CN104020260B - The ZnO hetero nano structure of a kind of NiO and Al doping and preparation and application method thereof - Google Patents
The ZnO hetero nano structure of a kind of NiO and Al doping and preparation and application method thereof Download PDFInfo
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- CN104020260B CN104020260B CN201410274016.1A CN201410274016A CN104020260B CN 104020260 B CN104020260 B CN 104020260B CN 201410274016 A CN201410274016 A CN 201410274016A CN 104020260 B CN104020260 B CN 104020260B
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Abstract
The invention belongs to material science, particularly to ZnO hetero nano structure and the preparation and application method thereof of a kind of NiO and Al doping.The ZnO hetero nano structure of NiO and Al of the present invention doping is the hairbrush shape hetero nano structure being made up of the nanometer rods of NiO nanofiber and the ZnO of Al doping；Described hetero nano structure be by method of electrostatic spinning prepare NiO nanofiber, prepare on the surface of NiO nanofiber Al doping ZnO nano is bar-shaped, sample sintering prepares.The ZnO hetero nano structure of described NiO and Al doping can be used in preparing gas sensor.Test result indicate that gas sensor based on ZnO and NiO hetero nano structure has the sensitivity of excellence and the highest selectivity for Triethylamine gas.
Description
Technical field
The invention belongs to material science, particularly to the heterogeneous nanometer of ZnO of a kind of NiO and Al doping
Structure and preparation and application method thereof.
Background technology
Nano material refers to the size of its construction unit material between 1nm～100nm scope.Due to
Its size is already close to the coherence length of electronics, owing to the strong relevant self-organizing brought makes its character to send out
Raw great changes.Further, its yardstick, close to the wavelength of light, adds that it has big skin effect, therefore
Its characteristic showed, such as fusing point, magnetic, optics, heat conduction, conductive characteristic etc., be often different from
The character that this material is showed when integrality.Nanometer semiconductor structure material is led at nano-device in recent years
Territory plays an important role, and the technology of preparing of semiconductor nano material is also advanced by leaps and bounds.People are at present
Explore the multiple process for preparing semiconductor nano fiber and nanometer rods.
ZnO one-dimensional nano structure not only has the advantages such as ZnO broad stopband and high exciton bind energy, has the most simultaneously
There are the various characteristics of monodimension nanometer material.Therefore the electronic device made based on ZnO one-dimensional nano structure exists
Optoelectronic areas has huge application prospect.ZnO one-dimensional nano structure material extensively should in recent years
For various nano electron devices, including light emitting diode, gas sensor, laser instrument, solar energy
Battery etc..Utilize the 1-dimention nano sized materials of different structure to build three-dimensional manometer composite construction material in recent years
Material has become as focus.Compared with common nano structural material, this structural material has the biggest ratio
Surface area, and the advantage that different nano structural material can be merged.Therefore it is led at electronics and photoelectric device
Territory has huge application potential.Further, since its intrinsic inspectable space is respectively and anisotropy, these
Structure will can produce the physical property of uniqueness.ZnO nano-wire has the best sensitivity to reducibility gas.
Research shows that the specific surface area of its structure has important impact for its gas sensing performance, and specific surface area is more
Its gas sensing performance big is the most excellent.Simultaneously when there is PN hetero-junctions in structure, PN hetero-junctions can change
The sensitivity of kind gas sensor.
Summary of the invention
Not enough for prior art, the invention provides the heterogeneous nano junction of ZnO of a kind of NiO and Al doping
Structure and preparation and application method thereof.
The ZnO hetero nano structure of a kind of NiO and Al doping, the ZnO of described NiO and Al doping is different
The heterogeneous nanometer of hairbrush shape that the nanometer rods of the ZnO that matter nanostructured is adulterated by NiO nanofiber and Al is constituted
Structure；Described hairbrush shape hetero nano structure has trunk and the multiple burrs composition being arranged on trunk, often
One end of individual burr is connected with trunk, and wherein trunk is NiO nanofiber, and burr is the ZnO of Al doping
Nanometer rods；Containing PN junction in the ZnO hetero nano structure of described NiO and Al doping.
The diameter of described NiO nanofiber is in 50nm～1 μm.
The draw ratio of described NiO nanofiber is (10～10000): 1.
A diameter of 20nm～500nm of the ZnO nanorod of described Al doping.
The draw ratio of the ZnO nanorod of described Al doping is (1～50): 1.
0wt%～30wt% that doping is ZnO mass of Al element in the ZnO nanorod of described Al doping.
The preparation method of the ZnO hetero nano structure of a kind of NiO and Al doping, initially with electrostatic spinning
Method prepares NiO nanofiber, then prepares the ZnO of Al doping on nanofiber by hydrothermal synthesis method and receive
Rice is excellent thus obtains hetero nano structure.
The application process of the ZnO hetero nano structure of a kind of NiO and Al doping, described NiO and Al adulterates
ZnO hetero nano structure be used for preparing gas sensor.
At Al2O3The ZnO hetero nano structure of described NiO and Al doping is prepared in plane interdigital electrode, logical
Cross hot pressed sintering thus obtain gas sensor.
The invention have the benefit that
In the past based on the gas sensor prepared by ZnO nano-wire for reducibility gas selectivity the most not
Being very strong, the sensitivity for Triethylamine gas is not the highest, and this allows for it and is subject to application when
Some limit.Comparing with conventional gas sensor, the gas sensor prepared by the present invention is for three second
Amine gas has the highest selectivity and excellent sensitivity, and when 250 DEG C, the sensitivity of sensor is the highest.
And the increase along with Triethylamine gas concentration is increased by the sensitivity of sensor.
Accompanying drawing explanation
Fig. 1 is preparation and the test flow chart of gas sensor based on hetero nano structure of the present invention；
Fig. 2 is the SEM figure of gained hetero nano structure in the embodiment of the present invention 1；
Fig. 3 is the XPS spectrum figure of Al2p energy level in gained hetero nano structure in the embodiment of the present invention 1；
Fig. 4 is the gas sensor response curve to gas with various in the embodiment of the present invention 1；
Fig. 5 be in the embodiment of the present invention 1 gas sensor at different temperatures to 200ppm Triethylamine gas
Response curve；
Fig. 6 be in the embodiment of the present invention 1 gas sensor when 250 DEG C to variable concentrations Triethylamine gas
Response curve.
Detailed description of the invention
The invention provides ZnO hetero nano structure and the preparation and application side thereof of a kind of NiO and Al doping
Method, the present invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.
Embodiment 1
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 70 DEG C, stir 12min after 700 μ L triethylamines.ZnO growth solution is by 1.4
The C of g6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.075g3)3·9H2O's and 100mL
Deionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 8h.Gas sensitive is finally utilized to survey
The air-sensitive performance of gained gas sensor is characterized by test system.
Embodiment 2
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 40 DEG C, stir 12min after 700 μ L triethylamines.ZnO growth solution is by 1.4
The C of g6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.075g3)3·9H2O's and 100mL
Deionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 8h.Gas sensitive is finally utilized to survey
The air-sensitive performance of gained gas sensor is characterized by test system.
Embodiment 3
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 70 DEG C, stir 5min after 700 μ L triethylamines.ZnO growth solution is by 1.4g
C6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.075g3)3·9H2O and 100mL goes
Ionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 8h.Gas sensitive is finally utilized to test
The air-sensitive performance of gained gas sensor is characterized by system.
Embodiment 4
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 70 DEG C, stir 12min after 700 μ L triethylamines.ZnO growth solution is by 1.4
The C of g6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.75g3)3·9H2O's and 100mL
Deionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 8h.Gas sensitive is finally utilized to survey
The air-sensitive performance of gained gas sensor is characterized by test system.
Embodiment 5
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 70 DEG C, stir 12min after 700 μ L triethylamines.ZnO growth solution is by 1.4
The C of g6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.075g3)3·9H2O's and 100mL
Deionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 3h.Gas sensitive is finally utilized to survey
The air-sensitive performance of gained gas sensor is characterized by test system.
Embodiment 6
First with method of electrostatic spinning at Al2O3NiO nanofiber is prepared on interdigital electrode substrate.Then exist
Have on the substrate of NiO nanofiber grow Al doping ZnO nanorod, by hot pressed sintering thus obtain
Obtain gas sensor.During preparation ZnO seed-solution, by the Zn (Ac) of 1.10g2·2H2O joins 50mL
Isopropanol in, drip at 70 DEG C, stir 12min after 700 μ L triethylamines.ZnO growth solution is by 2.4
The C of g6H12N4, the Zn (NO of 2.92g3)2·6H2Al (the NO of O, 0.075g3)3·9H2O's and 100mL
Deionized water forms.Hydro-thermal reaction parameter is set at 95 DEG C react 8h.Gas sensitive is finally utilized to survey
The air-sensitive performance of gained gas sensor is characterized by test system.
Claims (7)
1. the ZnO hetero nano structure of NiO and Al doping, it is characterised in that: described NiO and
The nanometer rods of the ZnO that the ZnO hetero nano structure of Al doping is adulterated by NiO nanofiber and Al is constituted
Hairbrush shape hetero nano structure；Described hairbrush shape hetero nano structure has trunk and is arranged on trunk many
Individual burr is constituted, and one end of each burr is connected with trunk, and wherein trunk is NiO nanofiber, and burr is
The ZnO nanorod of Al doping；Containing PN junction in the ZnO hetero nano structure of described NiO and Al doping；
A diameter of 20nm～500nm of the ZnO nanorod of described Al doping；
The draw ratio of the ZnO nanorod of described Al doping is (1～50): 1.
The ZnO hetero nano structure of a kind of NiO and Al the most according to claim 1 doping, it is special
Levy and be: a diameter of 50nm of described NiO nanofiber～1 μm.
The ZnO hetero nano structure of a kind of NiO and Al the most according to claim 1 doping, it is special
Levy and be: the draw ratio of described NiO nanofiber is (10～10000): 1.
The ZnO hetero nano structure of a kind of NiO and Al the most according to claim 1 doping, it is special
Levy and be: the 0wt%～30 that doping is ZnO mass of Al element in the ZnO nanorod of described Al doping
Wt%.
5. the ZnO of a kind of NiO and the Al doping as described in Claims 1 to 4 any one claim is different
The preparation method of matter nanostructured, it is characterised in that: prepare NiO nanofiber initially with method of electrostatic spinning,
On nanofiber, prepare the ZnO nanorod of Al doping by hydrothermal synthesis method again thus obtain heterogeneous nano junction
Structure.
6. the ZnO of a kind of NiO and the Al doping as described in Claims 1 to 4 any one claim is different
The application process of matter nanostructured, it is characterised in that: the heterogeneous nano junction of ZnO of described NiO and Al doping
Structure is used for preparing gas sensor.
The application of the ZnO hetero nano structure of a kind of NiO and Al the most according to claim 6 doping
Method, it is characterised in that: at Al2O3The ZnO preparing described NiO and Al doping in plane interdigital electrode is different
Matter nanostructured, by hot pressed sintering thus obtain gas sensor.
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| CN104990961A (en) * | 2015-07-23 | 2015-10-21 | 吉林大学 | Ethanol gas sensor based on Al-doped NiO nano rod-flower material and preparation method thereof |
| CN105118694B (en) * | 2015-09-18 | 2017-12-05 | 北京科技大学 | A kind of preparation method of Al-Doped ZnO nano-array |
| CN106702534A (en) * | 2016-11-18 | 2017-05-24 | 江南大学 | Preparation method of AZO (Al-doped ZnO) hollow nanofibers |
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| CN101378091A (en) * | 2008-09-19 | 2009-03-04 | 武汉大学 | n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof |
| CN102583227A (en) * | 2012-03-13 | 2012-07-18 | 浙江大学 | Three-dimensional ZnO homogeneous pn junction nano array and preparation method thereof |
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| KR100812357B1 (en) * | 2005-12-23 | 2008-03-11 | 한국과학기술연구원 | Ultra-sensitive metal oxide gas sensor and fbrication method thereof |
| CN102515716A (en) * | 2011-12-08 | 2012-06-27 | 东华大学 | Preparation method of NiO/gamma-Al2O3 composite ceramic nanofiber |
| CN103412000B (en) * | 2013-07-29 | 2015-08-19 | 浙江大学 | A kind of single bending nanowire heterojunction biology sensor of ZnO/NiO and preparation method |
| CN103776870B (en) * | 2014-02-27 | 2016-06-08 | 河南理工大学 | A kind of flower-shaped hierarchical Z nO/SnO2Nano composite air-sensitive material and its preparation method |
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| CN101378091A (en) * | 2008-09-19 | 2009-03-04 | 武汉大学 | n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof |
| CN102583227A (en) * | 2012-03-13 | 2012-07-18 | 浙江大学 | Three-dimensional ZnO homogeneous pn junction nano array and preparation method thereof |
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| Hydrogen and ethanol sensors based on ZnO nanorods,nanowires and nanotubes，;Chandra sekhar rout等;《Chemical Physics Letters》;20060206;第418卷;第586-590页 * |
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