105502564A (en) | Adsorbing agent capable of selectively removing dyes containing sulfonic acid groups in wastewater and method of adsorbing agent | |
| CN104625044A (en) | Ferroferric oxide/silver composite material and manufacturing method and application of ferroferric oxide/silver composite material | |
| CN100345764C (en) | Two-step method for preparing stannic oxide nano material | |
| CN102586767B (en) | Preparation method for loading Cu3.8Ni alloy crystal on carbon nanotube | |
| CN114280110B (en) | MOF-polystyrene microsphere composite material and preparation method and application thereof | |
| CN100519015C (en) | Chemical reduction process of preparing silver powder | |
| CN102674830A (en) | Alkaline earth metal titanate containing low free alkaline earth metal oxide and preparation method for alkaline earth metal titanate | |
| Beshkar et al. | Surfactant free synthesis of Sr 2 CeO 4 nanostructures and their application in removal of organic pollutions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |