CN106363165B - A kind of sheet of copper particle and preparation method thereof, catalyst, electrode - Google Patents
A kind of sheet of copper particle and preparation method thereof, catalyst, electrode Download PDFInfo
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- CN106363165B CN106363165B CN201610801199.7A CN201610801199A CN106363165B CN 106363165 B CN106363165 B CN 106363165B CN 201610801199 A CN201610801199 A CN 201610801199A CN 106363165 B CN106363165 B CN 106363165B
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- copper particle
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 130
- 239000010949 copper Substances 0.000 title claims abstract description 130
- 239000002245 particle Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 8
- 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 17
- 235000019441 ethanol Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical group COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 22
- 229940095102 methyl benzoate Drugs 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 8
- NUJGJRNETVAIRJ-UHFFFAOYSA-N 1-octanal group Chemical group C(CCCCCCC)=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 4
- 150000001299 aldehydes Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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
- 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
- 230000035484 reaction time Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 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
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 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
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 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
- 239000012528 membrane Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000126 substance Substances 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
- 238000003828 vacuum filtration Methods 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 a kind of sheet of copper particles and preparation method thereof, catalyst, electrode.It is the in the mixed solvent of 1:0.25~1 that preparation method of the invention, which includes: by the volume ratio that mantoquita is dissolved in oleic acid and ethyl alcohol, and surfactant is added, reducing agent is added, and obtains the mixed solution that mantoquita content is 1g/L~10g/L；The mixed solution that the mantoquita content is 1g/L~10g/L is packed into autoclave, it is reacted 8~15 hours under conditions of 170~200 DEG C, it is 500nm or less to obtain the average value of thickness, the absolute deviation average value of thickness is 50nm or less, and the maximum sized average value of plane is 5000nm~20000nm, and the maximum sized absolute deviation average value of plane is 1500nm sheet of copper particle below.This method simple process, obtained sheet of copper particle size is uniform, regular shape, monodispersity are preferable.
Description
Technical field
The present invention relates to a kind of sheet of copper particles and preparation method thereof, catalyst, electrode.
Background technique
Copper be widely studied as a kind of transition metal, because of its good performance, reserves abundant, cheap price and
Using.For example, copper particle can be used as sewage disposal device discharge electrode, catalytic reaction catalyst, high conductivity and high intensity are received
Rice copper material etc..The difference of the pattern of copper particle, size and structure keeps its performance different.For example, the biggish copper particle of surface area is suitable
Catalyst is made in conjunction, and regular shape, the more smooth copper particle in surface are suitable as sewage disposal device discharge electrode.Currently, system
Standby regular shape, the more smooth sheet of copper particle in surface is one of hot research direction.
The method of prior art preparation sheet of copper particle mainly has: template, electrolysis method, solution phase chemical reduction, machinery
Polishing, hydro-thermal method etc..For example, non-patent literature 1 (Chen Mingwei, Zhu Yongping, Zhang Weigang, using PEG600 as template liquid phase reduction
Method prepares flake copper powder [J], 2008,8 (5): 1003-1007) it discloses and uses cupric sulfate pentahydrate for copper source, PEG600 is template
Agent, sodium hypophosphite are that reducing agent prepares 10-40 μm of partial size, thick 1.5-2.5 μm of flake copper powder.For another example 2 (Cao of non-patent literature
Know state, Wu Bailin, chemical reduction method prepares the research [J] of conductive coating ultrafine flake copper powder, 2004,34 (6)) disclose with
Cupric sulfate pentahydrate is raw material, and ascorbic acid is reducing agent, and ammonium hydroxide is complexing agent, is prepared for the sheet of copper that particle diameter distribution is 1-10 μm
Powder.
In the implementation of the present invention, the inventor finds that the existing technology has at least the following problems:
The sheet of copper particle size of some complex process of the prior art, preparation is inhomogenous.
Summary of the invention
Sheet of copper particle size in order to solve the problems, such as prior art preparation is inhomogenous, and the embodiment of the present invention provides one kind
Sheet of copper particle and preparation method thereof.The technical solution is as follows:
In a first aspect, the embodiment of the present invention provides a kind of sheet of copper particle, the average value of the thickness of the sheet of copper particle
For 500nm hereinafter, the absolute deviation average value of the thickness is 50nm hereinafter, the plane of the sheet of copper particle is maximum sized
Average value is 5000nm~20000nm, and the maximum sized absolute deviation average value of plane is 1500nm or less.
Specifically, the plane of the sheet of copper particle is roughly circular or hexagon.
Specifically, the variance of the thickness of the sheet of copper particle is 500 or less.
Specifically, the variance of the planar dimension of the sheet of copper particle is 50 or less.
Specifically, the content of the impurity of the sheet of copper particle is 0.1% or less.
Specifically, the sheet of copper particle does not contain cuprous oxide and copper oxide.
Second aspect, the embodiment of the present invention provide a kind of deposit comprising sheet of copper particle, which includes:
Sheet of copper particle described in 90% or more first aspect of the embodiment of the present invention, and
Copper particle other than sheet of copper particle described in 10% first aspect of the embodiment of the present invention below.
The third aspect, the embodiment of the present invention provide a kind of preparation method of sheet of copper particle.Include:
It is the in the mixed solvent of 1:0.25~1 by the volume ratio that mantoquita is dissolved in oleic acid and ethyl alcohol, surfactant is added,
Reducing agent is added, obtains the mixed solution that mantoquita content is 1g/L~10g/L；
The mixed solution that the mantoquita content is 1g/L~10g/L is packed into autoclave, in 170~200 DEG C of item
It is reacted under part, obtains the mixed solution containing sheet of copper particle.
Preferably, the mantoquita is inorganic mantoquita.
Preferably, the inorganic mantoquita is copper nitrate, copper sulphate, copper acetate or copper chloride.
Preferably, the mixed solvent is the mixed solvent that the volume ratio of oleic acid and ethyl alcohol is 1:0.25~0.5.
Preferably, the surfactant is methyl benzoate.
Preferably, the content of the methyl benzoate is 3%~11%.
Preferably, the reducing agent is aldehydes reducing agent.
Preferably, the aldehydes reducing agent is long-chain aldehydes.
Preferably, the long-chain aldehydes is 1- octanal.
Preferably, the autoclave is flange form autoclave.
Preferably, the reaction time of the reaction is 8-15 hours.
Fourth aspect, the embodiment of the present invention provide a kind of catalyst, include piece described in first aspect of the embodiment of the present invention
Shape copper particle.
5th aspect, the embodiment of the present invention provide a kind of electrode, include sheet described in first aspect of the embodiment of the present invention
Copper particle.
Technical solution 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 particle, using a step hydrothermal synthesis method, using oleic acid and ethyl alcohol as molten
Inorganic mantoquita is dissolved in solvent by agent, using methyl benzoate as surfactant, 1- octanal as reducing agent, 170~
200 DEG C are reacted 8~15 hours, then obtain copper particle through suction filtration, washing, centrifuge separation and vacuum drying；This method simple process,
Obtained sheet of copper particle is that monodispersity is good, the particle of regular shape, size uniformity, and plane is roughly circular or six sides
Shape, the average value of the thickness of the sheet of copper particle be 500nm hereinafter, the absolute deviation average value of the thickness be 50nm with
Under.The maximum sized average value of plane of the sheet of copper particle is 5000nm~20000nm, and the plane is maximum sized absolutely
It is 1500nm or less to deviation average；And the sheet of copper particle does not include copper oxide and cuprous oxide, the content of impurity
It is 0.1% or less.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the scanning electron microscope diagram for multiple sheet of copper particles that the embodiment of the present invention 1 provides；
Fig. 2 is the scanning electron microscope diagram for the single sheet of copper particle that the embodiment of the present invention 1 provides；
Fig. 3 is the scanning electron microscope diagram for the single sheet of copper grain thickness that the embodiment of the present invention 1 provides；
Fig. 4 is the ratio distribution map of the sheet of copper particle plane full-size that the embodiment of the present invention 1 provides and thickness；
Fig. 5 is the X-ray diffractogram for the sheet of copper particle that the embodiment of the present invention 1 provides；
Fig. 6 is the energy spectrum diagram for the sheet of copper particle that the embodiment of the present invention 1 provides.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached 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 particle, the average value of the thickness of the sheet of copper particle is
500nm is hereinafter, the absolute deviation average value of the thickness is 50nm hereinafter, the plane of the sheet of copper particle is maximum sized average
Value is 5000nm~20000nm, and the maximum sized absolute deviation average value of plane is 1500nm or less.Wherein, plane is maximum
Size refers to an endpoint of plane to the maximum length of another endpoint.
It is as super although the restriction of the not no lower limit of the average value of the thickness of the sheet of copper particle in above-mentioned first aspect
0nm is crossed, can be 10~500nm, it is also possible to be preferably 490nm or less or 480nm or less or 460nm as an example
Below or 440nm or less or 420nm or less or 400nm or less or 380nm or less or 360nm or less or 340nm or less,
Or 320nm or less or 300nm hereinafter, can also be preferably 20nm or more or 30nm or more or 40nm or more or 50nm with
Upper or 60nm or more or 70nm or more or 80nm or more or 90nm or more or 100nm or more or 110nm or more or
120nm or more, more preferably 130~290nm, further preferably 150~250nm.
Although the restriction of the not no lower limit of the absolute deviation average value of the thickness of the sheet of copper particle, as an example, Ke Yiwei
0-50nm, it is also possible to be preferably 40nm or less or 30nm or less or 20nm hereinafter, more preferably 1-19nm, further excellent
It is selected as 5-10nm.
The maximum sized average value of the plane of the sheet of copper particle is 5000nm~20000nm, can also be preferably
5500nm~18000nm or 6000nm~17000nm or 6500nm~16000nm or 7000nm~15000nm, more preferably
For 7500nm~14000nm, further preferably 8000nm~13000nm.
Although the restriction of the not no lower limit of the maximum sized absolute deviation average value of the plane of the sheet of copper particle, as one
Example, can be 100-1500nm, it is also possible to be preferably 1400nm or less or 1300nm or less or 1200nm or less or
1100nm is hereinafter, can also be preferably 200nm or more or 300nm or more or 400nm or more or 500nm or more or 600nm
More than, more preferably 700-1000nm, further preferably 800-920nm.
Specifically, the plane of the sheet of copper particle is roughly circular or hexagon.
Specifically, the variance of the thickness of the sheet of copper particle is 500 or less.Wherein, the side of the thickness of the sheet of copper particle
Difference can be 10~500 as an example, it is also possible to be preferably 400 or less or 300 or less or 200 hereinafter, more preferably
100-200, more preferably 110-150.
Specifically, the variance of the planar dimension of the sheet of copper particle is 50 or less.Wherein, the plane meter of the sheet of copper particle
Very little variance as an example, can be 0~50, it is also possible to be preferably 40 or less or 30 or less or 20 hereinafter, or 10 with
Under, more preferably 0-9, more preferably 1-8.
Specifically, the content of the impurity of the sheet of copper particle is 0.1% or less.More preferably 0.05% hereinafter, more preferably
It is 0.02% or less.
Specifically, which does not contain cuprous oxide and copper oxide.
Second aspect, the embodiment of the present invention provide a kind of deposit comprising sheet of copper particle, which includes:
Sheet of copper particle in 90% or more first aspect of the embodiment of the present invention, and
The copper particle other than sheet of copper particle in 10% first aspect of the embodiment of the present invention below.
The third aspect, the embodiment of the present invention provide a kind of preparation method of sheet of copper particle.Include:
It is the in the mixed solvent of 1:0.25~1, oil by the volume ratio that 0.015g~0.15g mantoquita is dissolved in oleic acid and ethyl alcohol
The mixed solvent of acid and ethyl alcohol is 15mL, and the surfactant of 0.5~2.0mL is added, the reducing agent of 1mL is added, obtains mantoquita
Content is the mixed solution of 1g/L~10g/L；
Wherein, oleic acid and ethyl alcohol are mixed with volume ratio for the arbitrary proportion of 1:0.25~1, when ethanol content is less than 20%
When, it will form mixed and disorderly little particle, when ethanol content is greater than 50%, will form the copper particle of cube structure.Mantoquita content is
Sheet of copper particle could be formed when 1g/L~10g/L；
The mixed solution that the mantoquita content is 1g/L~10g/L is packed into autoclave, in 170~200 DEG C of item
It is reacted under part, obtains the mixed solution containing sheet of copper particle.
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
Preferably 2.94g/L~3.03g/L.
Preferably, mantoquita is inorganic mantoquita.
Preferably, inorganic mantoquita is copper nitrate, copper sulphate, copper acetate or copper chloride.
Preferably, mixed solvent is the mixed solvent that the volume ratio of oleic acid and ethyl alcohol is 1:0.25~0.5.
Preferably, surfactant is methyl benzoate.
Preferably, the content of methyl benzoate is 3%~11%, and the content of methyl benzoate could when being 3%~11%
Form sheet of copper particle.
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 reaction time of reaction is 8-15 hours.
Fourth aspect, the embodiment of the present invention provide a kind of catalyst, include piece described in first aspect of the embodiment of the present invention
Shape copper particle.
5th aspect, the embodiment of the present invention provide a kind of electrode, include sheet described in first aspect of the embodiment of the present invention
Copper particle.
Chemical reagent used in the embodiment of the present invention:
Ethyl alcohol: chemistry is pure, and producer is Beijing chemical reagents corporation；
Oleic acid: chemistry is pure, and producer is the Shantou, Guangdong city chemical plant Xi Long；
Copper nitrate: chemistry is pure, and producer is Beijing chemical reagents corporation；
Copper sulphate: chemistry is pure, and producer is Beijing chemical reagents corporation；
Copper chloride: chemistry is pure, and producer is Beijing chemical reagents corporation；
1- octanal: chemistry is pure, and producer is Beijing chemical reagents corporation；
Methyl benzoate: analysis is pure, and producer is Aladdin Reagent Company.
Instrument used in the embodiment of the present invention:
Flange form autoclave: customization, liner is polytetrafluoroethylene (PTFE), and shell is stainless steel；
TGL-16C type centrifuge, ANKE instrument company；
KQ-300GVDV type ultrasonic machine, Kunshan Ultrasonic Instruments Co., Ltd.；
Machine, Tianjin Stettlen Instrument Ltd. is filtered by vacuum in III type of SHZ-；
DZ-1BC type vacuum oven, Tianjin Stettlen Instrument Ltd.；
200 type scanning electron microscope of Sirion, Dutch FEI Co.
X-ray diffractometer, X ' Pert Pro MRD, Dutch Panaco company.
Embodiment 1
10mL oleic acid and 5mL ethyl alcohol are mixed to get mixed solvent, 0.05g copper nitrate is dissolved in the in the mixed solvent,
1mL methyl benzoate is added, adds 1mL 1- octanal, and be stirred, it is molten to obtain the mixing that nitric acid copper content is 2.94g/L
Liquid；The mixed solution is fitted into flange form autoclave, reaction temperature is 180 DEG C, and the reaction time is 10 hours；It takes out anti-
The vacuum filtration machine of the reaction product that should be obtained, the miillpore filter for being 0.22 μm with filter membrane filters the reaction product；It will filter
To filter cake be added 10mL ethyl alcohol in be cleaned by ultrasonic, clean repeatedly twice；It is centrifuged with the centrifuge that revolving speed is 5000 revs/min
Separation cleaning fluid and copper particle, filtering discards supernatant liquor after centrifugation；The copper particle that centrifugation obtains is put into vacuum oven
Drying.
Embodiment 2
The preparation method of sheet of copper particle provided in this embodiment difference from example 1 is that: by 0.05g sulfuric acid
Copper dissolution is in the in the mixed solvent of oleic acid and ethyl alcohol.
Embodiment 3
The preparation method of sheet of copper particle provided in this embodiment difference from example 1 is that: by 12mL oleic acid
Mixed solvent is mixed to get with 3mL ethyl alcohol.
Embodiment 4
The preparation method of sheet of copper particle provided in this embodiment difference from example 1 is that: 0.5mL benzene is added
Methyl formate；Obtain the mixed solution that nitric acid copper content is 3.03g/L.
Embodiment 5
The preparation method of sheet of copper particle provided in this embodiment difference from example 1 is that: 2mL benzene first is added
Sour methyl esters；Obtain the mixed solution that nitric acid copper content is 2.78g/L.
Embodiment 6
The present embodiment is using scanning electron microscope SEM (Scanning Electron Microscope) to passing through this hair
Sheet of copper particulate samples prepared by bright embodiment 1 are characterized, and can intuitively be reflected by the scanning electron microscope diagram of sample
The structure feature of sheet of copper particle and pattern etc. out.
Fig. 1 is the scanning electron microscope diagram of multiple sheet of copper particles, and Fig. 2 and Fig. 3 are the scanning of single sheet of copper particle
Electron microscope picture, as can be seen that the surface topography of the 1 sheet of copper particle being prepared is advised through this embodiment from above-mentioned figure
Then, plane is roughly circular or hexagon.
It is laggard to the plane full-size and thickness measure of 50 sheet of copper particulate samples of the offer of the embodiment of the present invention 1
Row statistical analysis, the plane full-size for obtaining lamellar structure is 6000-10000nm, with a thickness of 150-250nm.Plane is maximum
Size average is 8000nm, and the maximum sized absolute deviation average value of plane is 920nm, and the maximum sized variance of plane is
1.52, thickness average value 189nm, the absolute deviation average value of thickness are 8.85nm, and the variance of thickness is 144.2, are illustrated logical
Cross that the sheet of copper particle size that the embodiment of the present invention 1 is prepared is uniform, and monodispersity is preferable.And as shown in figure 4, Fig. 4 is
The ratio distribution map of sheet of copper particle plane full-size and thickness that the embodiment of the present invention 1 provides, the sheet of copper particulate samples
Plane full-size and its thickness ratio be 30~55, and have 79% copper particle plane full-size and thickness ratio
It falls in 35~45 sections, equally illustrates that the dimension scale of the sheet of copper particle is relatively unified.
Embodiment 7
The present embodiment is prepared using X-ray diffractometer XRD (X-Ray Diffraction) to through the embodiment of the present invention 1
Sheet of copper particulate samples characterized, pass through the crystal structure etc. of the available sheet of copper particle of the X-ray diffractogram of sample
Information.
Fig. 5 is the X-ray diffractogram of sheet of copper particle, and 02-1225 file can be with from Fig. 5 and PDF2002 database
It obtains, the diffraction maximum in figure is from left to right the diffraction maximum of the crystal faces such as copper (111), (200), (220) respectively, illustrates sheet of copper
Particle is copper crystal, and the content of its impurity is 0.1% or less.
Embodiment 8
The present embodiment utilizes energy disperse spectroscopy EDS (the Energy Dispersive in scanning electron microscope
Spectroscopy) the sheet of copper particulate samples of through the embodiment of the present invention 1 preparation are characterized, pass through the energy spectrum diagram of sample
The information such as the element that available sheet of copper particle contains.
Fig. 6 is the energy spectrum diagram of sheet of copper particle, from fig. 6, it can be seen that the peak of copper is main peaks in figure, 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 sheet of copper particle without copper oxide or cuprous oxide, the content of impurity is 0.1% or less.
For embodiment 2~5, detected using the mensuration mode for being similar to embodiment 6~8, as a result, it has been found that, Ge Xiangjie
Fruit is approximate with embodiment 1.
Technical solution 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 particle, using a step hydrothermal synthesis method, using oleic acid and ethyl alcohol as molten
Inorganic mantoquita is dissolved in solvent by agent, using methyl benzoate as surfactant, 1- octanal as reducing agent, 170~
200 DEG C are reacted 8~15 hours, then obtain copper particle through suction filtration, washing, centrifuge separation and vacuum drying；This method simple process,
Obtained sheet of copper particle is that monodispersity is good, the particle of regular shape, size uniformity, and plane is roughly circular or six sides
Shape, the average value of the thickness of the sheet of copper particle be 500nm hereinafter, the absolute deviation average value of the thickness be 50nm with
Under.The maximum sized average value of plane of the sheet of copper particle is 5000nm~20000nm, and the plane is maximum sized absolutely
It is 1500nm or less to deviation average；And the sheet of copper particle does not include copper oxide and cuprous oxide, the content of impurity
It is 0.1% or less.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of preparation method of sheet of copper particle, which is characterized in that the described method includes:
It is the in the mixed solvent of 1:0.25~0.5 by the volume ratio that mantoquita is dissolved in oleic acid and ethyl alcohol, surfactant is added, adds
Enter reducing agent, obtains the mixed solution that mantoquita content is 1g/L~10g/L；
The mixed solution that the mantoquita content is 1g/L~10g/L is packed into autoclave, under conditions of 170~200 DEG C
Reaction 8~15 hours, obtains the mixed solution containing sheet of copper particle,
The mantoquita is inorganic mantoquita；
The surfactant is methyl benzoate；
The reducing agent is 1- octanal,
The average value of the thickness of the sheet of copper particle be 500nm hereinafter, the absolute deviation average value of the thickness be 50nm with
Under, the maximum sized average value of plane of the sheet of copper particle is 5000nm~20000nm, and the plane is maximum sized absolutely
It is 1500nm or less to deviation average；
The variance of the thickness of the sheet of copper particle be 500 hereinafter, the variance of the planar dimension of the sheet of copper particle be 50 with
Under.
2. the preparation method of sheet of copper particle according to claim 1, which is characterized in that the inorganic mantoquita is nitric acid
Copper, copper sulphate, copper acetate or copper chloride.
3. the preparation method of sheet of copper particle according to claim 1, which is characterized in that the volume of the methyl benzoate
Content is 3%~11%.
4. the preparation method of sheet of copper particle according to claim 1, which is characterized in that the autoclave is flange
Formula autoclave.
5. a kind of sheet of copper particle, which is characterized in that the sheet of copper particle is by according to any one of claims 1 to 4
Preparation method is prepared；
The average value of the thickness of the sheet of copper particle be 500nm hereinafter, the absolute deviation average value of the thickness be 50nm with
Under, the maximum sized average value of plane of the sheet of copper particle is 5000nm~20000nm, and the plane is maximum sized absolutely
It is 1500nm or less to deviation average；
The variance of the thickness of the sheet of copper particle be 500 hereinafter, the variance of the planar dimension of the sheet of copper particle be 50 with
Under.
6. sheet of copper particle according to claim 5, which is characterized in that its plane is roughly circular or hexagon.
7. sheet of copper particle according to claim 5, which is characterized in that the content of impurity is 0.1% or less.
8. sheet of copper particle according to claim 5, which is characterized in that it does not contain cuprous oxide and copper oxide.
9. a kind of deposit comprising sheet of copper particle, which is characterized in that the deposit includes:
The sheet of copper particle of 90% or more preparation method according to any one of claims 1 to 4 preparation, and
Copper particle other than the sheet of copper particle of 10% preparation method preparation according to any one of claims 1 to 4 below.
10. a kind of catalyst, the sheet of copper particle comprising preparation method according to any one of claims 1 to 4 preparation.
11. a kind of electrode, the sheet of copper particle comprising preparation method according to any one of claims 1 to 4 preparation.
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