CN109647414B - NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof - Google Patents
NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109647414B CN109647414B CN201910077570.3A CN201910077570A CN109647414B CN 109647414 B CN109647414 B CN 109647414B CN 201910077570 A CN201910077570 A CN 201910077570A CN 109647414 B CN109647414 B CN 109647414B
- Authority
- CN
- China
- Prior art keywords
- nio
- zno
- nano
- spherical chain
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000012798 spherical particle Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 229910018605 Ni—Zn Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 90
- 239000011787 zinc oxide Substances 0.000 claims description 82
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 42
- 239000011701 zinc Substances 0.000 claims description 42
- 229910052725 zinc Inorganic materials 0.000 claims description 42
- 230000001476 alcoholic effect Effects 0.000 claims description 40
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000007146 photocatalysis Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 6
- 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
- 230000008859 change Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 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
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 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
- 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
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 35
- 239000004065 semiconductor Substances 0.000 abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 57
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 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
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 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
- 238000011534 incubation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 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
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000008543 heat sensitivity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity 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
- 229910001453 nickel ion Inorganic materials 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
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 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
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing 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
Images
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
Landscapes
- 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)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of nano materials, and particularly provides a NiO-ZnO spherical chain nano material, and a preparation method and application thereof. The NiO-ZnO spherical chain-shaped nano material is mainly formed by sequentially connecting NiO-ZnO spherical particles; the NiO-ZnO spherical particles are particles with a core-shell structure, wherein the Ni-Zn is used as a core, and the NiO-ZnO is used as a shell. The material has a p-n heterojunction structure and is in a spherical chain shape, and the material has excellent photocatalytic property, photoelectric property, pressure-sensitive property, gas-sensitive property and the like which cannot be achieved by a NiO semiconductor and a ZnO semiconductor.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a NiO-ZnO spherical chain nano material and a preparation method and application thereof.
Background
NiO is a typical p-type semiconductor, has good characteristics of heat sensitivity, gas sensitivity and the like, is a promising functional material, and is widely applied to industries such as metallurgy, chemistry, electronics and the like. The surface structure and the crystal structure of the nano nickel oxide are changed due to the superfine particle size of the nano nickel oxide, so that the surface effect, the small-size effect, the quantum size effect, the macroscopic quantum tunneling effect and the like are generated, and the excellent catalytic performance and the electrical performance are shown.
ZnO is a typical third-generation semiconductor material, has a forbidden band width of 3.37eV and an exciton confinement energy of 60meV, and belongs to II-VI group semiconductors; the material has large energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the semiconductor field. Among them, zinc oxide is an important class of gas sensitive materials, and can monitor toxic and harmful polluted gases in the environment. However, the problems of low sensitivity, high working temperature, poor selectivity and the like of the zinc oxide gas-sensitive material are also urgent to solve.
The one-dimensional nano material is a material with two dimensions of nano scale, and the one-dimensional nano material is an ideal system for researching the size and latitude effects of physical properties such as electronic transmission behavior, optical characteristics, mechanical properties and the like. Compared with zero-dimensional and two-dimensional nano materials, the one-dimensional nano material has unique advantages in the aspect of developing functional devices, can realize nanoscale connection and information transmission, can embody self quantum characteristics, and plays an important role in constructing functional elements such as nano electronic and optoelectronic devices.
At present, a great deal of related research is carried out on the preparation of one-dimensional nano materials, but most of the nano materials are ordinary linear nano structures, the synthesis and preparation of a spherical chain nano structure are rarely reported, and the spherical chain nano structure material which utilizes NiO and ZnO as two different semiconductor materials to form a p-n heterojunction is not reported.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first object of the present invention is to provide a NiO-ZnO spherical chain nanomaterial having a p-n heterojunction structure in a spherical chain shape, which has excellent photocatalytic properties, photoelectric properties, pressure-sensitive properties, gas-sensitive properties, and the like, which cannot be achieved by NiO semiconductors and ZnO semiconductors.
The second purpose of the invention is to provide a preparation method of NiO-ZnO spherical chain-shaped nano material, the method has simple and efficient process, and the nano material prepared by the method has clear structure, uniform size and obvious spherical chain shape.
The third purpose of the invention is to provide the application of the NiO-ZnO spherical chain nano material.
The fourth purpose of the invention is to provide a photocatalyst, a photoelectric detector or a gas detector which comprises NiO-ZnO spherical chain-shaped nanometer materials.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a NiO-ZnO spherical chain-shaped nano material, which is mainly formed by sequentially connecting NiO-ZnO spherical particles; the NiO-ZnO spherical particles are particles with a core-shell structure, wherein the Ni-Zn is used as a core, and the NiO-ZnO is used as a shell.
As a further preferable technical scheme, the diameter of the NiO-ZnO spherical particles is 300-500nm, preferably 350-450 nm;
preferably, the length of the nanomaterial is 20 to 40 μm, preferably 25 to 35 μm.
In a second aspect, the invention provides a preparation method of the NiO-ZnO spherical chain nanomaterial, which comprises the following steps:
uniformly mixing an alcoholic solution of a nickel source, an alcoholic solution of a zinc source and an alcoholic solution of an alkali metal hydroxide, then mixing with a reducing agent, then placing the mixed solution in a parallel magnetic field, carrying out solid-liquid separation after the heating reaction is finished, and washing, drying and oxidizing the separated solid product to obtain the nano material.
As a further preferred technical solution, the nickel source includes at least one of nickel chloride, nickel sulfate or nickel nitrate;
preferably, the concentration of the nickel source is 0.05-0.15 mol/L;
preferably, the zinc source comprises at least one of zinc chloride, zinc sulfate, zinc nitrate, or zinc acetate;
preferably, the concentration of the zinc source is 0.02-0.05 mol/L;
preferably, the alkali metal hydroxide comprises potassium hydroxide and/or sodium hydroxide;
preferably, the concentration of the alkali metal hydroxide is 1 to 1.5 mol/L;
preferably, the alcohol solution comprises a polyol solution;
preferably, the polyol solution comprises a polyol solution of C2-C4;
preferably, the polyol solution comprises a glycol solution;
preferably, the reducing agent comprises at least one of borohydride, lithium aluminum hydride, hydrazine hydrate or hydrogen;
preferably, the reducing agent is hydrazine hydrate;
preferably, the concentration of hydrazine hydrate is 80% -90%;
preferably, the molar ratio of the nickel source, the zinc source, the alkali metal hydroxide and the reducing agent is (0.4-0.6): (0.2-0.3): (25-35): (160-180).
As a further preferred embodiment, the alcoholic solution of a nickel source, the alcoholic solution of a zinc source, or the alcoholic solution of an alkali metal hydroxide is prepared by the following steps, independently of each other: dissolving a nickel source, a zinc source, or an alkali metal hydroxide in an alcohol solution independently of each other, and then performing ultrasonic treatment and stirring;
preferably, the stirring time is 20-40 min;
preferably, the mixing of the alcoholic solution of the nickel source, the alcoholic solution of the zinc source, and the alcoholic solution of the alkali metal hydroxide comprises: adding an alcoholic solution of alkali metal hydroxide into an alcoholic solution of a nickel source and an alcoholic solution of a zinc source, and uniformly stirring;
preferably, the mixing manner of the mixed solution of the alcohol solution of the nickel source, the alcohol solution of the zinc source, and the alcohol solution of the alkali metal hydroxide and the reducing agent includes: and (3) dropwise adding a reducing agent into the mixed solution while stirring until the solution does not change color any more.
In a more preferable embodiment, the magnetic induction of the parallel magnetic field is 0.35 to 0.45T.
As a further preferable technical scheme, the heating reaction is heating in water bath to 85-95 ℃, and keeping the temperature for 15-25 min;
preferably, the solid-liquid separation mode comprises centrifugation;
preferably, the rotation speed during centrifugation is 4000-6000rpm, and the centrifugation time is 230-250 s;
preferably, the washing method comprises: washing with acetone, ethanol and distilled water sequentially for 4-6 times;
preferably, the drying temperature is 70-90 ℃ and the drying time is 105-115 min.
As a further preferable embodiment, the oxidation treatment method includes: the dried solid product is incubated for 1-3h at 290 ℃ and 310 ℃.
In a third aspect, the invention provides an application of the NiO-ZnO spherical chain nano material in photocatalysis, photoelectric detection or gas detection.
In a fourth aspect, the invention provides a photocatalyst, a photoelectric detector or a gas detector comprising the NiO-ZnO spherical chain nano material.
Compared with the prior art, the invention has the beneficial effects that:
the NiO-ZnO spherical chain nano material provided by the invention has a p-n heterojunction structure, integrates the advantages of NiO and ZnO, and has excellent photocatalytic property, photoelectric property, pressure-sensitive property, gas-sensitive property and the like which cannot be achieved by a NiO semiconductor and a ZnO semiconductor.
The preparation method of the NiO-ZnO spherical chain-shaped nano material provided by the invention has the advantages that the process is simple and efficient, and the nano material prepared by the method has a clear structure and uniform size and presents an obvious spherical chain shape.
The nano material is applied to photocatalysis, photoelectric detection or gas detection, and the photocatalysis efficiency, the photoelectric detection and the gas detection efficiency and the accuracy can be obviously improved.
The photocatalyst, the photoelectric detector or the gas detector comprising the nano material have good photocatalytic effect, photoelectric detection effect and gas detection effect.
Drawings
FIG. 1 is an SEM image of the nanomaterial of example 1 at 5000 times magnification;
FIG. 2 is an SEM image of the nanomaterial in example 1 at 10000 times magnification;
FIG. 3 is EDS diagram of the nanomaterial in example 1;
FIG. 4 is a graph showing the results of the photocatalytic test.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the value range of "300-" 500 "represents that all real numbers between" 300- "500" have been listed herein, and "300-" 500 "is only an abbreviated representation of the combination of these values.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may or may not be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
In a first aspect, in at least one embodiment, a NiO-ZnO spherical chain nano material is provided, wherein the nano material is mainly formed by connecting NiO-ZnO spherical particles in sequence; the NiO-ZnO spherical particles are particles with a core-shell structure, wherein the Ni-Zn is used as a core, and the NiO-ZnO is used as a shell.
The nano material has a p-n heterojunction structure, integrates the advantages of NiO and ZnO, and has excellent photocatalytic property, photoelectric property, pressure-sensitive property, gas-sensitive property and the like which cannot be achieved by a NiO semiconductor and a ZnO semiconductor.
In a preferred embodiment, the NiO-ZnO spherical particles have a diameter of 300-500nm, preferably 350-450 nm. The above diameters are typically, but not limited to, 300nm, 320nm, 340nm, 360nm, 380nm, 400nm, 420nm, 440nm, 460nm, 480nm or 500 nm. The spherical particles in the particle size range can reduce the recombination probability of photon-generated carriers, improve the photocatalytic activity of the material, avoid the weakening of the response capability of the material to visible light, reduce the agglomeration phenomenon, ensure the pressure-sensitive performance and the gas-sensitive performance of the material and improve the conductivity of the material.
It should be understood that the diameter of the NiO-ZnO spherical particles is the diameter of the NiO-ZnO spherical chain nano-material.
In a preferred embodiment, the length of the nanomaterial is 20 to 40 μm, preferably 25 to 35 μm. The above length is typically, but not limited to, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm or 40 μm. When the length of the nano material is within the range, the material has better connectivity, the light absorption property of the material is better, and the capture capability of the surface of the material on photo-generated carriers is better, so that the photocatalysis performance and the photoelectric performance of the material are better.
In a second aspect, in at least one embodiment, there is provided a method for preparing the NiO-ZnO spherical chain nanomaterial, comprising the following steps:
uniformly mixing an alcoholic solution of a nickel source, an alcoholic solution of a zinc source and an alcoholic solution of an alkali metal hydroxide, then mixing with a reducing agent, then placing the mixed solution in a parallel magnetic field, carrying out solid-liquid separation after the heating reaction is finished, and washing, drying and oxidizing the separated solid product to obtain the nano material.
The above-mentioned "parallel magnetic field" refers to a magnetic field whose magnetic lines are parallel straight lines, and can be implemented by adopting the following method: two square magnets are placed opposite to each other, and the N pole of one magnet faces the S pole of the other magnet.
The method has simple and efficient process, and the nano material prepared by the method has clear structure and uniform size and presents an obvious spherical chain shape. The specific reaction mechanism of the method is as follows: the nickel source, the zinc source and the alkali metal hydroxide firstly react to form nickel hydroxide and zinc hydroxide, then the nickel hydroxide and the zinc hydroxide are heated in an external parallel magnetic field to carry out reduction reaction to generate nickel and zinc, nickel crystal nuclei grow up and are connected into a ball chain structure under the action of the external magnetic field, nickel oxide and zinc oxide are formed on the surfaces of the nickel and the zinc in the ball chain structure after oxidation treatment, and finally the nano material is obtained. The alcohol can be used as a solvent for dissolving a nickel source, a zinc source and alkali metal hydroxide, and can slow down the reaction speed, so that the required nano material can be uniformly and stably formed.
It should be noted that:
the "nickel source" is a salt containing a nickel element that can be dissolved in an alcohol, and the alcohol is a compound in which a hydrogen atom in a side chain of an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon is substituted with a hydroxyl group.
The "zinc source" is a salt of a zinc-containing element that is soluble in an alcohol, and the alcohol is a compound in which a hydrogen atom in a side chain of an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon is substituted with a hydroxyl group.
The term "alkali metal hydroxide" as used herein refers to hydroxides of alkali metals, including lithium, sodium, potassium, rubidium, cesium, francium.
In a preferred embodiment, the nickel source comprises at least one of nickel chloride, nickel sulfate, or nickel nitrate;
preferably, the concentration of the nickel source is 0.05 to 0.15 mol/L. The above concentrations refer to the molar concentration of the nickel source in the alcohol solution. The above concentration is typically, but not limited to, 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 0.15 mol/L.
In a preferred embodiment, the zinc source comprises at least one of zinc chloride, zinc sulfate, zinc nitrate, or zinc acetate;
preferably, the concentration of the zinc source is 0.02 to 0.05 mol/L. The concentrations mentioned above refer to the molar concentration of the zinc source in the alcoholic solution. Typical, but not limiting, such concentrations are 0.02mol/L, 0.025mol/L, 0.03mol/L, 0.035mol/L, 0.04mol/L, 0.045mol/L or 0.05 mol/L.
In a preferred embodiment, the alkali metal hydroxide comprises potassium hydroxide and/or sodium hydroxide;
preferably, the concentration of the alkali metal hydroxide is 1 to 1.5 mol/L. The above concentration refers to the molar concentration of the alkali metal hydroxide in the alcohol solution. The above concentration is typically, but not limited to, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, or 1.5 mol/L.
In a preferred embodiment, the alcohol solution comprises a polyol solution.
Preferably, the polyol solution comprises a C2-C4 polyol solution. The "C2-C4 polyol" refers to a polyol having 2, 3 or 4 carbon atoms, and includes, but is not limited to, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 2, 4-butanetriol, and the like.
Preferably, the polyol solution comprises an ethylene glycol solution.
In a preferred embodiment, the reducing agent comprises at least one of borohydride, lithium aluminum hydride, hydrazine hydrate, or hydrogen gas. The reducing agent has strong reducibility and high reaction rate, and the formed nano particles are mostly spherical or approximately spherical and have small size.
Preferably, the reducing agent is hydrazine hydrate. The nano material prepared by adopting hydrazine hydrate as a reducing agent has the advantages of small particle size, controllable shape and size, good dispersibility and uniform distribution.
Preferably, the concentration of hydrazine hydrate is 80% to 90%. The above concentration is a mass concentration. Such concentrations are typically, but not limited to, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%.
Optionally, the borohydride comprises at least one of sodium borohydride, potassium borohydride, or tetrabutylammonium borohydride.
Preferably, the molar ratio of the nickel source, the zinc source, the alkali metal hydroxide and the reducing agent is (0.4-0.6): (0.2-0.3): (25-35): (160-180). The above molar ratio is typically, but not limited to, 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 the molar ratio of the nickel source, the zinc source, the alkali metal hydroxide and the reducing agent is within the above range, the pH of the mixed solution and the amount of the reducing agent are effectively ensured, so that nickel ions and zinc ions are sufficiently reduced, and the yield is improved.
In a preferred embodiment, the alcoholic solution of the nickel source, the alcoholic solution of the zinc source, or the alcoholic solution of the alkali metal hydroxide is prepared by the following steps, independently of each other: the nickel source, zinc source, or alkali metal hydroxide are each independently dissolved in an alcohol solution, followed by sonication and stirring. The ultrasound and agitation enable the solid nickel source, zinc source, or alkali metal hydroxide to be more easily dissolved in the alcohol and uniformly dispersed.
Preferably, the stirring time is 20-40 min. The above stirring time is typically, but not limited to, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40 min.
In a preferred embodiment, the mixing of the alcoholic solution of the nickel source, the alcoholic solution of the zinc source, and the alcoholic solution of the alkali metal hydroxide comprises: adding an alcoholic solution of alkali metal hydroxide into an alcoholic solution of a nickel source and an alcoholic solution of a zinc source, and uniformly stirring.
In a preferred embodiment, the mixing of the alcohol solution of the nickel source, the alcohol solution of the zinc source, and the alcohol solution of the alkali metal hydroxide with the reducing agent comprises: and (3) dropwise adding a reducing agent into the mixed solution while stirring until the solution does not change color any more.
The mixing mode can fully and uniformly disperse the nickel and the zinc, and the dropping method can keep the reaction at a constant speed and a low speed all the time, thereby being beneficial to the full reaction.
In a preferred embodiment, the magnetic induction of the parallel magnetic field is 0.35-0.45T. The magnetic induction is typically, but not limited to, 0.35T, 0.36T, 0.37T, 0.38T, 0.39T, 0.4T, 0.41T, 0.43T, 0.44T, or 0.45T. The magnetic induction intensity is moderate, the nickel crystal nuclei can be sequentially connected into a chain shape, the length is moderate, and the size of the nanometer material with the spherical chain structure is uniform and neat. If the magnetic induction intensity is too low, the nickel crystal nuclei are induced by a magnetic field in the solution and distributed for more time, and the nickel crystal nuclei are continuously coated in the time to grow larger, so that the nickel crystal nuclei are not easy to form a chain shape or the chain shape is smaller in length, and the shape of the material is influenced; if the magnetic induction intensity is too high, the diameter of the obtained nano material is too small, and the length of the obtained nano material is too long.
In a preferred embodiment, the heating reaction is heating in a water bath to 85-95 ℃, and keeping the temperature for 15-25 min. The water bath heating can ensure that the solution is heated more uniformly, and the reaction temperature is easy to control. The temperature of the reaction is typically, but not limited to, 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; the incubation time is typically, but not limited to, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min or 25 min.
In a preferred embodiment, the means for solid-liquid separation comprises centrifugation.
Preferably, the rotation speed during centrifugation is 4000-6000rpm, and the centrifugation time is 230-250 s. Typical but not limiting rotational speeds are 4000rpm, 4200rpm, 4400rpm, 4600rpm, 4800rpm, 5000rpm, 5200rpm, 5400rpm, 5600rpm, 5800rpm or 6000 rpm; the above centrifugation time is typically, but not limited to, 230s, 232s, 234s, 236s, 238s, 240s, 242s, 244s, 246s, 248s, or 250 s. Within the rotating speed and time range, the nickel and the zinc in the solution can be completely separated, the separation efficiency is high, and the separation effect is good.
Preferably, the washing method comprises: washing with acetone, ethanol and distilled water sequentially for 4-6 times. After the washing in the mode, impurity ions and the like attached to the surface of the solid product can be washed clean, and the purity of the product is improved.
Preferably, the drying temperature is 70-90 ℃ and the drying time is 105-115 min. The drying temperature is typically, but not limited to, 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; the above drying time is typically, but not limited to, 105min, 106min, 107min, 108min, 109min, 110min, 111min, 112min, 113min, 114min or 115 min.
In a preferred embodiment, the manner of oxidation treatment includes: the dried solid product is incubated for 1-3h at 290 ℃ and 310 ℃. The temperature is typically, but not limited to, 290 deg.C, 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 incubation time is typically, but not limited to, 1h, 1.5h, 2h, 2.5h or 3 h.
Optionally, the dried solid product is subjected to an oxidation treatment in a tube furnace.
In a third aspect, the invention provides an application of the NiO-ZnO spherical chain nano material in photocatalysis, photoelectric detection or gas detection. The nano material is applied to photocatalysis, photoelectric detection or gas detection, and the photocatalysis efficiency, the photoelectric detection and the gas detection efficiency and the accuracy can be obviously improved.
It should be understood that photocatalysis refers to the technology of converting solar energy into chemical energy. Photodetection is a technique for detecting and identifying objects based on the characteristics of light waves radiated or reflected by the detected object. Gas detection refers to a technique of qualitatively and quantitatively analyzing a substance by measuring a change in the amount of gas by using the property of the substance that emits or absorbs gas in a biochemical reaction or a chemical reaction.
In a fourth aspect, the invention provides a photocatalyst, a photoelectric detector or a gas detector comprising the NiO-ZnO spherical chain nano material. The photocatalyst, the photoelectric detector or the gas detector comprising the nano material have good photocatalytic effect, photoelectric detection effect and gas detection effect.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A NiO-ZnO spherical chain nano material is mainly formed by sequentially connecting NiO-ZnO spherical particles; the NiO-ZnO spherical particles are particles with a core-shell structure, wherein the Ni-Zn is used as a core, and the NiO-ZnO is used as a shell.
The nano material is prepared by the following method:
(a) 0.119g of nickel chloride hexahydrate (NiCl) was weighed2·6H2O) and 0.0292g of zinc chloride (ZnCl)2) Dissolving in 5mL of Ethylene Glycol (EG) to obtain a solution I;
wherein the concentration of the nickel source is 0.1mol/L, and the concentration of the zinc source is 0.0428 mol/L;
(b) weighing 1.2g of sodium hydroxide (NaOH) and dissolving in 25mL of Ethylene Glycol (EG) to obtain a solution II;
wherein the concentration of the sodium hydroxide is 1.2 mol/L;
(c) respectively carrying out ultrasonic treatment on the solution I and the solution II, and stirring for 30min until the solutions are completely dissolved;
(d) after the solution is completely dissolved, slowly pouring the solution II into the solution I, mixing and uniformly stirring to obtain a mixed solution III;
(e) dropwise adding 10ml of hydrazine hydrate (with the concentration of 85 percent as a reducing agent) into the mixed solution (c), stirring while adding, and stirring until the color of the dark blue does not change to obtain a mixed solution (c);
(f) putting the mixed solution in an external parallel magnetic field of 0.4T, heating to 90 ℃ in a water bath, reacting and keeping the temperature for 20 min;
(g) after the reaction is finished, centrifuging at the rotating speed of 5000rpm for 240s to obtain a centrifugal product;
(h) washing the centrifugal product with acetone, ethanol and distilled water for 5 times in sequence, and then drying at 80 ℃ for 110min to obtain the nickel-zinc sphere chain-shaped nano-structure material;
(i) and (3) placing the nickel-zinc nanowires in a tubular furnace, setting the temperature at 300 ℃, and continuing for 2 hours to obtain the core-shell NiO-ZnO spherical chain nano-structure material.
As shown in fig. 1 and fig. 2, SEM images of the nanomaterial of example 1 show that the nanomaterial is in the form of spherical chain, and has uniform size, diameter of about 400nm, length of about 30 μm, large major diameter, clear structure, uniform dispersion, and less agglomeration.
As shown in FIG. 3, which is an EDS diagram of the nanomaterial in example 1, it can be seen that the nanomaterial contains nickel element, zinc element and oxygen element, thus indicating that NiO-ZnO nanomaterial was successfully synthesized, and a peak of Co element appears in the diagram since the nanomaterial was placed on a Co sample stage when EDS test was performed.
Example 2
A NiO-ZnO spherical chain nanometer material is different from the embodiment 1 in that the preparation method of the nanometer material comprises the following steps: the concentration of the nickel source is 0.15mol/L, the concentration of the zinc source is 0.02mol/L, the nickel source is nickel sulfate, and the zinc source is zinc sulfate. The rest is the same as in example 1.
The SEM observation shows that the nanometer material is in a spherical chain shape, the diameter is about 500nm, and the length is about 30 mu m.
Example 3
A NiO-ZnO spherical chain nano material, which is different from the embodiment 1 in that the preparation method of the nano material of the embodiment comprises the following steps (b): the concentration of sodium hydroxide was 1.5 mol/L. The rest is the same as in example 1.
The nanometer material is in a spherical chain shape through SEM observation, the diameter is about 410nm, and the length is about 30 mu m.
Example 4
A NiO-ZnO spherical chain nano-material, which is different from the embodiment 1 in that the preparation method of the nano-material of the embodiment comprises the following steps (e): the reducing agent is sodium borohydride. The rest is the same as in example 1.
The nanometer material is in a spherical chain shape through SEM observation, the diameter is about 450nm, and the length is about 30 mu m.
Example 5
A NiO-ZnO ball-chain nanomaterial, which is different from that in example 1, in step (f) of the preparation method of the nanomaterial in the present example: the magnetic induction intensity of the magnetic field is 0.45T, the water bath heating temperature is 85 ℃, and the heat preservation time is 25 min. The rest is the same as in example 1.
The SEM observation shows that the nanometer material is in a spherical chain shape, the diameter is about 400nm, and the length is about 40 mu m.
Example 6
A NiO-ZnO spherical chain nanometer material is different from the embodiment 1 in that the preparation method of the nanometer material comprises the following steps of (i): the temperature was 310 ℃ and the duration was 1 h. The rest is the same as in example 1.
The SEM observation shows that the nanometer material is in a spherical chain shape, the diameter is about 390nm, and the length is about 30 mu m.
Comparative example 1
A nanomaterial of this comparative example, different from example 1, in step (f) of this comparative example, the mixed solution (r) was heated in a water bath and kept warm without being placed in a 0.4T parallel magnetic field. The rest is the same as in example 1.
The nanometer material is observed by SEM and is spherical, and the diameter is about 510 nm.
Comparative example 2
A nanomaterial different from example 1 in that in steps (a) and (b) of this comparative example, ethylene glycol was replaced with water. The rest is the same as in example 1.
The SEM observation shows that the nanometer material is in a short rod shape, the diameter is about 1.1 mu m, and the length is about 10 mu m.
Photocatalytic test
Adding 20mL of rhodamine B (rhodamine B is also called Rose Bengal B or basic Rose Bengal, commonly called Pink flower) into two reaction containers, wherein the rhodamine B is an artificially synthesized dye with bright pink color and has a chemical formula of C28H31ClN2O3) Solution (5mg/L), wherein 3mg of the spherical chain-shaped nanomaterial of example 1 was further added to one reaction vessel, and a photocatalytic reaction was performed using a xenon lamp as a light source without adding a catalyst (as a blank control) to the other reaction vessel. Measuring the photocatalytic effect according to the ratio of absorbance before and after reaction, and defining the ordinateIs ct/c0Wherein c is0And ctThe absorbance of the solution before and after the reaction, respectively, and the abscissa is the irradiation time.
As shown in FIG. 4, under the condition of no catalyst, after 3 hours of illumination, rhodamine B is only degraded by less than 4%, while the nano material of the embodiment 1 is added as the photocatalyst, and after 3 hours of illumination, the rhodamine B is degraded by about 53%, obviously, the nano material as the photocatalyst can greatly improve the degradation speed of the rhodamine B solution, and the catalytic effect is good.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (30)
1. A preparation method of a NiO-ZnO spherical chain nano material is characterized by comprising the following steps:
uniformly mixing an alcoholic solution of a nickel source, an alcoholic solution of a zinc source and an alcoholic solution of an alkali metal hydroxide, then mixing with a reducing agent, then placing the mixed solution in a parallel magnetic field, carrying out solid-liquid separation after the heating reaction is finished, and washing, drying and oxidizing the separated solid product to obtain the nano material;
wherein the nano material is mainly formed by sequentially connecting NiO-ZnO spherical particles; the NiO-ZnO spherical particles are particles with a core-shell structure, wherein the Ni-Zn is used as a core, and the NiO-ZnO is used as a shell.
2. The method for preparing NiO-ZnO spherical chain nano-materials according to claim 1, wherein the nickel source comprises at least one of nickel chloride, nickel sulfate or nickel nitrate.
3. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the concentration of the nickel source is 0.05-0.15 mol/L.
4. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the zinc source comprises at least one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
5. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the concentration of the zinc source is 0.02-0.05 mol/L.
6. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the alkali metal hydroxide comprises potassium hydroxide and/or sodium hydroxide.
7. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the concentration of the alkali metal hydroxide is 1 to 1.5 mol/L.
8. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the alcohol solution comprises a polyol solution.
9. The method for preparing NiO-ZnO spherical chain nano-material according to claim 8, wherein the polyalcohol solution comprises polyalcohol solutions of C2-C4.
10. The method for preparing NiO-ZnO spherical chain nano-material according to claim 8, wherein the polyalcohol solution comprises glycol solution.
11. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the reducing agent comprises at least one of borohydride, lithium aluminum hydride, hydrazine hydrate or hydrogen.
12. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the reducing agent is hydrazine hydrate.
13. The method for preparing NiO-ZnO spherical chain nano-material according to claim 12, wherein the concentration of hydrazine hydrate is 80-90%.
14. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the molar ratio of the nickel source, the zinc source, the alkali metal hydroxide and the reducing agent is (0.4-0.6): (0.2-0.3): (25-35): (160-180).
15. The method for preparing NiO-ZnO spherical chain nano-materials according to claim 1, characterized in that the alcoholic solution of the nickel source, the alcoholic solution of the zinc source or the alcoholic solution of the alkali metal hydroxide is prepared by the following steps independently: the nickel source, zinc source, or alkali metal hydroxide are each independently dissolved in an alcohol solution, followed by sonication and stirring.
16. The method for preparing NiO-ZnO spherical chain nano-material according to claim 15, wherein the stirring time is 20-40 min.
17. The method for preparing NiO-ZnO spherical chain nano-material according to claim 15, wherein the mixing manner of the alcoholic solution of the nickel source, the alcoholic solution of the zinc source and the alcoholic solution of the alkali metal hydroxide comprises: adding an alcoholic solution of alkali metal hydroxide into an alcoholic solution of a nickel source and an alcoholic solution of a zinc source, and uniformly stirring.
18. The method for preparing NiO-ZnO spherical chain nanomaterial according to claim 15, wherein the mixing manner of the mixed solution of the alcoholic solution of the nickel source, the alcoholic solution of the zinc source, and the alcoholic solution of the alkali metal hydroxide and the reducing agent comprises: and (3) dropwise adding a reducing agent into the mixed solution while stirring until the solution does not change color any more.
19. The method for preparing the NiO-ZnO spherical chain nano-material according to claim 1, wherein the magnetic induction intensity of the parallel magnetic field is 0.35 to 0.45T.
20. The method for preparing the NiO-ZnO spherical chain nano material according to claim 1, wherein the heating reaction is heating in a water bath to 85-95 ℃, and keeping the temperature for 15-25 min.
21. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the solid-liquid separation mode comprises centrifugation.
22. The method for preparing NiO-ZnO spherical chain nano-material as claimed in claim 21, wherein the rotation speed during centrifugation is 4000-6000rpm and the centrifugation time is 230-250 s.
23. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the washing mode comprises the following steps: washing with acetone, ethanol and distilled water sequentially for 4-6 times.
24. The method for preparing NiO-ZnO spherical chain nano-material according to claim 1, wherein the drying temperature is 70-90 ℃ and the drying time is 105-115 min.
25. The method for preparing NiO-ZnO spherical chain nano-material according to any one of claims 1 to 24, wherein the oxidation treatment mode comprises the following steps: the dried solid product is incubated for 1-3h at 290 ℃ and 310 ℃.
26. NiO-ZnO spherical chain nano-material, which is prepared according to the preparation method of any one of claims 1 to 25.
27. The NiO-ZnO spherical chain nanomaterial of claim 26, wherein the NiO-ZnO spherical particles have a diameter of 300-500nm, and the nanomaterial has a length of 20-40 μm.
28. The NiO-ZnO spherical chain nanomaterial of claim 26, wherein the diameter of the NiO-ZnO spherical particles is 350-450 nm; the length of the nano material is 25-35 μm.
29. Use of the NiO-ZnO ball-chain nanomaterial of any of claims 26 to 28 in photocatalysis, photodetection or gas detection.
30. A photocatalyst, photodetector, or gas detector comprising the NiO-ZnO ball-chain nanomaterial of any of claims 26 to 28.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910077570.3A CN109647414B (en) | 2019-01-25 | 2019-01-25 | NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910077570.3A CN109647414B (en) | 2019-01-25 | 2019-01-25 | NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109647414A CN109647414A (en) | 2019-04-19 |
| CN109647414B true CN109647414B (en) | 2021-12-07 |
Family
ID=66121481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910077570.3A Expired - Fee Related CN109647414B (en) | 2019-01-25 | 2019-01-25 | NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109647414B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721689A (en) * | 2019-11-12 | 2020-01-24 | 江苏师范大学 | Porous spherical NiO/TiO2Heterostructure nano material and preparation method thereof |
| CN111659404B (en) * | 2020-06-30 | 2021-08-17 | 天津大学 | Supported core-shell structure ZnO catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549406A (en) * | 2009-04-03 | 2009-10-07 | 北京航空航天大学 | A method for controllable growth of uniform nano nickel chain array induced by magnetic field |
| CN105776357A (en) * | 2016-03-21 | 2016-07-20 | 西北工业大学 | Method for preparing nickel oxide/zinc oxide heterojunction nanometer materials |
| CN106654303A (en) * | 2016-10-14 | 2017-05-10 | 济南大学 | ZnO-NiO/rGO composite material with efficient electrocatalytic oxygen reduction performance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2995377A1 (en) * | 2014-09-09 | 2016-03-16 | ETH Zurich | Catalytic materials based on functionalized ZSM-5 |
| KR20190003799A (en) * | 2016-05-26 | 2019-01-09 | 바스프 코포레이션 | Core / shell catalyst particles and process for their preparation |
| CN108855126B (en) * | 2017-05-11 | 2021-06-01 | 中国石油化工股份有限公司 | Shell-core catalyst for synthesizing m-phenylenediamine and preparation method thereof |
-
2019
- 2019-01-25 CN CN201910077570.3A patent/CN109647414B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549406A (en) * | 2009-04-03 | 2009-10-07 | 北京航空航天大学 | A method for controllable growth of uniform nano nickel chain array induced by magnetic field |
| CN105776357A (en) * | 2016-03-21 | 2016-07-20 | 西北工业大学 | Method for preparing nickel oxide/zinc oxide heterojunction nanometer materials |
| CN106654303A (en) * | 2016-10-14 | 2017-05-10 | 济南大学 | ZnO-NiO/rGO composite material with efficient electrocatalytic oxygen reduction performance |
Non-Patent Citations (1)
| Title |
|---|
| Oxide-Modified Nickel Photocatalysts for the Production of Hydrocarbons in Visible Light;Zhao, Yufei et.;《Angewandte Chemie》;20161231;4287-4291 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109647414A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Mechanisms for· O 2-and· OH production on flowerlike BiVO4 photocatalysis based on electron spin resonance | |
| CN102963934B (en) | Preparation method of bismuth tungstate quantum dot and preparation method of bismuth tungstate quantum dot-graphene composite material | |
| Kou et al. | Beet juice‐induced green fabrication of plasmonic AgCl/Ag nanoparticles | |
| CN109678728B (en) | Core-shell perovskite quantum dot and preparation method thereof | |
| CN109647414B (en) | NiO-ZnO spherical chain-shaped nano material and preparation method and application thereof | |
| CN103586084B (en) | Process for preparing porphyrin-functionalized nano sulfide with one-step method | |
| CN102973948B (en) | Method for preparing drug carrier based on magnetic carbon quantum dot/chitosan composite microsphere | |
| Miao et al. | A facile synthetic route for the preparation of gold nanostars with magnetic cores and their reusable nanohybrid catalytic properties | |
| CN113403070B (en) | Preparation method of high-stability cesium-lead halogen perovskite homojunction colloidal quantum dot | |
| CN109110819B (en) | Synthesis method of chiral manganese oxide nanoparticles | |
| CN102522454A (en) | Preparation method of CdSe nanocrystal semiconductor film | |
| CN104726085A (en) | Core-shell structured quantum dot composite nanocrystalline fluorescence probe and preparation method thereof | |
| CN110013880A (en) | A kind of MIL-101 composite photocatalyst material, preparation method and application | |
| CN111849478A (en) | Preparation method of novel magnetic fluorescent difunctional nano material | |
| CN103103634B (en) | ZnFe2O4 nano particle and ZnO nanofiber composite nanomaterial for glucose color index sensing and preparation method thereof | |
| CN110144049B (en) | Copper-terephthalic acid nano-particle, preparation method and application thereof | |
| CN106041060B (en) | A kind of method for preparing nano composite material using laser welding in the liquid phase | |
| CN103128305B (en) | Method for preparing Ag/Co magnetic nano composites | |
| CN109319842A (en) | A kind of fast preparation method of the manganese dioxide nano particle of bovine serum albumin load | |
| CN112374528B (en) | Graphene surface-loaded zinc oxide nanoparticle composite material and preparation method and application thereof | |
| Ge et al. | Fast synthesis of fluorescent SiO 2@ CdTe nanoparticles with reusability in detection of H 2 O 2 | |
| Zhou et al. | Assembly of direct Z-scheme ZnIn2S4/BiVO4 composite for enhanced photodegradation of tetracycline hydrochloride | |
| CN106006710B (en) | A kind of β NaYF4:Yb/Tm@ZnO core shell nanoparticles and preparation method thereof | |
| Zhang et al. | Synthesis and optical property of water-soluble ZnS: Cu quantum dots by use of thioglycolic acid | |
| CN106390991A (en) | Preparation method and application of ultra-fine WO3 nanowire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211207 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |