CN109647414A - NiO-ZnO ball chain shape nano material and its preparation method and application - Google Patents
NiO-ZnO ball chain shape nano material and its preparation method and application Download PDFInfo
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- CN109647414A CN109647414A CN201910077570.3A CN201910077570A CN109647414A CN 109647414 A CN109647414 A CN 109647414A CN 201910077570 A CN201910077570 A CN 201910077570A CN 109647414 A CN109647414 A CN 109647414A
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- nio
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- nano material
- alcoholic solution
- ball chain
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000007146 photocatalysis Methods 0.000 claims abstract description 18
- 239000012798 spherical particle Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910018605 Ni—Zn Inorganic materials 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 93
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 86
- 239000011787 zinc oxide Substances 0.000 claims description 61
- 230000001476 alcoholic effect Effects 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 41
- 239000011701 zinc Substances 0.000 claims description 41
- 229910052725 zinc Inorganic materials 0.000 claims description 41
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- 150000005846 sugar alcohols Polymers 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010277 boron hydride Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 33
- 239000004065 semiconductor Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 58
- 230000000694 effects Effects 0.000 description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005622 photoelectricity Effects 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000005641 tunneling Effects 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
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The present invention relates to field of nanometer material technology, specifically, providing a kind of NiO-ZnO ball chain shape nano material and its preparation method and application.The NiO-ZnO ball chain shape nano material is mainly sequentially connected with by NiO-ZnO spherical particle；The NiO-ZnO spherical particle is using Ni-Zn as core, using NiO-ZnO as the particle of the core-shell structure of shell.The material has p-n heterojunction structure, is in ball chain shape, the material have NiO semiconductor and ZnO semiconductor inaccessiable excellent photocatalysis characteristic, photoelectric characteristic, pressure-sensitive character and gas-sensitive property etc..
Description
Technical field
The present invention relates to field of nanometer material technology, in particular to a kind of NiO-ZnO ball chain shape nano material and its preparation
Methods and applications.
Background technique
NiO is a kind of typical p-type semiconductor, has the characteristics such as good temperature-sensitive and air-sensitive, is a kind of up-and-coming
Functional material is widely used in the industries such as metallurgy, chemistry and electronics.The fine of nano-nickel oxide partial size, surface texture
Changed with crystal structure, causes to produce skin effect, small-size effect, quantum size effect and macroscopic quantum tunneling
Effect etc., to show excellent catalytic performance and electric property.
ZnO is typical third generation semiconductor material, has both the forbidden bandwidth of 3.37eV and the exciton bind energy of 60meV,
Belong to II-VI group semiconductor；Its band gap and exciton bind energy are larger, and transparency is high, there is excellent room temperature luminescent properties, half
There is application in the products such as liquid crystal display, thin film transistor (TFT), the light emitting diode in conductor field.Wherein, zinc oxide is air-sensitive
Important one kind in material can be monitored polluted gas toxic, harmful in environment.But zinc oxide gas sensitive
The problems such as sensitivity low, operating temperature is high, poor selectivity be also problem in the urgent need to address.
Monodimension nanometer material refers to that the material for nanoscale on two dimensions, monodimension nanometer material are that research electronics passes
The sizes of physical properties such as defeated behavior, optical characteristics and mechanics mechanical performance and the idealized system of latitude effect.With zero dimension and two
Dimension nano material is compared, and monodimension nanometer material has unique advantage in terms of developing function element, it can both realize a nanometer ruler
The connection of degree and information are transmitted, and can embody the quantum behavior of itself, and constructing, nanoelectronic and opto-electronic device etc. are functional
Important role is served as in element.
Currently, the preparation about monodimension nanometer material has a large amount of correlative study, but the overwhelming majority is common threadiness
Nanostructure, synthesis and preparation about ball chain-like nanometer structure are rarely reported, and utilize two kinds of NiO, ZnO different semiconductor materials
The ball chain shape nano structural material for constituting p-n heterojunction does not have been reported that even more.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of NiO-ZnO ball chain shape nano material, which has p-n heterojunction
Structure, be in ball chain shape, the material have NiO semiconductor and ZnO semiconductor inaccessiable excellent photocatalysis characteristic, photoelectricity
Characteristic, pressure-sensitive character and gas-sensitive property etc..
The second object of the present invention is to provide a kind of preparation method of NiO-ZnO ball chain shape nano material, this method work
Skill is simple, efficient, and the nanometer material structure being prepared using this method is clear, uniform in size, shows apparent ball chain shape.
The third object of the present invention is to provide a kind of NiO-ZnO ball chain shape applications to nanostructures.
The fourth object of the present invention is to provide a kind of photochemical catalyst, photoelectricity including NiO-ZnO ball chain shape nano material
Detector or gas detector.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the nano material is mainly by NiO- the present invention provides a kind of NiO-ZnO ball chain shape nano material
ZnO spherical particle is sequentially connected with；The NiO-ZnO spherical particle is using Ni-Zn as core, using NiO-ZnO as the nucleocapsid of shell
The particle of structure.
As further preferred technical solution, the diameter of the NiO-ZnO spherical particle is 300-500nm, preferably
350-450nm；
Preferably, the length of the nano material is 20-40 μm, preferably 25-35 μm.
Second aspect, the present invention provides a kind of preparation method of above-mentioned NiO-ZnO ball chain shape nano material, including it is following
Step:
By the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide after mixing again with
Mixed solution, is then placed in parallel magnetic field by reducing agent mixing, and heating is separated by solid-liquid separation after reaction, after separation
Solid product is washed, obtains the nano material after dry and oxidation processes.
As further preferred technical solution, nickel source includes at least one of nickel chloride, nickel sulfate or nickel nitrate；
Preferably, the concentration of nickel source is 0.05-0.15mol/L；
Preferably, zinc source includes at least one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate；
Preferably, the concentration in zinc source is 0.02-0.05mol/L；
Preferably, alkali metal hydroxide includes potassium hydroxide and/or sodium hydroxide；
Preferably, the concentration of alkali metal hydroxide is 1-1.5mol/L；
Preferably, alcoholic solution includes polyhydric alcohol solutions；
Preferably, polyhydric alcohol solutions include the polyhydric alcohol solutions of C2-C4；
Preferably, polyhydric alcohol solutions include ethylene glycol solution；
Preferably, reducing agent includes at least one of boron hydride, lithium aluminium hydride reduction, hydrazine hydrate or hydrogen；
Preferably, reducing agent is hydrazine hydrate；
Preferably, the concentration of hydrazine hydrate is 80%-90%；
Preferably, the molar ratio of nickel source, zinc source, alkali metal hydroxide and reducing agent is (0.4-0.6): (0.2-0.3):
(25-35): (160-180).
As further preferred technical solution, the alcoholic solution of nickel source, the alcoholic solution in zinc source or alkali metal hydroxide
Alcoholic solution is prepared using following steps each independently: nickel source, zinc source or alkali metal hydroxide is molten each independently
In alcoholic solution, ultrasound and stirring are then carried out；
Preferably, mixing time 20-40min；
Preferably, the hybrid mode of the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide
It include: the alcoholic solution of alkali metal hydroxide to be added in the alcoholic solution of nickel source and the alcoholic solution in zinc source and stirred evenly；
Preferably, the mixed solution of the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide
Hybrid mode with reducing agent includes: that reducing agent is added dropwise in mixed solution, stirring while adding, is stirred to solution no longer
Until discoloration.
As further preferred technical solution, the magnetic induction intensity of the parallel magnetic field is 0.35-0.45T.
As further preferred technical solution, the heating reaction is heating water bath to 85-95 DEG C, keeps the temperature 15-
25min；
Preferably, the mode of separation of solid and liquid includes centrifugation；
Preferably, revolving speed when centrifugation is 4000-6000rpm, centrifugation time 230-250s；
Preferably, the mode of washing includes: successively using acetone, ethyl alcohol and distillation water washing, and washing times are 4-6 times；
Preferably, drying temperature is 70-90 DEG C, drying time 105-115min.
As further preferred technical solution, the mode of oxidation processes includes: by the solid product after drying in 290-
1-3h is kept the temperature in 310 DEG C.
The third aspect, the present invention provides a kind of above-mentioned NiO-ZnO ball chain shape nano material photocatalysis, photodetection or
Application in detection of gas.
Fourth aspect, the present invention provides a kind of photochemical catalyst, photoelectricity including above-mentioned NiO-ZnO ball chain shape nano material
Detector or gas detector.
Compared with prior art, the invention has the benefit that
NiO-ZnO ball chain shape nano material provided by the invention has p-n heterojunction structure, which combines
The respective advantage of NiO and ZnO, have NiO semiconductor and ZnO semiconductor inaccessiable excellent photocatalysis characteristic, photoelectricity
Characteristic, pressure-sensitive character and gas-sensitive property etc..
The preparation method simple process of NiO-ZnO ball chain shape nano material provided by the invention, efficiently, using party's legal system
Standby obtained nanometer material structure is clear, uniform in size, shows apparent ball chain shape.
By above-mentioned Application of micron in photocatalysis, photodetection or detection of gas, photocatalysis effect can be significantly improved
Rate, photodetection and gas detection efficient and precision.
Photochemical catalyst, photodetector or gas detector including above-mentioned nano material are imitated with good photocatalysis
Fruit, photodetection effect and gas Effect on Detecting.
Detailed description of the invention
Fig. 1 is the SEM figure that nano material amplifies 5000 times in embodiment 1；
Fig. 2 is the SEM figure that nano material amplifies 10000 times in embodiment 1；
Fig. 3 is the EDS figure of nano material in embodiment 1；
Fig. 4 is photocatalysis test result figure.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the breviary of any real combinings between a to b
It indicates, wherein a and b is real number.Such as numberical range " 300-500 " expression all lists " 300-500 " herein
Between whole real numbers, " 300-500 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, each reaction or operating procedure can be carried out sequentially, can not also be in sequence
It carries out.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
In a first aspect, providing a kind of NiO-ZnO ball chain shape nano material, the nanometer material at least one embodiment
Material is mainly sequentially connected with by NiO-ZnO spherical particle；The NiO-ZnO spherical particle is using Ni-Zn as core, with NiO-
ZnO is the particle of the core-shell structure of shell.
Above-mentioned nano material has p-n heterojunction structure, which combines the respective advantage of NiO and ZnO, have
NiO semiconductor and ZnO semiconductor inaccessiable excellent photocatalysis characteristic, photoelectric characteristic, pressure-sensitive character and gas-sensitive property
Deng.
In a preferred embodiment, the diameter of the NiO-ZnO spherical particle is 300-500nm, preferably
350-450nm.Above-mentioned diameter it is typical but non-limiting for 300nm, 320nm, 340nm, 360nm, 380nm, 400nm,
420nm, 440nm, 460nm, 480nm or 500nm.Spherical particle in above-mentioned particle size range can not only reduce photo-generated carrier
Recombination probability improves the photocatalytic activity of material, moreover it is possible to avoid material to the decrease of visible light-responded ability, while reduce reunion
Phenomenon improves the conductivity of material moreover it is possible to guarantee the voltage-dependent characteristic and air-sensitive performance of material.
It should be understood that above-mentioned NiO-ZnO spherical particle diameter i.e. NiO-ZnO ball chain shape nano material it is straight
Diameter.
In a preferred embodiment, the length of the nano material is 20-40 μm, preferably 25-35 μm.It is above-mentioned
Typical but non-limiting length is 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm or 40 μ
m.When the length of nano material within the above range when, material have preferable connectivity, the light absorption of material is preferable, material
Surface is preferable to the capture ability of photo-generated carrier, thus the photocatalysis performance of material and photoelectric properties are preferable.
Second aspect provides a kind of preparation of above-mentioned NiO-ZnO ball chain shape nano material at least one embodiment
Method, comprising the following steps:
By the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide after mixing again with
Mixed solution, is then placed in parallel magnetic field by reducing agent mixing, and heating is separated by solid-liquid separation after reaction, after separation
Solid product is washed, obtains the nano material after dry and oxidation processes.
Above-mentioned " parallel magnetic field " refers to that the magnetic line of force is the magnetic field of parallel lines, following methods realization can be used: by two pieces of sides
Shape magnet is opposite and puts, the pole S of the pole N face another party's magnet of side's magnet.
Above method simple process, efficiently, the nanometer material structure being prepared using this method is clear, uniform in size,
Show apparent ball chain shape.The specific reaction mechanism of the above method are as follows: nickel source, zinc source and alkali metal hydroxide react first
Nickel hydroxide and zinc hydroxide are formed, then reduction reaction occurs for heating in the parallel magnetic field added outside with reducing agent again, generates
Nickel and zinc, nickel nucleus are connected to ball chain structure while growing up under the action of externally-applied magnetic field, the nickel and zinc of the ball chain structure
Its surface forms nickel oxide and zinc oxide after oxidation processes, finally obtains the nano material.Wherein, alcohol can not only be made
It is solvent for dissolving nickel source, zinc source and alkali metal hydroxide, moreover it is possible to slowed down reaction speed, convenient for uniform and stable formation institute
The nano material needed.
It should be understood that
Above-mentioned " nickel source " is the salt containing nickel element for referring to be dissolved in alcohol, and alcohol refers to aliphatic hydrocarbon, alicyclic or fragrance
Compound made of hydrogen atom in hydrocarbon side chain is optionally substituted by a hydroxyl group.
Above-mentioned " zinc source " is the salt containing Zn-ef ficiency for referring to be dissolved in alcohol, and alcohol refers to aliphatic hydrocarbon, alicyclic or fragrance
Compound made of hydrogen atom in hydrocarbon side chain is optionally substituted by a hydroxyl group.
Above-mentioned " alkali metal hydroxide " refers to that the hydroxide of alkali metal, alkali metal include lithium, sodium, potassium, rubidium, caesium, francium.
In a preferred embodiment, nickel source includes at least one of nickel chloride, nickel sulfate or nickel nitrate；
Preferably, the concentration of nickel source is 0.05-0.15mol/L.Above-mentioned concentration refers to that nickel source is mole dense in alcoholic solution
Degree.Typical but non-limiting above-mentioned concentration is 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/
L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L.
In a preferred embodiment, zinc source includes at least one in zinc chloride, zinc sulfate, zinc nitrate or zinc acetate
Kind；
Preferably, the concentration in zinc source is 0.02-0.05mol/L.Above-mentioned concentration refers to that zinc source is mole dense in alcoholic solution
Degree.Above-mentioned concentration it is typical but non-limiting for 0.02mol/L, 0.025mol/L, 0.03mol/L, 0.035mol/L,
0.04mol/L, 0.045mol/L or 0.05mol/L.
In a preferred embodiment, alkali metal hydroxide includes potassium hydroxide and/or sodium hydroxide；
Preferably, the concentration of alkali metal hydroxide is 1-1.5mol/L.Above-mentioned concentration refers to that alkali metal hydroxide exists
Molar concentration in alcoholic solution.Typical but non-limiting above-mentioned concentration is 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/
L, 1.4mol/L or 1.5mol/L.
In a preferred embodiment, alcoholic solution includes polyhydric alcohol solutions.
Preferably, polyhydric alcohol solutions include the polyhydric alcohol solutions of C2-C4.Above-mentioned " polyalcohol of C2-C4 " refers to carbon atom
The polyalcohol that number is 2,3 or 4, including but not limited to ethylene glycol, 1,2-PD, 1,3-PD, glycerine, 1,2- fourth two
Alcohol, 1,3-BDO, 2,3-butanediol or 1,2,4-butanetriol etc..
Preferably, polyhydric alcohol solutions include ethylene glycol solution.
In a preferred embodiment, reducing agent include in boron hydride, lithium aluminium hydride reduction, hydrazine hydrate or hydrogen extremely
Few one kind.The reproducibility of above-mentioned reducing agent is stronger, and reaction rate is very fast, and the nano particle of formation is mostly spherical or almost spherical,
And size is smaller.
Preferably, reducing agent is hydrazine hydrate.The partial size for the nano material being prepared using hydrazine hydrate as reducing agent compared with
It is small, shape size is controllable, good dispersion is evenly distributed.
Preferably, the concentration of hydrazine hydrate is 80%-90%.Above-mentioned concentration is mass concentration.Above-mentioned concentration typical case but non-limit
Property processed is 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%.
Optionally, boron hydride includes at least one of sodium borohydride, potassium borohydride or hydroboration tetrabutylammonium.
Preferably, the molar ratio of nickel source, zinc source, alkali metal hydroxide and reducing agent is (0.4-0.6): (0.2-0.3):
(25-35): (160-180).Above-mentioned molar ratio it is typical but non-limiting for 0.4:0.2:25:160,0.4:0.25:25:160,
0.4:0.3:25:160,0.5:0.2:25:160,0.6:0.2:25:160,0.4:0.2:30:160,0.4:0.2:35:160,
0.4:0.2:25:170,0.4:0.2:25:180,0.5:0.25:25:160,0.5:0.214:30:170,0.5:0.25:30:
160,0.5:0.25:30:170 or 0.5:0.25:30:180 etc..When rubbing for nickel source, zinc source, alkali metal hydroxide and reducing agent
When you compare within the above range, the amount of mixed solution pH and reducing agent is effectively ensured, so that nickel ion and zinc ion is abundant
Reduction improves yield.
In a preferred embodiment, the alcohol of the alcoholic solution of nickel source, the alcoholic solution in zinc source or alkali metal hydroxide
Solution is prepared using following steps each independently: nickel source, zinc source or alkali metal hydroxide are dissolved in each independently
In alcoholic solution, ultrasound and stirring are then carried out.Ultrasound and stirring can make nickel source, zinc source or the alkali metal hydroxide of solid
It is easier to be dissolved in alcohol, and is uniformly dispersed.
Preferably, mixing time 20-40min.Above-mentioned mixing time it is typical but non-limiting for 20min, 22min,
24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40min.
In a preferred embodiment, the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide
The hybrid mode of alcoholic solution includes: the alcoholic solution that the alcoholic solution of alkali metal hydroxide is added to nickel source and the alcoholic solution in zinc source
In and stir evenly.
In a preferred embodiment, the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide
The mixed solution of alcoholic solution and the hybrid mode of reducing agent include: that reducing agent is added dropwise in mixed solution, and side edged stirs
It mixes, stirs until solution no longer changes colour.
Above-mentioned hybrid mode can make nickel, zinc it is fully dispersed uniformly, dripping method make reaction remain at the uniform velocity, low speed,
Facilitate the abundant progress of reaction.
In a preferred embodiment, the magnetic induction intensity of the parallel magnetic field is 0.35-0.45T.Above-mentioned magnetic strength
Answer intensity it is typical but non-limiting for 0.35T, 0.36T, 0.37T, 0.38T, 0.39T, 0.4T, 0.41T, 0.41T, 0.43T,
0.44T or 0.45T.Above-mentioned induction level is moderate, and nickel nucleus is enabled to be sequentially connected with into chain, and moderate length,
The nano material size of ball chain structure is more uniformly and neat.If magnetic induction intensity is too low, nickel nucleus in the solution by
Induced by magnetic field simultaneously arranges and needs more times, and during this period of time nickel nucleus is constantly wrapped by grow bigger, thus
The length for being not easy into chain or chain is smaller, to influence the pattern of material；If magnetic induction intensity is excessively high, what is obtained is received
The diameter of rice material is too small, and length is too long.
In a preferred embodiment, the heating reaction is heating water bath to 85-95 DEG C, keeps the temperature 15-25min.
It is heated more uniformly that heating water bath can make solution, and is easy to control reaction temperature.The temperature of reaction is typical but non-limiting
It is 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C, 89 DEG C, 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C or 95 DEG C；Soaking time typical case but non-limit
Property processed is 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min or 25min.
In a preferred embodiment, the mode of separation of solid and liquid includes centrifugation.
Preferably, revolving speed when centrifugation is 4000-6000rpm, centrifugation time 230-250s.Above-mentioned revolving speed is typical but non-
It is restrictive for 4000rpm, 4200rpm, 4400rpm, 4600rpm, 4800rpm, 5000rpm, 5200rpm, 5400rpm,
5600rpm, 5800rpm or 6000rpm；Above-mentioned centrifugation time it is typical but non-limiting for 230s, 232s, 234s, 236s,
238s, 240s, 242s, 244s, 246s, 248s or 250s.In above-mentioned revolving speed and time range, can by solution nickel and
Zinc is kept completely separate out, and separative efficiency is high, good separating effect.
Preferably, the mode of washing includes: successively using acetone, ethyl alcohol and distillation water washing, and washing times are 4-6 times.
After the washing of aforesaid way, the washes cleans such as foreign ion that solid product surface is adhered to can be improved the pure of product
Cleanliness.
Preferably, drying temperature is 70-90 DEG C, drying time 105-115min.Above-mentioned drying temperature typical case but non-limit
Property processed is 70 DEG C, 72 DEG C, 74 DEG C, 76 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C；Above-mentioned drying time
It is typical but non-limiting for 105min, 106min, 107min, 108min, 109min, 110min, 111min, 112min,
113min, 114min or 115min.
In a preferred embodiment, the mode of oxidation processes includes: by the solid product after drying in 290-310
1-3h is kept the temperature in DEG C.It is 290 DEG C that above-mentioned temperature is typical but non-limiting, 292 DEG C, 294 DEG C, 296 DEG C, 298 DEG C, 300 DEG C,
302 DEG C, 304 DEG C, 306 DEG C, 308 DEG C or 310 DEG C；The time of heat preservation it is typical but non-limiting for 1h, 1.5h, 2h, 2.5h or
3h。
Optionally, the solid product after drying carries out oxidation processes in tube furnace.
The third aspect, the present invention provides a kind of above-mentioned NiO-ZnO ball chain shape nano material photocatalysis, photodetection or
Application in detection of gas.By above-mentioned Application of micron in photocatalysis, photodetection or detection of gas, it can significantly improve
Photocatalysis efficiency, photodetection and gas detection efficient and precision.
It should be understood that photocatalysis refers to the technology that solar energy is changed into chemical energy.Photodetection is according to being visited
The feature of the light wave of object radiation or reflection is surveyed to detect and identify the technology of object.Detection of gas refers to using substance in biochemistry
The property for releasing or absorbing gas in reaction or chemical reaction, the variation by measuring gas flow carry out qualitative, quantitative to substance
The technology of analysis.
Fourth aspect, the present invention provides a kind of photochemical catalyst, photoelectricity including above-mentioned NiO-ZnO ball chain shape nano material
Detector or gas detector.Photochemical catalyst, photodetector or gas detector including above-mentioned nano material have good
Photocatalysis effect, photodetection effect and gas Effect on Detecting.
Below with reference to embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of NiO-ZnO ball chain shape nano material, the nano material be mainly sequentially connected with by NiO-ZnO spherical particle and
At；The NiO-ZnO spherical particle is using Ni-Zn as core, using NiO-ZnO as the particle of the core-shell structure of shell.
Above-mentioned nano material is prepared using following methods:
(a) 0.119g Nickel dichloride hexahydrate (NiCl is weighed2·6H2) and 0.0292g zinc chloride (ZnCl O2) it is dissolved in 5mL
In ethylene glycol (EG), solution is obtained 1.；
Wherein, the concentration of nickel source is 0.1mol/L, and the concentration in zinc source is 0.0428mol/L；
(b) it weighs 1.2g sodium hydroxide (NaOH) to be dissolved in the ethylene glycol (EG) of 25mL, obtains solution 2.；
Wherein, the concentration of sodium hydroxide is 1.2mol/L；
(c) 1. respectively with solution, and stirs 30min to being completely dissolved；
(d) after solution is completely dissolved, 2. 1. solution is poured slowly into solution, is mixed and stirred for mixing, obtain mixing molten
Liquid is 3.；
(e) mixed solution is added dropwise 3. in 10ml hydrazine hydrate (concentration 85%, as reducing agent), it is stirring while adding,
Stirring is non-discolouring to navy blue, obtains mixed solution 4.；
(f) 4. mixed solution is placed in the additional parallel magnetic field of 0.4T, and heating water bath is reacted and kept the temperature to 90 DEG C
20min；
(g) after reaction, after being centrifuged 240s with 5000rpm revolving speed, centrifugation product is obtained；
(h) centrifugation product is successively used into acetone, ethyl alcohol and distilled water washing 5 times, in then 80 DEG C of dry 110min, obtained
Nickel-zinc ball chain shape nano structural material；
(i) nickel-zinc nano wire is placed in tube furnace, temperature is set as 300 DEG C, continues 2h, obtains nucleocapsid NiO-ZnO ball chain
Shape nano structural material.
It is as depicted in figs. 1 and 2 the SEM figure of the nano material in embodiment 1, it can be seen from the figure that the nano material
Uniform in size for ball chain shape, diameter is 400nm or so, and length is 30 μm or so, and major diameter is bigger, clear in structure, and disperse compared with
It is less agglomeration occur to be uniform.
It is illustrated in figure 3 the EDS figure of the nano material in embodiment 1, it can be seen from the figure that containing in the nano material
Nickel element, Zn-ef ficiency and oxygen element illustrate to successfully synthesize NiO-ZnO nano material, additionally, due to when carrying out EDS test,
Nano material is placed on Co sample stage, thus occurs the peak of Co element in figure.
Embodiment 2
A kind of NiO-ZnO ball chain shape nano material, unlike the first embodiment, the preparation side of the present embodiment nano material
In method step (a): the concentration of nickel source is 0.15mol/L, and the concentration in zinc source is 0.02mol/L, and nickel source is nickel sulfate, and zinc source is sulphur
Sour zinc.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in ball chain shape, diameter is 500nm or so, and length is 30 μm or so.
Embodiment 3
A kind of NiO-ZnO ball chain shape nano material, unlike the first embodiment, the preparation side of the present embodiment nano material
In method step (b): the concentration of sodium hydroxide is 1.5mol/L.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in ball chain shape, diameter is 410nm or so, and length is 30 μm or so.
Embodiment 4
A kind of NiO-ZnO ball chain shape nano material, unlike the first embodiment, the preparation side of the present embodiment nano material
In method step (e): reducing agent is sodium borohydride.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in ball chain shape, diameter is 450nm or so, and length is 30 μm or so.
Embodiment 5
A kind of NiO-ZnO ball chain shape nano material, unlike the first embodiment, the preparation side of the present embodiment nano material
In method step (f): the magnetic induction intensity in magnetic field is 0.45T, and the temperature of heating water bath is 85 DEG C, soaking time 25min.Remaining
It is same as Example 1.
Through SEM it has been observed that the nano material is in ball chain shape, diameter is 400nm or so, and length is 40 μm or so.
Embodiment 6
A kind of NiO-ZnO ball chain shape nano material, unlike the first embodiment, the preparation side of the present embodiment nano material
In method step (i): temperature is 310 DEG C, duration 1h.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in ball chain shape, diameter is 390nm or so, and length is 30 μm or so.
Comparative example 1
A kind of nano material in this comparative example step (f), 4. mixed solution is not placed in unlike the first embodiment
In the parallel magnetic field of 0.4T, directly carries out heating water bath and keep the temperature.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in spherical, diameter is 510nm or so.
Comparative example 2
In this comparative example step (a) and (b), ethylene glycol is replaced with unlike the first embodiment for a kind of nano material
Water.Remaining is same as Example 1.
Through SEM it has been observed that the nano material is in corynebacterium, diameter is 1.1 μm or so, and length is 10 μm or so.
Photocatalysis test
Take two reaction vessels, be added in two reaction vessels 20mL rhodamine B (rhodamine B be also known as rose red b,
Or basic rhodamine, it is commonly called as that pollen is red, is a kind of artificial synthesized dyestuff with fresh pink, chemical formula is
C28H31ClN2O3) solution (5mg/L), the ball chain shape nano material being additionally added in one of reaction vessel in 3mg embodiment 1,
Catalyst (as blank control) is not added in another reaction vessel, uses xenon lamp as light source, carries out light-catalyzed reaction.According to
The ratio of front and back absorbance is reacted to measure photocatalysis effect, and definition ordinate is ct/c0, wherein c0And ctBefore respectively reacting
With the absorbance of solution after reaction, abscissa is irradiation time.
As shown in figure 4, after illumination 3h, rhodamine B is only degraded less than 4%, and is added in the case where not adding catalyst
The nano material of embodiment 1 is as photochemical catalyst, and after illumination 3h, rhodamine B has degraded about 53%, it is clear that the nano material
The degradation speed of rhodamine B solution, good catalytic activity can be greatly improved as photochemical catalyst.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of NiO-ZnO ball chain shape nano material, which is characterized in that the nano material is mainly by NiO-ZnO spherical particle
It is sequentially connected with；The NiO-ZnO spherical particle is using Ni-Zn as core, using NiO-ZnO as the particle of the core-shell structure of shell.
2. NiO-ZnO ball chain shape nano material according to claim 1, which is characterized in that the NiO-ZnO spherical particle
Diameter be 300-500nm, preferably 350-450nm；
Preferably, the length of the nano material is 20-40 μm, preferably 25-35 μm.
3. the preparation method of NiO-ZnO ball chain shape nano material of any of claims 1 or 2, which is characterized in that including following step
It is rapid:
By the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide after mixing again with reduction
Mixed solution, is then placed in parallel magnetic field by agent mixing, and heating is separated by solid-liquid separation after reaction, consolidating after separation
Body product is washed, obtains the nano material after dry and oxidation processes.
4. the preparation method of NiO-ZnO ball chain shape nano material according to claim 3, which is characterized in that nickel source includes
At least one of nickel chloride, nickel sulfate or nickel nitrate；
Preferably, the concentration of nickel source is 0.05-0.15mol/L；
Preferably, zinc source includes at least one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate；
Preferably, the concentration in zinc source is 0.02-0.05mol/L；
Preferably, alkali metal hydroxide includes potassium hydroxide and/or sodium hydroxide；
Preferably, the concentration of alkali metal hydroxide is 1-1.5mol/L；
Preferably, alcoholic solution includes polyhydric alcohol solutions；
Preferably, polyhydric alcohol solutions include the polyhydric alcohol solutions of C2-C4；
Preferably, polyhydric alcohol solutions include ethylene glycol solution；
Preferably, reducing agent includes at least one of boron hydride, lithium aluminium hydride reduction, hydrazine hydrate or hydrogen；
Preferably, reducing agent is hydrazine hydrate；
Preferably, the concentration of hydrazine hydrate is 80%-90%；
Preferably, the molar ratio of nickel source, zinc source, alkali metal hydroxide and reducing agent is (0.4-0.6): (0.2-0.3): (25-
35): (160-180).
5. the preparation method of NiO-ZnO ball chain shape nano material according to claim 3, which is characterized in that the alcohol of nickel source
The alcoholic solution of solution, the alcoholic solution in zinc source or alkali metal hydroxide is prepared using following steps each independently: by nickel
Source, zinc source or alkali metal hydroxide are dissolved in alcoholic solution each independently, then carry out ultrasound and stirring；
Preferably, mixing time 20-40min；
Preferably, the hybrid mode packet of the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide
It includes: the alcoholic solution of alkali metal hydroxide being added in the alcoholic solution of nickel source and the alcoholic solution in zinc source and stirred evenly；
Preferably, the mixed solution of the alcoholic solution of the alcoholic solution of nickel source, the alcoholic solution in zinc source and alkali metal hydroxide with also
The hybrid mode of former agent includes: that reducing agent is added dropwise in mixed solution, stirring while adding, and stirring no longer changes colour to solution
Until.
6. the preparation method of NiO-ZnO ball chain shape nano material according to claim 3, which is characterized in that described parallel
The magnetic induction intensity in magnetic field is 0.35-0.45T.
7. the preparation method of NiO-ZnO ball chain shape nano material according to claim 3, which is characterized in that the heating
Reaction is heating water bath to 85-95 DEG C, keeps the temperature 15-25min；
Preferably, the mode of separation of solid and liquid includes centrifugation；
Preferably, revolving speed when centrifugation is 4000-6000rpm, centrifugation time 230-250s；
Preferably, the mode of washing includes: successively using acetone, ethyl alcohol and distillation water washing, and washing times are 4-6 times；
Preferably, drying temperature is 70-90 DEG C, drying time 105-115min.
8. according to the preparation method of the described in any item NiO-ZnO ball chain shape nano materials of claim 3-7, which is characterized in that
The mode of oxidation processes includes: that the solid product after drying is kept the temperature 1-3h in 290-310 DEG C.
9. NiO-ZnO ball chain shape nano material of any of claims 1 or 2 is in photocatalysis, photodetection or detection of gas
Using.
10. including photochemical catalyst, photodetector or the gas of NiO-ZnO ball chain shape nano material of any of claims 1 or 2
Detector.
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