CN106115803B - A kind of Co3O4Nano dot Aqueous phase synthetic method - Google Patents
A kind of Co3O4Nano dot Aqueous phase synthetic method Download PDFInfo
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- CN106115803B CN106115803B CN201610521213.8A CN201610521213A CN106115803B CN 106115803 B CN106115803 B CN 106115803B CN 201610521213 A CN201610521213 A CN 201610521213A CN 106115803 B CN106115803 B CN 106115803B
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- 239000008346 aqueous phase Substances 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 239000002096 quantum dot Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000002156 adsorbate Substances 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims 2
- 230000003111 delayed effect Effects 0.000 claims 1
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 one week Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
A kind of Co3O4Nano dot Aqueous phase synthetic method, configures A, and tri- kinds of solution of B, C, first to C solution is added in reactor, solution A, B solution are slowly dropped in C solution simultaneously, and it is 1 that final solution A is added dropwise volume with C solution volume ratio:2‑1:100, control B solution rate of addition makes course of reaction total solution pH remain constant, and A, B solution time for adding terminal is consistent；Product is separated again, cobalt hydroxide nano dot particle is obtained, by cobalt hydroxide nano dot particle 300 500oC temperature lower calcinations, or 150 250oHydro-thermal is that can obtain Co at a temperature of C3O4Nano dot material, the method low production cost, preparation efficiency is high, method is simple to operation, and course of reaction is used without toxic raw materials, and overall energy consumption is relatively low, and waste, waste water are repeatable using environmentally safe by treatment after reaction, it is possible to achieve heavy industrialization application.
Description
Technical field
The present invention relates to Co3O4A kind of nano material synthetic technology, and in particular to Co3O4Nano dot Aqueous phase synthetic method.
Background technology
Co3O4Nano material is widely used in lithium ion battery, super capacitor due to its outstanding physical and chemical performance
The fields such as device, F- T synthesis, electro-catalysis and photocatalysis.
With going deep into for research, scholars have found Co3O4With the reduction of its particle size, its specific surface increases nano material
Greatly, surface adsorption property and surface reaction can be significantly increased all.This is based on, scholars constantly explore how to prepare and provide
There is the Co of low particle size3O4Nano dot material.By the end of preparation Co that is current, having developed3O4The method of nano dot material has
A lot, its summary and induction can be broadly divided into hydro-thermal-solvent-thermal method, sol-gel process, LSS methods, micella-reverse micelle method（Including
Micro emulsion method）, spray pyrolysis, chemical precipitation method etc..Although these methods can all realize Co substantially3O4The preparation of nano dot, but
It is several big problems of their generally existings：
1）Production cost is higher；2）Operating process is complicated；3）Production efficiency is relatively low；4）Product cut size；5）Part Methods are big
Amount uses organic matter, and its production waste can cause severe contamination to environment.
Current existing preparation Co is caused just because of this several big problem3O4The method major part of nano dot cannot all be realized
Industrialized production.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the invention to provide a kind of Co3O4Nano dot Aqueous phase synthesizes
Method, realizes Co3O4Nano dot low cost, high efficiency is simple and easy to apply, and nontoxic pollution-free preparation.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of Co3O4Nano dot Aqueous phase synthetic method, comprises the following steps:
1）Configuration A, tri- kinds of solution of B, C：
Solution A：The mixed solution of cobalt salt, alcohol and water, cobalt salt concentration is 0.01~4 mol/L, and the ratio of alcohol and water is 1:1
~1:100；
B solution：Alkaline buffer reagent, alcohol and the aqueous solution, alkaline buffer reagent concentration are 0.01-4 mol/L, alcohol and water
Ratio is 1:1~1:100；
C solution：Hydrogen peroxide, buffer reagent, alcohol and the aqueous solution, hydrogen peroxide account for the 0.1~20% of total solution volume, buffering examination
Agent concentration according to need to by C solution pH maintain 8-14 between matched, the ratio of alcohol and water is 1:1~1:100；
2）Course of reaction：
First to adding C solution, controlling reaction temperature to maintain 4-40 in reactoroBetween C, regulation mixing speed is caused
Stirring fully but not spatter liquid, solution A, B solution is slowly dropped in C solution simultaneously, and final solution A is added dropwise volume and C
Liquor capacity ratio is 1:2-1:100, control B solution rate of addition makes course of reaction total solution pH remain constant, A, B solution
Time for adding terminal is consistent；
3）Product is separated
Question response stands reaction solution half an hour after terminating, and product is reunited and is deposited in reactor bottom, isolates product product
And removal product nano-material surface adsorbate is washed, and purees is obtained after centrifugal dehydration, purees is freezed into blocking rear freezing
Drying obtains cobalt hydroxide nano dot particle by removing moisture removal, by cobalt hydroxide nano dot particle in 300-500oC temperature
The lower calcining of degree, or in 150-250oHydro-thermal is that can obtain Co at a temperature of C3O4Nano dot material.
Described cobalt salt can be cobaltous sulfate, and cobalt chloride, cobalt nitrate, the arbitrary proportion of one or more in cobalt acetate is mixed
Compound.
During alcohol in described solution A, B solution and C solution can be methyl alcohol, ethanol, propyl alcohol, butanol, amylalcohol, hexanol
The arbitrary proportion mixture of one or more.
Described alkaline buffer reagent can be sodium phthalate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen
Sodium oxide molybdena, the arbitrary proportion mixture of one or more in sodium tetraborate.
Described buffer reagent can be sodium phthalate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, hydroxide
Sodium, the sodium tetraborate arbitrary proportion mixture of one or more.
The beneficial effects of the invention are as follows：
Can prepare that particle diameter distribution is homogeneous, particle size is smaller, crystalline phase is single using the present invention, better crystallinity degree and without miscellaneous
The Co of matter3O4Nano dot.Compared with existing method, low production cost of the present invention, preparation efficiency is high, and method is simple to operation, reaction
Process is used without toxic raw materials, and overall energy consumption is relatively low, and waste, waste water are utilized to environment without dirt by the way that treatment is repeatable after reaction
Dye, it is possible to achieve heavy industrialization application.
Brief description of the drawings
Fig. 1 is the XRD spectrum of product 1 and product 2 in the embodiment of the present invention.
Fig. 2 is the XPS collection of illustrative plates of product 1 and product 2 in the embodiment of the present invention, wherein a is wide range, and b is the narrow spectrums of Co 2p.
Fig. 3 is the TEM collection of illustrative plates of product 1 in the embodiment of the present invention, wherein a low powers TEM pictures, and b is HRTEM pictures, and c is
HRTEM picture enlarged drawings, d is particle diameter distribution.
Fig. 4 is the TEM collection of illustrative plates of product 2 in the embodiment of the present invention, wherein a low powers TEM pictures, and b is HRTEM pictures, and c is
HRTEM picture enlarged drawings, d is particle diameter distribution.
Fig. 5 is the UV-Vis collection of illustrative plates of product 1 and product 2 in the embodiment of the present invention.
Fig. 6 is that the visible light catalytic of product 1 in the embodiment of the present invention decomposes pure water product hydrogen product oxygen performance map.
Specific embodiment
The present invention is further discussed below with reference to embodiments, but the present invention is not limited to following examples.
Embodiment 1
Solution A selects cobaltous sulfate, ethanol, water mixed solution, and cobalt sulfate concentration is 1 mol/L, and the ratio of ethanol and water is
1:4.B solution selects NaOH, ethanol, the aqueous solution, and naoh concentration is the ratio and solution A of 4 mol/L, ethanol and water
It is identical.C solution selects hydrogen peroxide, sodium tetraborate, NaOH, ethanol, the aqueous solution, hydrogen peroxide to account for total solution volume fraction and be
1%, sodium tetraborate concentration is 1 mol/L, and adjustment naoh concentration causes that pH is 10, the ratio and solution A phase of ethanol and water
Together.
Take 1 L C solutions to be added in the reactor with thermostat, strict controlling reaction temperature maintains 5oC, adjusts
Section mixing speed is 800 r/min.A, B solution are slowly dropped in C solution simultaneously, solution A rate of addition is 15 mL/h,
Dropwise addition volume is 60 mL, and control B solution rate of addition makes course of reaction total solution pH remain at 10 constant, A, B solution drop
Plus terminal is consistent.
Question response stands reaction solution half an hour after terminating, and product can reunite and be deposited in reactor bottom, isolate product simultaneously
Washing removal product nano-material surface adsorbate, obtains purees after centrifugal dehydration, it is dry that purees is freezed into blocking rear freezing
Dry water removal, then 200oThe h of hydro-thermal 4 is that can obtain product 1 under C.
The XRD spectrum of product 1 is as shown in Figure 1, it can be seen that the XRD spectrum of product 1 is 31.2 in 2 θ valueso, 36.9 o,
38.4 o, 44.8 o, 55.6 o, 59.1oWith 65.1oWhen all there is diffraction maximum, these peak positions and PDF cards（JCPDS No.
00-001-1152）In corresponding diffraction maximum position fit like a glove, correspond respectively to crystal face（220）,（311）,（222）,（400）,
（422）,（511）,（440）, this explanation product 1 is Emission in Cubic Co3O4.Fig. 2（a）And Fig. 2（b）The XPS collection of illustrative plates of product 1 is illustrated,
It can be seen that product 1 only exists Co, tri- kinds of elements of O, C from wide range.Narrow spectrum display product 1 can be 780.3 in combination,
Difference existing characteristics peak at 782.1,795.3,797.8 eV, tables look-up and understands that these peaks correspond respectively to CoIII（2p3/2）,
CoII（2p3/2）, CoIII（2p1/2）And CoII（2p1/2）.In Co 2p1/2With Co 2p3/2All to that should have Co behind characteristic peakII
（2p3/2）Shake-up satellites, and CoII（2p1/2）Shake-up satellites.By calculating we can see that product 1
CoIIAnd CoIIIPeak area ratio be about 1:2, this explanation product 1 is pure Co3O4。
The transmission electron microscope of product 1（TEM）Image is as shown in figure 3, by Fig. 3（a）It can be seen that product 1 is by countless
The particle composition of individual size uniformity particle diameter very little.Fig. 3（b）Illustrate the high-resolution electronic projection microscope of product 1（HRTEM）Figure
Picture, by being clear that each short grained lattice fringe in product 1 in figure, each little particle in this explanation product 1
It is a monocrystalline.Further HRTEM images are amplified and obtains Fig. 3（c）, the lattice of the particle of product 1 can be accurately measured from figure
2.0 are spaced about, with PDF cards（JCPDS No. 00-001-1152）In（400）Crystal face correspondence, this is also reconfirmed
Product 1 is Emission in Cubic Co3O4.To Fig. 3（b）In the granule number of each size count obtaining Fig. 3（d）, as can be seen from Figure
Using the Co of present invention synthesis3O4Product particle size is all between 2-5 nm and most with the particle of 2-3 nm, distribution of particles
Narrow range.
Embodiment 2
Preparation process is same as Example 1 with preparation condition, and hydrogen peroxide preparation is only added without in C solution, can make
Go out product 2.
The XRD spectrum of product 2 is as shown in Figure 1, it can be seen that the XRD spectrum of product 2 is similar to product 1, is in 2 θ values
31.2o, 36.9 o, 38.4 o, 44.8 o, 55.6 o, 59.1oWith 65.1oWhen there is diffraction maximum, with PDF cards（JCPDS No.
00-001-1152）Middle crystal face（220）,（311）,（222）,（400）,（422）,（511）,（440）Peak is corresponding, and this explanation is produced
Product 2 are also Emission in Cubic Co3O4.Fig. 2（a）And Fig. 2（b）The XPS collection of illustrative plates of product 2 is illustrated, it can be seen that product 2 from wide range
Only exist Co, tri- kinds of elements of O, C.Narrow spectrum display product 2 also can be at 780.3,782.1,795.3,797.8 eV in combination
It is respectively present and corresponds respectively to CoIII（2p3/2）, CoII（2p3/2）, CoIII（2p1/2）And CoII（2p1/2）Characteristic peak.In Co
2p1/2With Co 2p3/2All to that should have Co behind characteristic peakII（2p3/2）Shake-up satellites, and CoII（2p1/2） shake-
Up satellites.By calculating we can see that the Co of product 2IIAnd CoIIIPeak area ratio also close to being 1:2, this explanation
Product 2 is also pure Co3O4。
The transmission electron microscope of product 2（TEM）Image is as shown in fig. 6, by Fig. 4（a）、4（b）With 4（c）It can be seen that producing
Product 2 are made up of larger nano particle, and the interplanar distance of particle is about 2.44, with PDF cards（JCPDS No. 00-001-
1152）In（311）Crystal face corresponds to this and has also reconfirmed that product 2 is Emission in Cubic Co3O4.Equally, by Fig. 4（d）It can be seen that producing
The granular size of product 2 between 10-50 nm, and with the particle of 20-30 nm at most, and particle distribution range is very wide.
Embodiment 3
The specific surface area of product 1 and product 2 is measured using BET methods, we can obtain the ratio of product 1 and product 2
Surface area is respectively 259.86 m2·g-1With 7.84 m2·g-1.Product 1 and product 2 are dispersed in water respectively, such as Fig. 5 institutes
Show, product 1 can disperse to be formed well will not be precipitated in colloid, one week, and product 2 forms suspension after disperseing, a few minutes
It is interior with regard to precipitated and separated.UV-Vis collection of illustrative plates carrys out the optical absorption characteristic of analysis product 1 and product 2, as can be seen from Figure 5, product 1 and product
2 have two ABSORPTION EDGEs, and, about in 675 nm and 950 nm, the ABSORPTION EDGE of product 1 is about in 515 nm and 815 for the ABSORPTION EDGE of product 2
At nm.Compared with product 2, the ABSORPTION EDGE of product 1 there occurs obvious blue shift.
Embodiment 4
Using 100 mL pure water as reaction solution, decomposing pure water performance to product 1 and the visible light catalytic of product 2 is carried out
Test.From 130 mL Pyrex glass reactors of side-irradiation, catalytic amount is 10 mg to reactor, and irradiation light is 180
mW cm-2Band stop filter (λ>420 nm) xenon lamp, under differential system test, purge gass are argon gas, purging speed be 1
mL min-1, reaction temperature is maintained at 30oC, the testing time is 500 min.By test we have found that product 2 does not possess visible
Photocatalysis Decomposition pure water produces the performance that hydrogen produces oxygen, and product 1 possesses visible light catalytic and decomposes the performance that pure water produces hydrogen product oxygen.Fig. 6
The visible light catalytic for illustrating product 1 decomposes pure water product hydrogen product oxygen performance, it can be seen that in 500 min reactions, producing
It is not very big, speed kept stable that the speed of decomposition pure water product hydrogen product oxygen changes over time fluctuating range under the visible ray of product 1,
The decomposition water hydrogen producing Mean Speed of product 1 is tried to achieve using linear fit be about 0.871 μm of ol h-1, oxygen averagely produces speed about
It is 0.466 μm of ol h-1, hydrogen and oxygen actual average output rate ratios are 1.87:1, close to 2:1, this explanation product 1 has
There is non-loaded visible light catalytic to decompose the performance that pure water simultaneous hydrogen production produces oxygen.
Claims (5)
1. a kind of Co3O4Nano dot Aqueous phase synthetic method, it is characterised in that comprise the following steps:
1）Prepare A, tri- kinds of solution of B, C：
Solution A：The mixed solution of cobalt salt, alcohol and water, cobalt salt concentration is 0.01~4 mol/L, and the ratio of alcohol and water is 1:1~1:
100；
B solution：Alkaline buffer reagent, alcohol and the aqueous solution, alkaline buffer reagent concentration are the ratio of 0.01-4 mol/L, alcohol and water
It is 1:1~1:100；
C solution：Hydrogen peroxide, buffer reagent, alcohol and the aqueous solution, hydrogen peroxide account for the 0.1~20% of total solution volume, and buffer reagent is dense
Degree according to need to by C solution pH maintain 8-14 between matched, the ratio of alcohol and water is 1:1~1:100；
2）Course of reaction：
First to adding C solution, controlling reaction temperature to maintain 4-40 in reactoroBetween C, regulation mixing speed causes stirring
Fully but not spatter liquid, solution A, B solution are slowly dropped in C solution simultaneously, final solution A is added dropwise volume and C solution
Volume ratio is 1:2-1:100, control B solution rate of addition makes course of reaction total solution pH remain constant, and A, B solution is added dropwise
End time is consistent；
3）Product is separated
Question response stands reaction solution half an hour after terminating, and product is reunited and is deposited in reactor bottom, is isolated product product and is washed
Removal product nano-material surface adsorbate is washed, purees is obtained after centrifugal dehydration, purees is freezed into blocking rear freeze-drying
Cobalt hydroxide nano dot particle is obtained by removing moisture removal, by cobalt hydroxide nano dot particle in 300-500oAt a temperature of C
Calcining, or in 150-250oHydro-thermal is that can obtain Co at a temperature of C3O4Nano dot material.
2. a kind of Co according to claim 13O4Nano dot Aqueous phase synthetic method, it is characterised in that described cobalt salt can
Being cobaltous sulfate, cobalt chloride, cobalt nitrate, the arbitrary proportion mixture of one or more in cobalt acetate.
3. a kind of Co according to claim 13O4Nano dot Aqueous phase synthetic method, it is characterised in that described solution A,
Alcohol in B solution and C solution can be the arbitrary proportion of one or more in methyl alcohol, ethanol, propyl alcohol, butanol, amylalcohol, hexanol
Mixture.
4. a kind of Co according to claim 13O4Nano dot Aqueous phase synthetic method, it is characterised in that described alkalescence is delayed
It can be sodium phthalate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, NaOH, in sodium tetraborate one to rush reagent
Plant or several arbitrary proportion mixtures.
5. a kind of Co according to claim 13O4Nano dot Aqueous phase synthetic method, it is characterised in that described buffering examination
Agent can be sodium phthalate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, NaOH, sodium tetraborate one or more
Arbitrary proportion mixture.
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