CN107033877B - Metal organic frame thin-film material and preparation method thereof for ammonia fluorescence sense under low concentration - Google Patents
Metal organic frame thin-film material and preparation method thereof for ammonia fluorescence sense under low concentration Download PDFInfo
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- CN107033877B CN107033877B CN201710240062.3A CN201710240062A CN107033877B CN 107033877 B CN107033877 B CN 107033877B CN 201710240062 A CN201710240062 A CN 201710240062A CN 107033877 B CN107033877 B CN 107033877B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000000463 material Substances 0.000 title claims abstract description 112
- 239000010409 thin film Substances 0.000 title claims abstract description 65
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010408 film Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- -1 rare earth ion Chemical class 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052594 sapphire Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims description 2
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001449 indium ion Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 238000001917 fluorescence detection Methods 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000012876 topography Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 206010011224 Cough Diseases 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 206010062717 Increased upper airway secretion Diseases 0.000 description 2
- 206010036790 Productive cough Diseases 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 208000026435 phlegm Diseases 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000288140 Gruiformes Species 0.000 description 1
- 208000000616 Hemoptysis Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 201000007100 Pharyngitis Diseases 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 230000002008 hemorrhagic effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 210000003800 pharynx Anatomy 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 206010037833 rales Diseases 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 206010039083 rhinitis Diseases 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 210000001562 sternum Anatomy 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004861 thermometry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
Fluorescence detection metal organic frame thin-film material disclosed by the invention for ammonia under low concentration.Using solvent-thermal method in Al2O3Fabricated in situ MIL-124 thin-film material, the trivalent ion and simple ligand 1 of the IIIA element of this material use rich content, 2,4- benzenetricarboxylic acids synthesize in aqueous solution in substrate, and preparation method is simple, at low cost.By post-decoration method, fluorescence radiation center is introduced on MIL-124 film, europium ion obtains new metal organic frame thin-film material MIL-124Eu3+.Since the material has barish carboxyl, can react with ammonia, so as to cause the fluorescent quenching of europium ion.Test shows this material when ammonia density is 0~1500ppm, and there are linear relationships with ammonia concentration for the fluorescent quenching degree of europium ion, it is achieved that detection limit has actual application prospect down to 26.2ppm to the fluorescence detection of low concentration ammonia.
Description
Technical field
The present invention relates to a kind of metal organic frame thin-film materials and preparation method thereof, in particular for ammonia under low concentration
Metal organic frame thin-film material of fluorescence sense and preparation method thereof.
Background technique
Ammonia has highly important application in modern industry, and in particular with agrotechnical development, nitrogenous fertilizer is in agriculture
Very important effect is played in industry production.In general, the production of nitrogenous fertilizer industrially generallys use nitrogen firstly the need of fixed nitrogen
Gas and hydrogen are produced after obtaining ammonia by high-temperature catalytic, further produce other products.In chemical industry synthesis field, ammonia
Very extensive application is obtained.However, ammonia is a kind of irritative gas with hypotoxicity, a large amount of ammonia are briefly being contacted
After gas, human body mucous membrane will receive serious stimulation, cause to have difficulty in breathing, blindness, and the symptoms such as oedema are even dead when serious.Ammonia
With certain irritation, but when ammonia is lower than 50ppm in ambient concentration, human smell is difficult to perceive depositing for ammonia
When movable in this environment for a long time, ammonia inhalation poisoning can caused, be mainly presented with rhinitis, pharyngitis, laryngalgia, pronunciation are neighed
It is mute.Ammonia enters trachea-bronchial epithelial cell and can cause to cough, cough up phlegm, have blood in phlegm.It can spit blood when serious and pulmonary edema, have difficulty in breathing, cough up
White or hemorrhagic frothy sputum, double lungs are covered with big, medium bubbling rales.Patient has pharynx cusalgia, cough, expectoration or hemoptysis, uncomfortable in chest and breastbone
Pain etc. afterwards.
Fluorescence sense possesses sensitivity relative to traditional chemistry, mechanical pick-up device as a kind of novel detection means
Height, non-cpntact measurement, passive measurement, the advantages such as real-time monitoring.In recent years, metal-organic framework material show gradually its
Advantage above fluorescence sense, since metal-organic framework material is a kind of porous material, large specific surface area can divide with being detected
Son generates biggish area of interaction, enhances its fluorescence detection effect.In the frame material modified after rare earth ion, rare earth due to
It is with the characteristics of luminescence abundant, and stable luminescence, sensitivity of thermometry is high, and it is a kind of very potential glimmering that spatial resolution is high
Light sensing material.Organic ligand with suitable triplet energy level effectively can pass energy to rare earth ion, to be had
The metal-organic framework material of strong characteristic fluorescence transmitting and highly sensitive rear modification.Certainly, the triplet energy level of ligand is easy
It is influenced by extraneous factor, such as the factors such as coordination environment, temperature and humidity, therefore changes ligand to rare earth ion energy transmission
Efficiency realizes the fluorescence detection to specific molecular to change fluorescence intensity.
Fluorescence detection of the metal-organic framework material for gas is research direction emerging in recent years, since metal is organic
Frame material large specific surface area, thus it is also big with the active area of gas, therefore be highly suitable for making gas fluorescence detection.Gold
When belonging to organic framework materials and being used for gas detection, it is thin-film material that when test, which generally requires material, however metal organic frame material
Material is relatively difficult to be self-assembly of thin-film material, existing preparation method more complicated valuableness mostly.
Based on above-mentioned advantage and there are the problem of, metal-organic framework material is a kind of very potential gas detection
Material.But since metal organic frame thin-film material preparation method is complicated, preparation difficulty is big, and this application reported at present is also
Seldom.Therefore, the synthetic method for developing a kind of metal organic frame thin-film material of simple cheap is significantly, together
When, this material also very has realistic meaning to the detection of low concentration ammonia.The material of device and good performance allow this
The potentiality that kind material obtains practical application are very huge.
Summary of the invention
The object of the present invention is to provide a kind of metal organic frame thin-film materials and preparation method thereof, in particular for low dense
Spend the metal organic frame thin-film material and preparation method thereof of lower ammonia fluorescence sense.
Metal organic frame thin-film material for ammonia fluorescence sense under low concentration of the invention, the material are modification
The MIL-124 thin-film material of rare earth ion, and the carboxyl coordination in the rare earth ion and MIL-124.Specifically, be
Al2O3Pass through the MIL-124 thin-film material of fabricated in situ in substrate, the metal ion used is the trivalent ion of Group IIIA, is matched
Body is 1,2,4- benzenetricarboxylic acids, and uses after rare earth ion carries out and modify.
The method of the metal organic frame thin-film material of ammonia fluorescence sense under low concentration of the invention, including following step
It is rapid:
By Al2O3Substrate is cleaned for several times in acetone, water or ethyl alcohol, vertical to be placed in Group IIIA trivalent ion and 1,2,4-BTC
In mixed aqueous solution, is reacted 16~36 hours at 160 DEG C -220 DEG C, obtain MIL-124 film.The MIL-124 film that will be obtained
It is cleaned up, is immersed in containing in rare earth ion methanol solution with organic solvent or deionized water, room temperature is to keeping the temperature 12 at 80 DEG C
~36 hours.Then washed with methanol solution obtain for several times it is thin for the metal organic frame of ammonia fluorescence sense under low concentration
Membrane material.
In the present invention, the Group IIIA trivalent metal ion includes aluminium ion, gallium ion, indium ion and thallium ion.
In the present invention, the rare earth ion include cerium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, terbium ion,
Dysprosium ion, erbium ion, thulium ion and lutetium ion.
In the present invention, the Al2O3Substrate includes α-Al2O3Ceramics, high-purity alumina ceramic, common aluminium oxide ceramics
And porous aluminas.High-purity alumina ceramic is Al in material composition2O3The ceramic material of content >=99.5%.Described is common
Aluminium oxide ceramics is Al in ingredient2O3The lower ceramic material of content, usually less than 99.5%.
In the present invention, the organic solvent typically refers to methanol, ethyl alcohol or N, N '-dimethyl formamide.
Metal organic frame thin-film material based on MIL-124 of the invention has the ammonia under low concentration sensitive fast
It responds fastly, concentration range is 0~1500ppm.Solvent-thermal method used in the present invention is in Al2O3Fabricated in situ in substrate
Metal organic frame thin-film material, this method are compared compared to the methods of LBL self-assembly, nano wire synthesis, have and implement letter
Folk prescription just, it is economic and practical the advantages that.In addition, the metal organic frame thin-film material synthesized in this way is compared to spin-coating method
Have many advantages, such as strong, simple and convenient with substrate caking power.During being modified after to MIL-124 film, by by film material
Material is dipped into the solution containing rare earth ion, and by rare earth ion modification to the film, to introduce the centre of luminescence, method is simple
It is single clear, it modifies high-efficient.
It is the influence of metal organic frame thin-film material of the invention to ammonia within the scope of 0~1500ppm in ammonia concentration
High sensitivity.Its to ammonia have sensitive response reason be the ligand in this frame material can to the rare earth of rear modification from
Son pass can, and when ammonia touches this thin-film material, can react with the carboxyl being not yet coordinated in material, formation-
COONH4, the change of ligand triplet energy level is resulted in, the change of this triplet energy level will affect ligand to rare earth ion
Energy is passed, the fluorescent quenching of rare earth ion is caused.Since other interference gas, such as nitrogen, oxygen, carbon dioxide etc. will not be with
Carboxyl reaction, therefore the interference of other factors will not be generated, while by heating the thin-film material after reacting with ammonia, it is glimmering
Luminous intensity can be restored again, lay the foundation for the practical application of this material.
The specific beneficial effect of the present invention is:
1, the invention proposes a kind of method for preparing MIL-124 metal organic frame thin-film material, this method has
The advantages of easy to operate, economy.
2, it is substrate present invention uses cheap firm alumina material, ensure that the long-term steady of this ammonia gas sensor
It is qualitative, it ensure that its synthesis cost is low, easily prepared feature.
3, it is glimmering to generate specificity to ammonia within the scope of 0~1500ppm to metal organic frame thin-film material of the invention
Photoresponse shows that it has the characteristics that being applied to ammonia detects.
4, metal organic frame thin-film material of the invention can keep good stability before and after ammonia detection, especially
This material, which can be put, to be kept stablizing at least three months in air, and its x-ray diffractogram of powder spectrum can still be closed with rigid
At out when it is corresponding, it was demonstrated that it ensure that its application in ammonia detection with good stability.
5, metal organic frame thin-film material good cycling stability of the invention passes through after multiple ammonia detection recycles
40-100 DEG C after heating 5-10 minute still to the ammonia of low concentration with fluorescence response, this recycling performance guarantee its
Cost is relatively low for commercial applications.
Detailed description of the invention
Fig. 1 is the XRD spectrum of metal organic frame thin-film material of the invention；
Fig. 2 is the Eu 3d energy level and 4d energy level open score of the XPS map of metal organic frame thin-film material of the invention；
Fig. 3 is the stereoscan photograph of metal organic frame thin-film material of the invention；
Fig. 4 is the fluorescence radiation intensity of metal-organic framework material of the invention under different ammonia concentrations.
Specific embodiment
Embodiment 1:
Using inidum chloride and 1,2,4 benzenetricarboxylic acid by the hot method of situ solvent in porous α-Al2O3Gold is synthesized in substrate
Belong to organic frame thin-film material, specific synthetic route is as follows:
1,2, the 4- benzenetricarboxylic acids of the inidum chloride of 0.98g and 0.98g are dissolved in the deionized water of 10mL, then by α-
Al2O3Substrate is cleaned by ultrasonic three times in acetone soln, the clean α-Al that will be obtained2O3Substrate is vertically placed to inidum chloride
In the mixed aqueous solution of trimellitic acid.Above-mentioned solution is placed in 210 DEG C of baking oven, is reacted 24 hours.It is thin by what is obtained
Film takes out, and is respectively cleaned three times with deionized water and DMF, obtains metal organic frame thin-film material.This thin-film material that will be obtained
It is put into the Eu (NO of 0.2mol/L3)3Methanol solution in, at 60 DEG C keep the temperature under stand 48 hours, modified after having obtained europium ion
Metal organic frame thin-film material.
It can be obtained by powder and film XRD x ray diffraction analysis x (such as Fig. 1), MIL-124 (In) thin-film material and MIL-
124Eu3+Thin-film material remains the crystal form of MIL-124 powder.MIL-124 crystal perpendicular to b axis direction have one it is exposed
Carboxyl shows MIL-124Eu by XPS analysis (such as Fig. 2)3+Europium ion in thin-film material just with this exposed carboxyl with
Coordinate bond combines.
We demonstrate the surface topography and cross-section morphology of this thin-film material, it is found that this thin-film material continuity is complete
It is whole, and close combination can be formed with substrate.When the intact MIL-124 film of surface topography is immersed in Eu (NO3)3First
In alcoholic solution two days later, surface topography still maintains intact, cross-section morphology show its still with α-Al2O3Substrate is securely tied
It closes (Fig. 3).
Under the ultraviolet excitation of 298nm, its most strong glow peak is 615nm.It is 0~1500ppm's in ammonia concentration
In range, the intensity of this glow peak linear reduction, the relationship between them can be used such as with the increase of ammonia concentration
Lower formula is fitted:
1-I/I0=0.05172-2.014 × 10-4CNH3
Wherein, I0It is luminous peak intensity of the glow peak of 615nm under air environment, I is the practical strong light at the peak 615nm
Degree, CNH3For the concentration (as unit of ppm) of ammonia, Fig. 4 is seen.
According to IUPAC standard, detection limit LOD=3 σ/K, we calculate to obtain this ammonia detection metal organic frame film
Detection be limited to 26.2ppm.This detection limit is safety post that is relatively low, setting up lower than U.S.'s Occupational Safety and Health Division
Quasi- (50ppm).
The MIL-124Eu after ammonia is detected3+The X ray diffracting spectrum of film can simulate X with the monocrystalline before detection and penetrate
Ray diffraction diagram spectrum is extraordinary to coincide, it was demonstrated that this material is not destroyed in the detection process.Then, we are by this material
It placed in air three months, x-ray diffractogram of powder spectrum remains to remain unchanged, it was demonstrated that this material good stabilization
Property.MIL-124Eu3+Film is after having detected ammonia, and by heating five minutes at 90 DEG C, most strong glow peak can return to it
Green strength, it was demonstrated that it has great actual application prospect with good cyclical stability.
Embodiment 2:
Gold is synthesized in porous oxidation aluminium substrate by the hot method of situ solvent using aluminium chloride and 1,2,4 benzenetricarboxylic acid
Belong to organic frame thin-film material, specific synthetic route is as follows:
1,2, the 4- benzenetricarboxylic acids of the aluminium chloride of 0.98g and 0.98g are dissolved in the deionized water of 10mL, it then will be porous
Alumina substrate is cleaned by ultrasonic three times in acetone soln, and obtained clean porous oxidation aluminium substrate is vertically placed to chlorine
In the mixed aqueous solution for changing aluminium and trimellitic acid.Above-mentioned solution is placed in 210 DEG C of baking oven, is reacted 24 hours.It will obtain
Film take out, respectively cleaned three times with deionized water and DMF, obtain metal organic frame thin-film material.This film that will be obtained
Material is put into the Eu (NO of 0.2mol/L3)3DMF solution in, at 40 DEG C keep the temperature under stand 48 hours, after having obtained europium ion
The metal organic frame thin-film material of modification.
It can be obtained by powder and film XRD x ray diffraction analysis x, MIL-124 (Al) thin-film material and MIL-124Eu3+Film
Material remains the crystal form of MIL-124 powder.MIL-124 crystal is having an exposed carboxyl perpendicular to b axis direction, passes through
XPS analysis shows MIL-124Eu3+Europium ion in thin-film material just with this exposed carboxyl with coordinate bond in conjunction with.
We demonstrate the surface topography and cross-section morphology of this thin-film material, it is found that this thin-film material continuity is complete
It is whole, and close combination can be formed with substrate.When the intact MIL-124 film of surface topography is immersed in Eu (NO3)3First
In alcoholic solution two days later, surface topography still maintains intact, and cross-section morphology shows that it is still firm with porous oxidation aluminium substrate
Consolidation is closed
Under the ultraviolet excitation of 298nm, its most strong glow peak is 615nm.It is 0~1500ppm's in ammonia concentration
In range, the intensity of this glow peak can with the increase of ammonia concentration linear reduction.
The MIL-124Eu after ammonia is detected3+The X ray diffracting spectrum of film can simulate X with the monocrystalline before detection and penetrate
Ray diffraction diagram spectrum is extraordinary to coincide, it was demonstrated that this material is not destroyed in the detection process.Then, we are by this material
It placed in air three months, x-ray diffractogram of powder spectrum remains to remain unchanged, it was demonstrated that this material good stabilization
Property.MIL-124Eu3+Film is after having detected ammonia, and by heating five minutes at 90 DEG C, most strong glow peak can return to it
Green strength, it was demonstrated that it is with good cyclical stability.
Embodiment 3:
Gold is synthesized on common aluminium oxide ceramics by the hot method of situ solvent using indium nitrate and 1,2,4 benzenetricarboxylic acid
Belong to organic frame thin-film material, specific synthetic route is as follows:
1,2, the 4- benzenetricarboxylic acids of the indium nitrate of 0.98g and 0.98g are dissolved in the deionized water of 10mL, it then will be common
Aluminium oxide ceramics substrate is cleaned by ultrasonic three times in acetone soln, vertically by obtained clean common alumina ceramic-base bottom
It is placed in the mixed aqueous solution of indium nitrate and trimellitic acid.Above-mentioned solution is placed in 210 DEG C of baking oven, reaction 24 is small
When.Obtained film is taken out, is respectively cleaned three times with deionized water and DMF, obtains metal organic frame thin-film material.It will obtain
This thin-film material be put into the Eu (NO of 0.2mol/L3)3Methanol solution in, at 80 DEG C keep the temperature under stand 48 hours, obtain
The metal organic frame thin-film material modified after europium ion.
It can be obtained by powder and film XRD x ray diffraction analysis x, MIL-124 (In) thin-film material and MIL-124Eu3+Film
Material remains the crystal form of MIL-124 powder.MIL-124 crystal is having an exposed carboxyl perpendicular to b axis direction, passes through
XPS analysis shows MIL-124Eu3+Europium ion in thin-film material just with this exposed carboxyl with coordinate bond in conjunction with.
Under the ultraviolet excitation of 298nm, its most strong glow peak is 615nm.It is 0~1500ppm's in ammonia concentration
In range, the intensity of this glow peak can with the increase of ammonia concentration linear reduction, the detection of ammonia is limited to
26.2ppm, the safety standard set up lower than U.S.'s Occupational Safety and Health Division (50ppm).
The MIL-124Eu after ammonia is detected3+The X ray diffracting spectrum of film can simulate X with the monocrystalline before detection and penetrate
Ray diffraction diagram spectrum is extraordinary to coincide, it was demonstrated that this material is not destroyed in the detection process.Then, we are by this material
It placed in air three months, x-ray diffractogram of powder spectrum remains to remain unchanged, it was demonstrated that this material good stabilization
Property.MIL-124Eu3+Film is after having detected ammonia, and by heating five minutes at 90 DEG C, most strong glow peak can return to it
Green strength, it was demonstrated that it has very big actual application prospect with good cyclical stability.
Embodiment 4:
Using gallium chloride and 1,2,4 benzenetricarboxylic acid by the hot method of situ solvent in porous α-Al2O3Gold is synthesized in substrate
Belong to organic frame thin-film material, specific synthetic route is as follows:
1,2, the 4- benzenetricarboxylic acids of the gallium chloride of 0.98g and 0.98g are dissolved in the deionized water of 10mL, then by α-
Al2O3Substrate is cleaned by ultrasonic three times in acetone soln, the clean α-Al that will be obtained2O3Substrate is vertically placed to gallium chloride
In the mixed aqueous solution of trimellitic acid.Above-mentioned solution is placed in 210 DEG C of baking oven, is reacted 24 hours.It is thin by what is obtained
Film takes out, and is respectively cleaned three times with deionized water and DMF, obtains metal organic frame thin-film material.This thin-film material that will be obtained
It is put into the Eu (NO of 0.2mol/L3)3DMF solution in, at 60 DEG C keep the temperature under stand 48 hours, modified after having obtained europium ion
Metal organic frame thin-film material.
It can be obtained by powder and film XRD x ray diffraction analysis x, MIL-124 (Ga) thin-film material and MIL-124Eu3+Film
Material remains the crystal form of MIL-124 powder.MIL-124 crystal is having an exposed carboxyl perpendicular to b axis direction, passes through
XPS analysis shows MIL-124Eu3+Europium ion in thin-film material just with this exposed carboxyl with coordinate bond in conjunction with.
We demonstrate the surface topography and cross-section morphology of this thin-film material, it is found that this thin-film material continuity is complete
It is whole, and close combination can be formed with substrate.When the intact MIL-124 film of surface topography is immersed in Eu (NO3)3First
In alcoholic solution two days later, surface topography still maintains intact, cross-section morphology show its still with α-Al2O3Substrate is securely tied
It closes
Under the ultraviolet excitation of 298nm, its most strong glow peak is 615nm.It is 0~1500ppm's in ammonia concentration
In range, the intensity of this glow peak can with the increase of ammonia concentration linear reduction.
The MIL-124Eu after ammonia is detected3+The X ray diffracting spectrum of film can simulate X with the monocrystalline before detection and penetrate
Ray diffraction diagram spectrum is extraordinary to coincide, it was demonstrated that this material is not destroyed in the detection process.Then, we are by this material
It placed in air three months, x-ray diffractogram of powder spectrum remains to remain unchanged, it was demonstrated that this material good stabilization
Property.MIL-124Eu3+Film is after having detected ammonia, and by heating five minutes at 90 DEG C, most strong glow peak can return to it
Green strength, it was demonstrated that it is with good cyclical stability.
Claims (7)
1. a kind of purposes of metal organic frame thin-film material, which is characterized in that the metal organic frame thin-film material is modification
The MIL-124 thin-film material of rare earth ion, and the carboxyl coordination in the rare earth ion and MIL-124, the material be used for
The detection of ammonia, the material heat through 40-100 DEG C after completing an ammonia detection, can be repeated for ammonia next time
Detection.
2. purposes as described in claim 1, which is characterized in that 5-10 minutes a length of when heating.
3. purposes as described in claim 1, which is characterized in that the preparation method of the metal organic frame thin-film material,
The following steps are included:
By Al2O3Substrate cleans up, and vertical be placed in contains Group IIIA trivalent metal ion and 1, in 2,4-BTC aqueous solution,
160oC-220 oC reacts 16 ~ 36 hours, obtains MIL-124 film；By obtained MIL-124 film using organic solvent or
Deionized water cleaning, is immersed in the methanol solution containing rare earth ion, room temperature to 80o12 ~ 36 hours are kept the temperature under C, after taking-up
It is washed with methanol solution, obtains the metal organic frame thin-film material for ammonia fluorescence sense under low concentration.
4. purposes as claimed in claim 3, which is characterized in that the Group IIIA trivalent metal ion includes aluminium ion, gallium
Ion, indium ion or thallium ion.
5. purposes as claimed in claim 3, which is characterized in that the rare earth ion be cerium ion, neodymium ion, samarium ion,
Europium ion, gadolinium ion, terbium ion, dysprosium ion, erbium ion, thulium ion or lutetium ion.
6. purposes as claimed in claim 3, which is characterized in that the Al2O3Substrate includes α-Al2O3Ceramic, high pure zirconia
Aluminium ceramics, common aluminium oxide ceramics and porous aluminas.
7. purposes as claimed in claim 3, which is characterized in that the organic solvent refers to methanol, ethyl alcohol or N, N '-two
Methylformamide.
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