CN104492367A - Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof - Google Patents

Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof Download PDF

Info

Publication number
CN104492367A
CN104492367A CN201410686529.3A CN201410686529A CN104492367A CN 104492367 A CN104492367 A CN 104492367A CN 201410686529 A CN201410686529 A CN 201410686529A CN 104492367 A CN104492367 A CN 104492367A
Authority
CN
China
Prior art keywords
zno
nano
micro
zno micro
hierarchy
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.)
Granted
Application number
CN201410686529.3A
Other languages
Chinese (zh)
Other versions
CN104492367B (en
Inventor
金震
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei Institutes of Physical Science of CAS
Original Assignee
Hefei Institutes of Physical Science of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hefei Institutes of Physical Science of CAS filed Critical Hefei Institutes of Physical Science of CAS
Priority to CN201410686529.3A priority Critical patent/CN104492367B/en
Publication of CN104492367A publication Critical patent/CN104492367A/en
Application granted granted Critical
Publication of CN104492367B publication Critical patent/CN104492367B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a preparation method of a super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure, and the method is as follows: 1, synthesis of a micro-nano hierarchical structure comprising ultrathin porous nano single crystal ZnO nanosheets; 2, modification of the ZnO micro-nano hierarchical structure; and 3, preparation of the precious metal-modified ZnO micro-nano hierarchical structure. The super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure prepared by the method has the characteristics of single crystal, ultrathin thin, porous and hierarchical structure and assistant precious metal nanoparticle modification, the points are beneficial to improvement of the sensitivity of ZnO to organic gaseous pollutants, compared with the ZnO materials in the prior art, the super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure has super high gas sensitivity, and the detection limit is less than 1ppb.

Description

A kind of supersensitive noble metal decorated ZnO micro-nano hierarchy and preparation method thereof
Technical field
The present invention relates to the detecting instrument of organic gaseous contamination thing, be specifically related to a kind ofly to organic pollution, there is supersensitive noble metal decorated ultra thin single crystalline porous ZnO micro-nano hierarchy and preparation method thereof.
Background technology
The organic gaseous contamination thing ethanol, formaldehyde, benzene, toluene etc. that are brought by finishing material, have very large infringement to the healthy of people, easily cause the diseases such as breathing problem, pneumonia and tracheitis, even also has carcinogenic risk.Therefore the detection of organic gaseous contamination thing and Real-Time Monitoring are widely paid close attention to always.The detection conventional art of current organic gaseous contamination thing is chemical analysis, such as gas-chromatography and MS, and this detection method workload is large, program is complicated, apparatus expensive, and can not realize real-time detection.The electricity gas sensor of based semiconductor oxide, owing to having the advantages such as low in energy consumption, response is fast, structure simple, technical maturity, is with a wide range of applications in the detection and Real-Time Monitoring of organic pollution.
ZnO is as a kind of broad stopband (3.37eV) semiconductor, and have the features such as electron mobility is high, chemical stability is good, it all embodies good gas-sensitive property to indoor air pollutants.But traditional sensors is often based on the ZnO sensitive material of block, therefore its sensitivity is not high.Research shows, have ultra-thin, monocrystalline, porous, the ZnO material of hierarchy and be aided with noble metal nano particles and modify and all can improve the sensitivity of ZnO to indoor air pollutants, because: (1) is when ZnO size is less than 2 times of depletion width (22nm), whole particle all becomes depletion layer, the mobile charge of nearly all semi-conducting material is all bound on the oxygen molecule of absorption, when particle surface target acquisition molecule release electric charge, electronics is discharged by adsorption oxygen molecule, cause the great variety of response current, thus improve the sensitivity of sensor, (2) mono-crystalline structures is not then owing to having crystal boundary, do not have loss when electronics transmits in vivo, not only can improve sensitivity, can also ensure the stability of sensor, (3) loose structure is conducive to the specific area increasing material, thus increases the activated adoption site to determinand, (4) hierarchy then not only can provide the passage required for gas to be measured diffusion, and can also ensure that ultra-thin materials avoids reuniting, (5) noble metal nano particles is owing to having high catalytic activity, can increase the reactivity of sensitive material.
The existing sensor based on ZnO is all often that above utilizing, or several of mentioning in five realizes the lifting of sensitivity, however can realize simultaneously this five but have no report.Therefore, how to prepare the hierarchy with ultra-thin porous single crystal ZnO and how to realize the huge challenge be modified into improve transducer sensitivity of precious metal material nanometer.
Summary of the invention
The present invention is directed to based on traditional Z nO material under-sensitive shortcoming, propose the ZnO micro-nano hierarchy of the ultra thin single crystalline porous ZnO nanometer sheet composition that a kind of noble metal granule is modified.
A preparation method for supersensitive noble metal decorated ZnO micro-nano hierarchy, comprises the steps:
(1) ZnO micro-nano hierarchy is synthesized:
By zinc acetate (Zn (CH 3cOO) 2) and urea (CO (NH 2) 2) dissolve form clear solution in a solvent; Then after being carried out by clear solution sealing, being incubated 3-24h, centrifugation is carried out to it, washing, drying obtain ultrathin nanometer ZnO precursor; Finally ultrathin nanometer ZnO precursor is carried out annealing in process, namely obtain the ZnO micro-nano hierarchy be made up of ultra thin single crystalline porous ZnO nanometer sheet;
(2) modification of ZnO micro-nano hierarchy:
By ultrasonic disperse be in the polymer coupler solution of 7.5-9 in pH value by the ZnO micro-nano hierarchy prepared through (1), after stirring, again ZnO micro-nano hierarchy separated by centrifugal, and dry to obtain modification ZnO micro-nano hierarchy;
(3) noble metal nano particles colloidal sol is prepared:
Be first that the soluble precious-metal solution of 0.1%-4% adds in deionized water and boils by mass concentration, reducing agent is added in boiling process, then continue heating after 5-10 minute, namely cooling obtains having certain size and the noble metal nano particles colloidal sol of favorable dispersibility naturally;
(4) noble metal decorated ZnO micro-nano hierarchy is prepared:
Modification ZnO micro-nano hierarchy is mixed with noble metal nano particles colloidal sol, stirs 0.5-4h, namely on ZnO micro-nano hierarchy, modify noble metal granule by electrostatic interaction, centrifugal, dry and obtain noble metal decorated ZnO micro-nano hierarchy.
Further, in described step (1), the mass ratio of zinc acetate and urea is 0.5-2:1-8;
Described solvent is by volume for 0.5-5:1 is formed by deionized water and ethylene glycol.
Further, in described step (1), insulation 3-24h refers in temperature to be incubated 3-24h in the baking oven of 70-110 DEG C;
Described annealing in process refers to that in temperature be annealing in process in the Muffle furnace of 250-500 DEG C or tube furnace.
Further, in described step (1), ultra thin single crystalline porous ZnO nanometer sheet refers to the ZnO nano sheet that length is 1-20 μm, width is 50nm-10 μm, thickness is no more than 22nm, crystalline phase is buergerite phase;
Described ZnO micro-nano hierarchy refers to that flower-shaped or spherical, the particle diameter be made up of ZnO nano sheet is the hierarchy of 1-100 μm.
Further, in described step (2), polymer coupler refers to amino silicane coupling agent, mercaptosilane coupling agents or polymine.
Further, the time 2-24h stirred after ultrasonic disperse in described step (2); Described oven dry refers to dries in the baking oven of temperature lower than 80 DEG C.
Further, soluble precious-metal described in described step (3) refers to that granular size is the gold, silver of 5-100nm, platinum or palladium; Described soluble precious-metal solution comprises chlorauric acid solution, liquor argenti nitratis ophthalmicus, platinum acid chloride solution and chlorine palladium acid solution etc.
Further, citric acid solution or the citric acid three sodium solution of reducing agent to be mass concentration be 0.1%-4% in described step (3), the mass ratio of described soluble precious-metal solution and reducing agent is 0.5:1-1:5.
Further, the weight ratio 1:0.005-0.05 of the middle modification ZnO micro-nano hierarchy of described step (4) and noble metal nano particles.
Another object of the present invention is to provide a kind of noble metal decorated ZnO micro-nano hierarchy prepared by above-mentioned preparation method, the form of described noble metal decorated ZnO micro-nano hierarchy is spherical or flower-shaped, particle diameter is 1-100 μm, and it has hypersensitivity to low concentration organic gaseous contamination thing.
Because ZnO is amphoteric metal oxide, if the pH of high molecular polymer dispersion liquid is too high, alkalescence is crossed can cause by force the dissolving in a polymer solution of ZnO hierarchy, and therefore its pH value must control at 7.5-9 within the scope of this.
The ZnO precursor with spherical or flower-shaped hierarchy that the present invention is made up of at the smooth ZnO nano sheet pile body of 100nm-10 μm size hydro-thermal method; Carry out annealing in process by ZnO precursor again and obtain the ZnO micro-nano hierarchy be made up of ultra thin single crystalline porous ZnO nanometer sheet; Then modification is carried out.Finally modification ZnO micro-nano hierarchy is mixed with noble metal nano particles colloidal sol, modified by electrostatic interaction, obtain noble metal decorated ZnO micro-nano hierarchy.Namely the noble metal decorated ZnO micro-nano hierarchy that prepared by the present invention utilizes the feature of its porous and hierarchy to improve the adsorption capacity of molecules detected on ZnO surface; Utilize ultra-thin, monocrystalline and noble metal decorated advantage to increase sensitivity and the stability of sensor, thus realize detecting the hypersensitivity of low concentration organic gaseous contamination thing.
So beneficial effect of the present invention has:
1, the noble metal decorated ZnO micro-nano hierarchy that prepared by the present invention has ultra-thin, monocrystalline, porous, hierarchy feature, and be aided with noble metal nano particles modify all can improve the sensitivity of ZnO to indoor air pollutants, it is relative to existing ZnO material, to organic gaseous contamination thing ethanol, formaldehyde, acetone etc., there is superelevation Gas-sensing measurment, detectability can reach 1ppb, than highly sensitive three orders of magnitude in existing ZnO block and powder body material, also far above conventional nano material.
2, the noble metal decorated ZnO micro-nano hierarchy that prepared by the present invention utilizes the feature of porous and hierarchy to improve the adsorption capacity of molecules detected on ZnO surface, utilize ultra-thin, monocrystalline and noble metal decorated advantage to increase sensitivity and the stability of sensor, thus realize detecting the hypersensitivity of low concentration organic gaseous contamination thing.
3, preparation method of the present invention can accurate its loose structure of porous ultra thin single crystalline ZnO nano sheet, size and thickness of the size of control ZnO micro-nano hierarchy, pattern and composition, all be conducive to the raising of ZnO micro-nano hierarchy sensitivity, specifically: by size and the pattern of control ZnO micro-nano hierarchy, can pore structure in Effective Regulation hierarchy, can make testing molecule can effectively in ZnO material diffusion inside; By controlling the pore structure of its porous ultra thin single crystalline ZnO nano sheet of composition, the active adsorption sites in ZnO material can be increased, thus effectively catch testing molecule; By controlling size and the thickness of nanometer sheet, the ratio of depletion layer on ZnO nano sheet can be controlled, reducing the internal loss of electronics.
4, the present invention is the concentration that 7.5-9 regulates polymer coupler solution by controlling polymer coupler solution ph, can also effectively prevent the ZnO caused excessively by force due to polymer coupler solution alkaline from dissolving while realizing the modification of ZnO micro-nano hierarchy.
5, the invention provides a kind of method of modifying noble metal granule on ZnO micro-nano hierarchy of novelty, accurately can control the modification amount needing the noble metal granule modified, and effectively increase the Gas-sensing measurment of ZnO micro-nano hierarchy.Meanwhile, Preparation equipment small investment, synthesis technique is simple, processing ease.
6, the mentality of designing of ZnO sensitive material provided by the present invention and preparation method, for the practical application of the sensor sensing material with superelevation sensitive property provides new mentality of designing and preparation method.
Accompanying drawing explanation
Fig. 1 is the electron-microscope scanning figure of the ZnO micro-nano hierarchy prepared by the present invention.
Fig. 2 is electron-microscope scanning figure and the electron diffraction diagram of the ultra thin single crystalline porous ZnO nanometer sheet forming ZnO micro-nano hierarchy.
Fig. 3 is electron-microscope scanning figure and the transmission plot of the ZnO micro-nano hierarchy that Argent grain is modified.
Fig. 4 is the XRD spectra contrast of the ZnO micro-nano hierarchy before Argent grain is modified and after modifying.
Fig. 5 be Argent grain modify before and modify after ZnO micro-nano hierarchy to the air-sensitive detection figure of ethanol.
Detailed description of the invention
Embodiment 1
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 1g 3cOO) 2) and 4g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 40ml is made up of for 3:1 by volume deionized water and ethylene glycol, stir and form clear solution; Transfer them to again in the conical flask of a sealing, and be positioned in the baking oven of 90oC temperature, insulation 10h; Then carry out centrifugation and go out white precipitate, put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally by the ZnO precursor of drying annealing in process in the Muffle furnace or tube furnace of 400oC, namely obtain the ZnO micro-nano hierarchy be made up of ultra thin single crystalline porous ZnO nanometer sheet.
ZnO micro-nano hierarchy prepared by the present embodiment is as shown in 1d in Fig. 1, and its shape is flower-shaped.
In addition, as shown in Figure 2, it is about 5 μm, width about 1 μm, thickness is about 10nm, and nano aperture is evenly distributed in whole nanometer sheet for the electron-microscope scanning figure of ultra thin single crystalline porous ZnO nanometer sheet prepared by the present embodiment and electron diffraction diagram.2a, 2b wherein in Fig. 2 are front and the side electron-microscope scanning figure of ultra thin single crystalline porous ZnO nanometer sheet prepared by the present embodiment, the cavernous structure of the ZnO nano sheet of visible monolithic and ultra-thin thickness; 2c, 2d are the transmission photos of monolithic ZnO nano sheet, and its loose structure is high-visible; 2e is the electron diffraction diagram of monolithic ZnO nano sheet, and its diffraction pattern is rendered as the dots structure of rule, and which illustrating nanometer sheet is mono-crystalline structures; 2f is the lattice fringe picture of ZnO nano sheet, and the arrangement of its lattice fringe in good order as seen, also demonstrates the mono-crystalline structures of ZnO nano sheet.
(2) modification of ZnO micro-nano hierarchy: getting 50mg through the flower-shaped ZnO micro-nano hierarchy ultrasonic disperse prepared by (1) is in the polyethylenimine solution of 8.5 in pH value, by centrifugal, modified ZnO micro-nano hierarchy is separated from solution after stirring 3h, and dry in 75oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the liquor argenti nitratis ophthalmicus 100ml of 1wt%, liquor argenti nitratis ophthalmicus and 1wt% citric acid solution is added in boiling process, the mass ratio of liquor argenti nitratis ophthalmicus and citric acid solution is 1:3, and continuation heating cools after 10 minutes naturally can obtain the Argent grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the silver sol of silver-containing nanoparticles 1mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 0.5h, namely on flower-shaped ZnO micro-nano hierarchy, modify Argent grain by electrostatic interaction, then centrifugal, dry and obtain load capacity be 1% Argent grain modify flower-shaped ZnO micro-nano hierarchy.
The electron-microscope scanning figure of the flower-shaped ZnO micro-nano hierarchy that Argent grain prepared by the present invention is modified is as shown in 3a, 3b in Fig. 3, and what visible Ag was a large amount of is distributed in the nanometer sheet of micro-nano structure; Its transmission plot, as shown in 3c, 3d in Fig. 3, can find out Argent grain uniform particle diameter, and is uniformly distributed on the surface at ZnO nano sheet.
The XRD spectra of modified ZnO micro-nano hierarchy is as shown in 4a in Fig. 4, and the XRD spectra of the flower-shaped ZnO micro-nano hierarchy that Argent grain is modified is as shown in 4b in Fig. 4, the XRD diffraction maximum of the ZnO micro-nano hierarchy before visible Argent grain modification all belongs to buergerite ZnO structure, and Argent grain has obviously occurred a diffraction maximum belonging to Ag (200) face after modifying, demonstrate the modification of Ag in the classification of ZnO micro-nano; And except Zn and O in 4b figure, also occur the peak of Ag, also demonstrated Ag and be modified in the classification of ZnO micro-nano.
Have excellent response sensitivity to the ZnO micro-nano hierarchy that the Argent grain after the present embodiment preparation is modified to organic gaseous contamination thing, its air-sensitive to ethanol detects as shown in 5a in Fig. 5, and it can reach 1 ppb to the detectability of ethanol; And its response sensitivity and gas concentration linear relationship chart are shown in Fig. 5 shown in 5b, the response of ZnO micro-nano hierarchy to ethanol of visible Ag particle modification also exists good linear, is expected to be applied to actual ethanol sensor and detects.
Embodiment 2
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 0.5g 3cOO) 2) and 3g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 50ml is made up of for 1:1 by volume deionized water and ethylene glycol, stir 3min and form clear solution; Transfer them to again in the conical flask of a sealing, and be positioned in the baking oven of 75oC temperature, insulation 8h; Then use centrifugal method to be separated from solution by the white precipitate obtained, and put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally by the ZnO precursor of drying annealing in process under 300oC, the spherical ZnO micro-nano hierarchy as shown in 1c in Fig. 1 can be obtained, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 2 μm, width is about 400nm, thickness is about 8nm, and nano aperture is evenly distributed in whole nanometer sheet.
(2) modification of ZnO micro-nano hierarchy: getting the flower-shaped ZnO micro-nano hierarchy ultrasonic disperse that 50mg prepared through (1) is in the polyethylenimine solution of 7.8 in pH value, stirs 2h.Then by centrifugal, modification ZnO micro-nano hierarchy is separated from solution, dry in 70oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorauric acid solution 100ml of 0.5 wt %.In boiling process, add 0.5% trisodium citrate, the mass ratio of its chlorauric acid solution and trisodium citrate is 1:2, and then continuation heating naturally cools after 10 minutes and can obtain the aurosol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the aurosol containing gold nano grain 10mg by modified spherical ZnO micro-nano hierarchy 1000mg, stir 1h, the modification of gold grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the gold grain modification of 1%, it has excellent response sensitivity to organic gaseous contamination thing, and wherein the detectability of PARA FORMALDEHYDE PRILLS(91,95) can reach 0.05 ppm.
Embodiment 3
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 0.5g 3cOO) 2) and 1g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 40ml is made up of for 1:1 by volume deionized water and ethylene glycol, stir and form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 75oC temperature, insulation 5h; Then use centrifugal method to be separated from solution by the white precipitate obtained, and put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying is annealed under 300oC, can obtain the spherical ZnO micro-nano hierarchy as shown in 1b in Fig. 1, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 4 μm, and width is about 500nm, thickness is about 12nm, and nano aperture is evenly distributed in whole nanometer sheet.
(2) modification of ZnO micro-nano hierarchy: getting the flower-shaped ZnO micro-nano hierarchy ultrasonic disperse that 50mg prepared through (1) is in the polyethylenimine solution of 8 in pH value, stirs 5h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 65oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the platinum acid chloride solution 100ml of 1wt %.In boiling process, add 1% citric acid, the mass ratio of its platinum acid chloride solution and citric acid is 1:2; Then continuation heating naturally cools after 10 minutes and can obtain the platinum grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the platinum colloidal sol containing Pt nanoparticle 2mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 1h, the modification of platinum grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the platinum grain modification of 2%, it has excellent response sensitivity to organic gaseous contamination thing, wherein can reach 10 ppb to the detectability of acetone.
Embodiment 4
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 0.8g 3cOO) 2) and 3.5g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 80ml is made up of for 2:1 by volume deionized water and ethylene glycol, stir and form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 80oC temperature, insulation 8h; Then centrifugal method is used to be separated from solution by the white precipitate obtained.Put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying annealed under 300oC, can obtain the spherical ZnO micro-nano hierarchy as shown in 1c in Fig. 1, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 5 μm, and width is about 800nm, and thickness is about 10nm.
(2) modification of ZnO micro-nano hierarchy: get the flower-shaped ZnO micro-nano hierarchy that 50mg is prepared through (1), ultrasonic disperse is in the polyethylenimine solution of 8 in 100ml pH value, stirs 12h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 70oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorine palladium acid solution 100ml of 0.1 wt %.In boiling process, add 0. 1% citric acid solution, the mass ratio of its chlorine palladium acid solution and citric acid solution is add in the ratio of 1:1, and then continuation heating naturally cools after 10 minutes and can obtain the palladium particle colloidal sols with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the palladium colloidal sol containing palladium nano-particles 2mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 2h, the modification of palladium particle on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the palladium particle modification of 2%, it has excellent response sensitivity to organic gaseous contamination thing, wherein can reach 5 ppb to the detectability of acetone.
Embodiment 5
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 1g 3cOO) 2) and 1g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 30ml is made up of for 0.5:1 by volume deionized water and ethylene glycol, stir 5min to form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 70oC temperature, be incubated 8h; Then centrifugal method is used to be separated from solution by the white precipitate obtained.Put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying is annealed under 300oC, can obtain the spherical ZnO micro-nano hierarchy as shown in 1a in Fig. 1, the ultra thin single crystalline porous ZnO nanometer sheet forming it is about 1 μm, and width is about 50nm, thickness is about 8nm, and nano aperture is evenly distributed in whole nanometer sheet.
(2) modification of ZnO micro-nano hierarchy: get the flower-shaped ZnO micro-nano hierarchy that 50mg is prepared through (1), ultrasonic disperse is in the polyethylenimine solution of 8 in 100ml pH value, stirs 18h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 75oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorauric acid solution 100ml of 0.1 wt %.In boiling process, add 0.1% citric acid solution, the mass ratio of its chlorauric acid solution and citric acid solution is 1:1, and then continuation heating naturally cools after 10 minutes and can obtain the gold grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the aurosol containing gold nano grain 5mg by modified spherical ZnO micro-nano hierarchy 1000mg, stir 0.5h, the modification of gold grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the gold grain modification of 0.5%, it has excellent response sensitivity to organic gaseous contamination thing, and wherein the detectability of PARA FORMALDEHYDE PRILLS(91,95) can reach 0.05 ppm.
Embodiment 6
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 1.3g 3cOO) 2) and 5.5g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 40ml is made up of for 4:1 by volume deionized water and ethylene glycol, stir a period of time to form clear solution, again this transparent solution is transferred in the conical flask of a sealing, and is positioned in the baking oven of 100oC temperature, insulation 12h; Then centrifugal method is used to be separated from solution by the white precipitate obtained.Put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying annealed under 400oC, can obtain flower-shaped ZnO micro-nano hierarchy, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 10 μm, and width about 2 μm, thickness is about 8nm.
(2) the flower-shaped ZnO micro-nano hierarchy that the modification of ZnO micro-nano hierarchy: 50mg is prepared through (1) is got, and ultrasonic disperse is in the polyethylenimine solution of 9 in 100ml pH value, stirs 3h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 80oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorauric acid solution 100ml of 1wt %.In boiling process, add 1% citric acid solution, the mass ratio of its chlorauric acid solution and citric acid solution is 1:4, and then continuation heating naturally cools after 10 minutes and can obtain the gold grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the aurosol containing gold nano grain 3mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 3h, the modification of gold grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the gold grain modification of 3%, it has excellent response sensitivity to organic gaseous contamination thing, and wherein the detectability of PARA FORMALDEHYDE PRILLS(91,95) can reach 0.08 ppm.
Embodiment 7
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 1.5g 3cOO) 2) and 6g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 40ml is made up of for 5:1 by volume deionized water and ethylene glycol, stir a period of time to form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 110oC temperature, be incubated 18h; Then centrifugal method is used to be separated from solution by the white precipitate obtained.Put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying annealed under 500oC, can obtain flower-shaped ZnO micro-nano hierarchy, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 15 μm, and width about 5 μm, thickness is about 8nm.
(2) modification of ZnO micro-nano hierarchy: get the flower-shaped ZnO micro-nano hierarchy that 50mg is prepared through (1), ultrasonic disperse is in the polyethylenimine solution of 8 in 100ml pH value, stirs 24h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 75oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorauric acid solution 100ml of 4 wt %.In boiling process, add 2% citric acid solution, the mass ratio of its chlorauric acid solution and citric acid solution is 1:5, and then continuation heating naturally cools after 10 minutes and can obtain the gold grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed in proportion with the aurosol containing gold nano grain 5mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 4h, the modification of gold grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the gold grain modification of 5%, it has excellent response sensitivity to organic gaseous contamination thing, wherein can reach 0.01 ppm to the detectability of ethanol.
Embodiment 8
(1) synthesis of ZnO micro-nano hierarchy: by the zinc acetate (Zn (CH of 2g 3cOO) 2) and 8g urea (CO (NH 2) 2) be dissolved in the mixed solvent that 40ml is made up of for 8:1 by volume deionized water and ethylene glycol, stir and form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 110oC temperature, insulation 24h; Then centrifugal method is used to be separated from solution by the white precipitate obtained.Put it into after being cleaned 2-3 time by deionized water 60oC vacuum drying chamber dry ZnO precursor; Finally the ZnO precursor of drying annealed under 500oC, can obtain flower-shaped ZnO micro-nano hierarchy, what form its ultra thin single crystalline porous ZnO nanometer sheet is about 20 μm, and width about 10 μm, thickness is about 22nm.
(2) modification of ZnO micro-nano hierarchy: get the flower-shaped ZnO micro-nano hierarchy that 50mg is prepared through (1), ultrasonic disperse is in the polyethylenimine solution of 7.5 in 100ml pH value, stirs 4h.Then by centrifugal, ZnO micro-nano hierarchy is separated from solution, dry in 80oC baking oven.
(3) noble metal nano particles colloidal sol is prepared: first boiled by the chlorauric acid solution 100ml of 4wt %.In boiling process, add 2% citric acid solution, the mass ratio of its chlorauric acid solution and citric acid solution is 1:5, and then continuation heating naturally cools after 10 minutes and can obtain the gold grain colloidal sol with certain size favorable dispersibility.
(4) noble metal decorated ZnO micro-nano hierarchy is prepared: mixed with the aurosol containing gold nano grain 2.5mg by modified spherical ZnO micro-nano hierarchy 100mg, stir 4h, the modification of gold grain on spherical ZnO micro-nano hierarchy can be realized by electrostatic interaction, centrifugal, dry and obtain the spherical ZnO micro-nano hierarchy that load capacity is the gold grain modification of 2.5%, it can reach 0.01 ppm to the detectability of PARA FORMALDEHYDE PRILLS(91,95).
Above embodiment is not limited only to protection scope of the present invention, all modify based on fundamental idea of the invention or change all belong to protection scope of the present invention.

Claims (10)

1. a preparation method for supersensitive noble metal decorated ZnO micro-nano hierarchy, is characterized in that: comprise the steps:
(1) ZnO micro-nano hierarchy is synthesized:
By zinc acetate (Zn (CH 3cOO) 2) and urea (CO (NH 2) 2) dissolve form clear solution in a solvent; Then after being carried out by clear solution sealing, being incubated 3-24h, centrifugation is carried out to it, washing, drying obtain ultrathin nanometer ZnO precursor; Finally ultrathin nanometer ZnO precursor is carried out annealing in process, namely obtain the ZnO micro-nano hierarchy be made up of ultra thin single crystalline porous ZnO nanometer sheet;
(2) modification of ZnO micro-nano hierarchy:
By ultrasonic disperse be in the polymer coupler solution of 7.5-9 in pH value by the ZnO micro-nano hierarchy prepared through (1), after stirring, again ZnO micro-nano hierarchy separated by centrifugal, and dry to obtain modification ZnO micro-nano hierarchy;
(3) noble metal nano particles colloidal sol is prepared:
Be first that the soluble precious-metal solution of 0.1%-4% adds in deionized water and boils by mass concentration, reducing agent is added in boiling process, then continue heating after 5-10 minute, namely cooling obtains having certain size and the noble metal nano particles colloidal sol of favorable dispersibility naturally;
(4) noble metal decorated ZnO micro-nano hierarchy is prepared:
Modification ZnO micro-nano hierarchy is mixed with noble metal nano particles colloidal sol, stirs 0.5-4h, namely on ZnO micro-nano hierarchy, modify noble metal granule by electrostatic interaction, centrifugal, dry and obtain noble metal decorated ZnO micro-nano hierarchy.
2. preparation method according to claim 1: it is characterized in that: in described step (1), the mass ratio of zinc acetate and urea is 0.5-2:1-8;
Described solvent is by volume for 0.5-5:1 is formed by deionized water and ethylene glycol.
3. preparation method according to claim 1: it is characterized in that: in described step (1), insulation 3-24h refers in temperature to be incubated 3-24h in the baking oven of 70-110 DEG C;
Described annealing in process refers to that in temperature be annealing in process in the Muffle furnace of 250-500 DEG C or tube furnace.
4. preparation method according to claim 1: it is characterized in that: in described step (1), ultra thin single crystalline porous ZnO nanometer sheet refers to the ZnO nano sheet that length is 1-20 μm, width is 50nm-10 μm, thickness is no more than 22nm, crystalline phase is buergerite phase;
Described ZnO micro-nano hierarchy refers to that flower-shaped or spherical, the particle diameter be made up of ZnO nano sheet is the hierarchy of 1-100 μm.
5. preparation method according to claim 1: it is characterized in that: in described step (2), polymer coupler refers to amino silicane coupling agent, mercaptosilane coupling agents or polymine.
6. preparation method according to claim 1: it is characterized in that: the time 2-24h stirred after ultrasonic disperse in described step (2); Described oven dry refers to dries in the baking oven of temperature lower than 80 DEG C.
7. preparation method according to claim 1: it is characterized in that: soluble precious-metal described in described step (3) refers to that granular size is the gold, silver of 5-100nm, platinum or palladium; Described soluble precious-metal solution comprises chlorauric acid solution, liquor argenti nitratis ophthalmicus, platinum acid chloride solution and chlorine palladium acid solution.
8. preparation method according to claim 1: it is characterized in that: citric acid solution or the citric acid three sodium solution of reducing agent to be mass concentration be 0.1%-4% in described step (3), the mass ratio of described soluble precious-metal solution and reducing agent is 0.5:1-1:5.
9. preparation method according to claim 1: it is characterized in that: the weight ratio 1:0.005-0.05 of modification ZnO micro-nano hierarchy and noble metal nano particles in described step (4).
10. the noble metal decorated ZnO micro-nano hierarchy prepared by the preparation method described in any one of claim 1-9, it is characterized in that: the form of described noble metal decorated ZnO micro-nano hierarchy is spherical or flower-shaped, particle diameter is 1-100 μm, and it has hypersensitivity to low concentration organic gaseous contamination thing.
CN201410686529.3A 2014-11-26 2014-11-26 Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof Expired - Fee Related CN104492367B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410686529.3A CN104492367B (en) 2014-11-26 2014-11-26 Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410686529.3A CN104492367B (en) 2014-11-26 2014-11-26 Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104492367A true CN104492367A (en) 2015-04-08
CN104492367B CN104492367B (en) 2017-05-03

Family

ID=52933869

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410686529.3A Expired - Fee Related CN104492367B (en) 2014-11-26 2014-11-26 Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104492367B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107064220A (en) * 2017-01-23 2017-08-18 吉林大学 Using the spherical multi-slice structure ZnO of ultra-fine Au Nanoparticle Modifieds as the acetylene gas sensor and preparation method of sensitive layer
CN109507251A (en) * 2018-09-29 2019-03-22 中国科学院合肥物质科学研究院 It palladium modification zinc oxide nanometer sheet, preparation method and its is applied in gas sensor
CN109725039A (en) * 2019-01-10 2019-05-07 沈阳化工大学 A kind of preparation and its application of Pd modification ZnO nano-rod array
CN109954481A (en) * 2019-04-04 2019-07-02 重庆大学 The method for preparing the ZnO@ZIF-8 nano flower compound of Ag doping
CN109975367A (en) * 2019-03-11 2019-07-05 陕西科技大学 The WO less than 60nm based on the modification of Ag quantum dot3-SnO2Solid nanospheres acetone sensor and preparation method
CN110801804A (en) * 2019-12-09 2020-02-18 安徽建筑大学 Metal oxide nano adsorption material with micro-nano hierarchical structure and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2495074A (en) * 2011-09-12 2013-04-03 Univ Swansea ZnO nanomaterials and gas sensors made using the nanomaterials
CN103046132A (en) * 2011-10-12 2013-04-17 华东理工大学 Preparation and application of ZnO nanometer monocrystal with porous flower-like structure
CN103318944A (en) * 2013-06-24 2013-09-25 上海大学 Preparation method of zinc oxide multi-stage nanometer structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2495074A (en) * 2011-09-12 2013-04-03 Univ Swansea ZnO nanomaterials and gas sensors made using the nanomaterials
CN103046132A (en) * 2011-10-12 2013-04-17 华东理工大学 Preparation and application of ZnO nanometer monocrystal with porous flower-like structure
CN103318944A (en) * 2013-06-24 2013-09-25 上海大学 Preparation method of zinc oxide multi-stage nanometer structure

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107064220A (en) * 2017-01-23 2017-08-18 吉林大学 Using the spherical multi-slice structure ZnO of ultra-fine Au Nanoparticle Modifieds as the acetylene gas sensor and preparation method of sensitive layer
CN107064220B (en) * 2017-01-23 2019-07-23 吉林大学 A kind of the zno-based acetylene sensor and preparation method of ultra-fine Au particle modification
CN109507251A (en) * 2018-09-29 2019-03-22 中国科学院合肥物质科学研究院 It palladium modification zinc oxide nanometer sheet, preparation method and its is applied in gas sensor
CN109725039A (en) * 2019-01-10 2019-05-07 沈阳化工大学 A kind of preparation and its application of Pd modification ZnO nano-rod array
CN109975367A (en) * 2019-03-11 2019-07-05 陕西科技大学 The WO less than 60nm based on the modification of Ag quantum dot3-SnO2Solid nanospheres acetone sensor and preparation method
CN109954481A (en) * 2019-04-04 2019-07-02 重庆大学 The method for preparing the ZnO@ZIF-8 nano flower compound of Ag doping
CN110801804A (en) * 2019-12-09 2020-02-18 安徽建筑大学 Metal oxide nano adsorption material with micro-nano hierarchical structure and preparation method thereof

Also Published As

Publication number Publication date
CN104492367B (en) 2017-05-03

Similar Documents

Publication Publication Date Title
Guo et al. Gas sensor based on MOFs-derived Au-loaded SnO2 nanosheets for enhanced acetone detection
Yin et al. Fabrication, characterization and n-propanol sensing properties of perovskite-type ZnSnO3 nanospheres based gas sensor
Xu et al. An excellent triethylamine (TEA) sensor based on unique hierarchical MoS2/ZnO composites composed of porous microspheres and nanosheets
CN104492367A (en) Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof
Hao et al. Construction of porous LaFeO3 microspheres decorated with NiO nanosheets for high response ethanol gas sensors
Li et al. Fabrication of porous SnO2 nanowires gas sensors with enhanced sensitivity
Wang et al. A highly sensitive gas sensor based on CuO nanoparticles synthetized via a sol–gel method
Huang et al. Ultrasensitive formaldehyde gas sensor based on Au-loaded ZnO nanorod arrays at low temperature
Sun et al. Metal-organic framework-derived Cr-doped hollow In2O3 nanoboxes with excellent gas-sensing performance toward ammonia
Hoa et al. Effective decoration of Pd nanoparticles on the surface of SnO2 nanowires for enhancement of CO gas-sensing performance
Sui et al. The effect of different crystalline phases of In2O3 on the ozone sensing performance
Liu et al. Enhanced gas sensing characteristics of the flower-like ZnFe2O4/ZnO microstructures
CN102275981B (en) Preparation method of self-substrate SnO2 nanorod array
Sun et al. Synthesis and room-temperature H2S sensing of Pt nanoparticle-functionalized SnO2 mesoporous nanoflowers
Li et al. High-response and low-temperature nitrogen dioxide gas sensor based on gold-loaded mesoporous indium trioxide
Xu et al. Preparation of mesoporous SnO2 by solvothermal method using Stahlianthus involucratus leaves and application to n-butanol sensor
Hou et al. Enhanced triethylamine-sensing properties of hierarchical molybdenum trioxide nanostructures derived by oxidizing molybdenum disulfide nanosheets
Hassan et al. Fabrication and characterization of gas sensor micro-arrays
Munusami et al. Development of high sensitivity LPG and NO2 gas sensor based ZnGa2O4/graphene nanoplates hybrid structure-A novel approach
Bi et al. Synthesis of Rh–SnO2 nanosheets and ultra-high triethylamine sensing performance
Bai et al. Pine dendritic bismuth vanadate loaded on reduced graphene oxide for detection of low concentration triethylamine
Wang et al. Sensing performance for ethylene glycol of hydrothermally self-assembled 3D WO3
CN103713016A (en) Palladium-doped stannic oxide wrapped carbon nano tube as well as preparation method and application of nano tube
Zhang et al. Facile hydrothermal synthesis of mesoporous In2O3 nanoparticles with superior formaldehyde-sensing properties
CN108918633A (en) Pd-SnO2Nanocomposite preparation and the application in hydrogen gas sensor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170503

Termination date: 20181126