CN105510395A - Metal oxide-metal-organic frameworks (MOX@MOFs) nanometer core-shell structure one-dimensional array as well as preparation method and application thereof - Google Patents
Metal oxide-metal-organic frameworks (MOX@MOFs) nanometer core-shell structure one-dimensional array as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an MOX@MOFs (metal oxide-metal-organic frameworks) nanometer core-shell structure one-dimensional array film which is characterized in that the film thickness is 2 to 4 micrometers, and the film is formed by a one-dimensional MOX@MOFs core-shell structure, wherein the diameter of a core MOX nanowire is 50 to 100nm, the thickness of a shell MOFs can be adjusted between 1nm to 200nm, metal nodes and organic chains of the MOFs can be adjusted. A typical preparation method comprises the steps of setting an MOX face of a ZnO one-dimensional array film downwards, adding into a mixed solution of water in which zinc salt, cobalt salt and organic ligands are dissolved and DMF, sealing a reaction still, then heating for reacting, after reacting, washing the surface of a compound array film, and drying the film in the air. The MOX@MOFs core-shell structure one-dimensional array film provided by the invention has excellent gas-sensitive property, not only can humidity interference be selectively eliminated, but also the working temperature can be reduced and the sensitivity can be improved through a Co catalysis. Meanwhile, the film also has the advantages that the method is simple, and the cost is low.
Description
Technical field
The present invention relates to gas sensor field, particularly relate to metal oxide (MOX) thermometal organic framework materials (MOFs) nano-core-shell structure one-dimensional array film of a kind of detection volatile organic compounds gas sensor for the interference of selectivity eliminating humidity and its production and use.
Background technology
Volatile organic compounds (volatileorganiccompounds, VOCs) refers at normal temperatures, the various organic compounds of boiling point 50 DEG C-260 DEG C.VOCs by its chemical constitution, can be further divided into: alkanes, aromatic hydrocarbons, ester class, aldehydes and other etc.What identified at present has kind more than 300.Modal have acetone, benzene,toluene,xylene, styrene, triclene, methenyl choloride, trichloroethanes, diisocyanate (TDI), two isocyanide toluene esters etc.Be easy to cause acute poisoning during Volatile Organic Compounds in Indoor Air excessive concentration, the lighter there will be headache, dizziness, cough, Nausea and vomiting or is dead drunk liquor-saturated shape; Severe one there will be hepatotoxicity and even goes into a coma very soon, and what have also may be in peril of one's life.For above-mentioned reasons, VOCs is detected quickly and accurately seem very important.
Metal oxide (metaloxide, MOX) gas sensor has the advantage such as low price, long working life, easily production in enormous quantities, but, although MOX gas sensor obtains certain achievement in sensitivity and working temperature, and existing part bibliographical information can produce certain selectivity to certain class gas according to special properties (as p-n junction conversion, gas polarity etc.), but the technology of universality is lacked always to the selective enumeration method (selectivity) of pure gas.Therefore, develop a kind of easy, cheap, selectivity to get well and the high sensitivity high selectivity gas sensitive of the universality that possesses skills, detect gaseous species and simplification and alternative electronic nose in expansion alternative significant, the high humility interference involved by the practical applications such as solution Smart Home, intelligent automobile, wearable device, accurate factory building and multi-component complex atmosphere cross response problem provide new thinking.
Metal-organic framework materials (Metal – OrganicFrameworks, MOFs) is the crystalline state porosint with regular network structure that a class is self-assembled into by the coordination between them, supermolecular mechanism, hydrogen bond etc. by inorganic node (metallic ion or metal cluster) and organic ligand.This material has superelevation porosity (can reach 90%), specific surface area is (the highest more than 10000m
2/ g) and abundant topological structure, can provide abundant gas absorption and reaction site, controllability, Scalability that its duct orientation, pore-size and inwall is modified make this material have potential using value in gas-selectively adsorptive separation.
The existing a small amount of report of research of MOX superficial growth MOFs layer, current MOX-MOFs compound substance just tentatively achieves the coated of MOX surface MOFs layer in preparation.But, realize the controlled epitaxial growth of the thickness of thermometal compound MOFs film, duct orientation and aperture wall ornamentation on MOX surface, and systematically study its preparation displine aspect and there is no report.
Summary of the invention
Gas sensitive is the core of gas sensor, and its performance determines the performance of gas sensor.MOFs is wrapped in highly sensitive MOX material outer layer, after forming compound, the powerful gas by MOFs selects separating power, is expected to the air-sensitive selectivity keeping MOX high sensitivity simultaneously to promote MOX material.Meanwhile, as a class formation important in MOFs, the catalytic capability of the Co system ZIFs of imidazole radicals part has the potentiality promoting the sensitivity of MOX cryogenic gas, but thermally-stabilised poor (air atmosphere, 240-300 DEG C loses crystal formation or decomposition); Although Zn system ZIFs does not have obvious low-temperature catalyzed ability, there is good thermal stability (air atmosphere, minimum steady fixed temperature reaches 330 DEG C); The two and composite solid solution thereof have identical crystal structure and close hydrophobic ability, and CoZn compound ZIFs can realize good hydrophobicity (moisture-resistant degree ability) and thermal stability (minimum reach 330 DEG C) simultaneously.MOX-MOFs composite nano materials by conjunction with the advantage in each comfortable sensitivity and selectivity, thus solves the problem of current MOX gas sensitive poor selectivity, prepares high selectivity high sensitivity chemistry resistance-type gas sensor.
The present inventor, through a series of exploration, by solwution method, by regulation and control reaction conditions, at MOX nanowire surface epitaxial growth CoZn mixing ZIF film, obtain a kind of adjustable by metal ratio, imidazole radicals part is variable, thickness and the coated MOXMOFs nano-core-shell structure one-dimensional nano-array film of the controlled compound MOF layer of aperture wall ornamentation.This material with the ZnO nano-wire of 50-100nm for core MOX conductive network and high sensitivity gas sensitive, with the MOFs shell of CoZn mixing ZIF film for selectivity moisture-resistant degree material, the Co element of CoZn mixing ZIF film near MOX surface has low-temperature catalyzed ability simultaneously, further reduction air-sensitive working temperature and lifting sensitivity, make this material possess extremely sensitive low temperature VOCs detectability and optionally promote its anti-psychometric performance.
MOXMOFs nano-core-shell structure one-dimensional nano-array film provided by the invention, the overall one-dimensional nano-array being made up of nucleocapsid structure MOX outer cladding compound MOFs, single MOX nanowire diameter is at 50-100nm, compound ZIFs shell thickness is adjustable at 1-200nm, in compound ZIFs shell, Co, Zn ratio is controlled, and organic ligand type is adjustable.
In some preferred preparation methods, described MOXMOFs nano-core-shell structure one-dimensional nano-array film, described MOX is ZnO, and described MOFs is the organic ligand of Co, Zn thermometal mixing ZIFs of imidazole radicals part, described ZIFs is imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 4-methylimidazole, 4,5-methylimidazole, 2,4,5-tri-methylimidazolium and benzimidazole.
The present invention also provides the preparation method of described MOXMOFs nano-core-shell structure one-dimensional nano-array film.Typical preparation method is, take zinc salt cobalt salt add water and DMF be dissolved in reactor, proportionally add imidazole radicals part to stir, form clear solution, the MOX of inculating crystal layer method MOX one-dimensional array film of hydrothermal/solvent heat growth on sapphire/polycrystal alumina sheet is faced down, puts into solution, after sealed reactor, add thermal response, react complete composite array film surface is rinsed well, dry in atmosphere.
In some preferred preparation methods, described zinc salt is zinc acetate, zinc sulfate or zinc chloride, and described cobalt salt is cobalt acetate, cobaltous sulphate or cobalt chloride.
In some preferred embodiments, the organic ligand of described ZIF series MOFs is imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 4-methylimidazole, 4,5-methylimidazole, 2,4,5-tri-methylimidazolium or benzimidazole.
In some preferred embodiments, described zinc salt: cobalt salt mol ratio is 0:1-3:1.
In some preferred embodiments, the temperature of reaction of described hydro-thermal reaction is 25-125 DEG C, and the reaction time is 0.5-36h.
In some preferred embodiments, the volume ratio of described water and DMF is 0:16 – 3:1.
The present invention also provides the purposes of described MOXMOFs nano-core-shell structure one-dimensional nano-array film, the application of described MOXMOFs nano-core-shell structure one-dimensional array film in volatile organic compounds gas sensor, described MOXMOFs nano-core-shell structure one-dimensional array film is as gas sensitive, described MOX is as main body air-sensitive responsive materials, and described MOFs is as catalysis and gas adsorption and separation material.。
The present invention passes through the hot method of hydrothermal/solvent at the heat-staple hydrophobic CoZn compound ZIFs layer of MOX nanowire surface epitaxial growth, hydrone can selectivity foreclose by CoZn compound ZIFs shell on the one hand, object gas absorption can be sent to MOX surface again, realize the response of selectivity moisture-resistant air-sensitive; The low-temperature catalyzed ability of the Co element of interface on the other hand, promotes the low temperature sensitivity of MOX further, realizes the high-sensitivity detection (260 DEG C of the bests) under low temperature; The two is comprehensive, makes MOXMOFs nano-core-shell structure one-dimensional array film provided by the invention have selectivity humidity-proof ability and low-temperature high-sensitivity to volatile organic compounds simultaneously.The present invention simultaneously also has the advantage that method is simple, with low cost, be easy to popularization.
Accompanying drawing explanation
Accompanying drawing is that MOXMOFs nano-core-shell structure one-dimensional array film sections SEM prepared by the present invention schemes and the TEM of single nanometer rods schemes (take methylimidazole as the ZnOZIF-CoZn of part be example).
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described.
The preparation of MOXMOFs nano-core-shell structure one-dimensional array film: the MOX of inculating crystal layer method MOX one-dimensional array film of hydrothermal/solvent heat growth on sapphire/polycrystal alumina sheet is faced down, add in the water and DMF mixed solution being dissolved with slaine and organic ligand, thermal response is added after sealed reactor, react complete composite array film surface is rinsed well, dry in atmosphere.
The sign of MOXMOFs nano-core-shell structure one-dimensional array film: sample topography adopts scanning electron microscope (SEM, JEOLJSM-6700F) and transmission electron microscope (TEM, JEOLJEM-2100) to observe.
MOXMOFs nano-core-shell structure one-dimensional array film gas-sensitive performance test: the substrate of gas sensor adopts the wide 8mm thickness of long 10mm to be (001) crystal face sapphire sheet of 0.6mm, then the Au line that conductive silver paste fixes two conductive tests is coated at two ends, the middle insulation position not being coated with conductive silver paste is gas sensitive test main region, takes out and room temperature cooling after 550 DEG C of calcining 30min.Can directly as gas sensor according to the MOXMOFs nano-core-shell structure one-dimensional array film grown on above-mentioned substrate that preparation method obtains.After prepared by gas sensor, at 260 DEG C, stablize 20h.Tubular furnace provides constant working temperature for gas sensor, the VOCs gas of certain concentration is then realized by mass flowmeter (CS-200C, Beijing Qixing Huachuang Electronics Co., Ltd) control VOCs Standard Gases (synthesis of air dispersion) and the ratio of synthesis of air.Charge flow rate is constant is 600ml/min, and operating voltage is 5V, and electric current collection is completed (Keithley2602BSourcemeter, KeithleyInstrumentInc., USA) by digital electronic ammeter.Response (R, response) is defined as sensor resistance (R in air
air) and detect resistance (R in gas
gas) ratio, i.e. R=R
air/ R
gas– 1.Be defined as sensor resistance response/release time respectively and arrive/return to the time that 90%/10% each leisure is detected saturated resistance value in gas and synthesis of air.
The film growth of inculating crystal layer method MOX one-dimensional array:
ZnO one-dimensional array film: substrate after water, acetone, EtOH Sonicate cleaning-drying, with reference to Greene etc.
[1]method, by 0.005MZnAc
2ethanolic solution drips on (3-5 time) substrate repeatedly, and after 10s, nitrogen dries up, and 350 DEG C of heating 20min in atmosphere after circulation 3-5 time, obtain ZnO inculating crystal layer.Array growth is with reference to Kang etc.
[2], the ZnAc of the volumetric molar concentrations (0.01M) such as employing
2with HMT solution 80ml, pour in 100mL teflon (Teflon) liner, seed crystal substrate is vertically immersed in solution, after the good reactor of screwing hermetic, put into drying box, 95 DEG C of hydro-thermals 16 hours.After having reacted, take out substrate, in air, spend deionized water for several times, drying at room temperature.
Embodiment 1
Take zinc chloride and cobalt chloride (Zn:Co=1:1, total mol concentration 0.86mM) add 2.5mL water and 13.5mLDMF is dissolved in reactor, add glyoxal ethyline (30.4mM) to stir, form clear solution,, put into solution by the ZnO one-dimensional array pellicular front of inculating crystal layer method hydrothermal growth in sapphire sheet down, 60 DEG C of reaction 2h after sealed reactor, react complete composite array film surface is rinsed well, dry in atmosphere.
Embodiment 2
Take zinc nitrate and cobalt nitrate (Zn:Co=0:1, total mol concentration 0.86mM) add 0mL water and 16mLDMF is dissolved in reactor, add glyoxal ethyline (76.0mM) to stir, form clear solution, by the TiO of inculating crystal layer method solvent thermal growth in sapphire sheet
2one-dimensional array pellicular front, puts into solution down, and after sealed reactor, 25 DEG C of reaction 12h, react complete and rinsed well by composite array film surface, dry in atmosphere.
Embodiment 3
Take zinc chloride and cobalt chloride (Zn:Co=3:1, total mol concentration 0.86mM) add 4mL water and 12mLDMF is dissolved in reactor, add imidazoles (30.4mM) to stir, form clear solution, by the SnO of inculating crystal layer method hydrothermal growth on polycrystalline alumina ceramic sheet
2one-dimensional array pellicular front, puts into solution down, and after sealed reactor, 120 DEG C of reaction 0.5h, react complete and rinsed well by composite array film surface, dry in atmosphere.
Embodiment 4
Take zinc nitrate and cobalt nitrate (Zn:Co=1:3, total mol concentration 8.60mM) add 4mL water and 12mLDMF is dissolved in reactor, add 2-ethyl imidazol(e) (76.0mM) to stir, form clear solution,, put into solution by the ZnO one-dimensional array pellicular front of inculating crystal layer method hydrothermal growth in sapphire sheet down, 60 DEG C of reaction 12h after sealed reactor, react complete composite array film surface is rinsed well, dry in atmosphere.
Embodiment 5
Take zinc acetate and cobalt acetate (Zn:Co=3:1, total mol concentration 0.86mM) add 4mL water and 12mLDMF is dissolved in reactor, add benzimidazole (76.0mM) to stir, form clear solution, by the SnO of inculating crystal layer method hydrothermal growth on polycrystalline alumina ceramic sheet
2one-dimensional array pellicular front, puts into solution down, and after sealed reactor, 120 DEG C of reaction 3h, react complete and rinsed well by composite array film surface, dry in atmosphere.
Embodiment 6
Take zinc acetate and cobalt acetate (Zn:Co=3:1, total mol concentration 0.86mM) add 0mL water and 12mLDMF is dissolved in reactor, add 4,5-methylimidazole (76.0mM) stirs, and forms clear solution, by the ZnO one-dimensional array pellicular front of inculating crystal layer method hydrothermal growth on polycrystalline alumina ceramic sheet down, put into solution, after sealed reactor, 125 DEG C of reaction 12h, react complete and are rinsed well by composite array film surface, dry in atmosphere.
By the MOXMOFs nano-core-shell structure one-dimensional array films test air-sensitive performance prepared.For ZnO coated 2-5nmCoZn mixing ZIF (glyoxal ethyline), table 1 compared for anti-psychometric performance and the response of acetone air-sensitive of coated front and back, demonstrate this composite air-sensitive material and not only there is good low temperature air-sensitive response, and there is good anti-psychometric performance (0% is respectively to humidity, 10%, 30%, 50%, after the response R of the 10ppm acetone of 70% and 90% asks standard variance, with the deviation percent of mean value, i.e. anti-humidity=stdev. (all)/average (all) × 100%).Because ZnOZIF-67 sample thermal stability is too poor, (namely 220 DEG C decomposed, slaine is cobalt salt only), ZnOZIF-8 sample does not have the low-temperature catalyzed of Co to cause 200-300 DEG C of response too low (slaine is Zn salt only), is not thus suitable for performance comparison.
The response of the different sample of table 1 and moisture-resistant degree performance comparison
List of references:
[1]Greene,L.E.,Law,M.,Tan,D.H.,etc.GeneralroutetoverticalZnOnanowirearraysusingtexturedZnOseeds[J].NanoLett,2005,5(7):1231-1236.
[2]Kang,B.S.,Pearton,S.J,Ren,F.Lowtemperature(<100℃)patternedgrowthofZnOnanorodarraysonSi[J].Appl.Phys.Lett.,2007,90:083104.
Claims (10)
1. a MOXMOFs nano-core-shell structure one-dimensional array film, it is characterized in that, monolithic film membrane thickness 2-4 μm, array film is made up of one dimension MOXMOFs nano-core-shell structure, wherein core MOX nanowire diameter 50-100nm, shell MOFs thickness is adjustable from 1nm to 200nm, the metal node of shell MOFs and organic chain adjustable.
2. MOXMOFs nano-core-shell structure one-dimensional array film according to claim 1, it is characterized in that, described MOX is ZnO, and described MOFs is Co, Zn thermometal mixing MOFs based on imidazole radicals part.
3. a preparation method for MOXMOFs nano-core-shell structure one-dimensional array film described in claim 1 or 2, is characterized in that, comprise the following steps:
The MOX of inculating crystal layer method MOX one-dimensional array film of hydrothermal/solvent heat growth on sapphire/polycrystal alumina sheet is faced down, add in the water and DMF mixed solution being dissolved with zinc salt, cobalt salt and organic ligand, thermal response is added after sealed reactor, react complete composite array film surface is rinsed well, dry in atmosphere.
4. preparation method according to claim 3, is characterized in that, described zinc salt is zinc acetate, zinc sulfate or zinc chloride, and described cobalt salt is cobalt acetate, cobaltous sulphate or cobalt chloride.
5. preparation method according to claim 3, is characterized in that, described organic ligand is imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 4-methylimidazole, 4,5-methylimidazole, 2,4,5-tri-methylimidazolium and benzimidazole.
6. preparation method according to claim 3, is characterized in that, the temperature of reaction of described solvent thermal reaction is 25-120 DEG C, and the reaction time is 0.5-36h.
7. preparation method according to claim 3, is characterized in that, the volume ratio of water and DMF is 0: 16-3: 1.
8. preparation method according to claim 3, is characterized in that, described zinc salt: cobalt salt mol ratio is 0:1-3:1.
9. the application of MOXMOFs nano-core-shell structure one-dimensional array film in volatile organic compounds gas sensor described in claim 1 or 2.
10. the application of MOXMOFs nano-core-shell structure one-dimensional array film in gas sensitive described in claim 1 or 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109317067A (en) * | 2018-11-05 | 2019-02-12 | 国家纳米科学中心 | A kind of nucleocapsid heterojunction structure composite material and preparation method |
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| CN109853030A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of metallic oxide nanocrystal and its preparation method and application of metal organic frame film coated |
| CN111044582A (en) * | 2019-12-04 | 2020-04-21 | 中国工程物理研究院化工材料研究所 | Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof |
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| CN115060767A (en) * | 2022-07-13 | 2022-09-16 | 安徽维纳物联科技有限公司 | Preparation method of gas-sensitive material for food safety detection, prepared gas-sensitive material and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001547A (en) * | 2014-06-16 | 2014-08-27 | 上海师范大学 | Preparation method and application of environment-friendly core shell one-dimensional nanometer copper wire-organic metallic framework ZIF-8 composite catalyst |
| CN104084238A (en) * | 2014-07-08 | 2014-10-08 | 大连理工大学 | ZIF-8 film-coated Pd/ZnO core-shell catalyst and preparation method thereof |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN104370820A (en) * | 2013-08-13 | 2015-02-25 | 中国科学院大连化学物理研究所 | Preparation method and applications of porous metal organic skeleton material |
-
2015
- 2015-12-13 CN CN201510923955.9A patent/CN105510395B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370820A (en) * | 2013-08-13 | 2015-02-25 | 中国科学院大连化学物理研究所 | Preparation method and applications of porous metal organic skeleton material |
| CN104001547A (en) * | 2014-06-16 | 2014-08-27 | 上海师范大学 | Preparation method and application of environment-friendly core shell one-dimensional nanometer copper wire-organic metallic framework ZIF-8 composite catalyst |
| CN104084238A (en) * | 2014-07-08 | 2014-10-08 | 大连理工大学 | ZIF-8 film-coated Pd/ZnO core-shell catalyst and preparation method thereof |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| FEI KE ET.AL.: "Fe3O4@MOFcore–shell magnetic microspheres with a designable metal–organic framework shell", 《J. MATER. CHEM.》 * |
| LIANGCAN HE ET.AL.: "Core–Shell Noble-Metal@Metal-Organic-Framework Nanoparticles with Highly Selective Sensing Property", 《ANGEW. CHEM. INT. ED.》 * |
| WEN-WEN ZHAN ER.AL.: "Semiconductor@Metal−Organic Framework Core−ShellHeterostructures: A Case of ZnO@ZIF 8 Nanorods with SelectivePhotoelectrochemical Response", 《 J. AM. CHEM. SOC.》 * |
| 张红卫 等: "具有核壳结构的金属有机框架纳米材料的研究进展", 《上海师范大学学报( 自然科学版)》 * |
| 王仕英 等: "核壳型纳米金属氧化物复合材料研究进展", 《化工进展》 * |
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