CN109467567A - A kind of porphyrin naphthalene cyanines double-level-metal complex and its preparation method and application - Google Patents
A kind of porphyrin naphthalene cyanines double-level-metal complex and its preparation method and application Download PDFInfo
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 230000004044 response Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 6
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 78
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 57
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 238000007689 inspection Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract 1
- 238000001548 drop coating Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 14
- 238000005452 bending Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010023379 Ketoacidosis Diseases 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011309 routine diagnosis Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The present invention relates to a kind of porphyrin naphthalene cyanines double-level-metal complexs and its preparation method and application, belong to organic semiconducting materials technical field of chemistry.The present invention has synthesized La (TBPP) (TBNc) for the first time, and has prepared La (TBPP) (TBNc) film for the first time.La (TBPP) (TBNc) film is will to prepare in La (TBPP) (TBNc) solution drop coating to ITO/PET interdigital electrode and using solvent vapo(u)r annealing method.Preparation method of the invention is simple and effective, experimentation is easily controllable.The present invention obtains a kind of sensor element that air-sensitive performance is excellent, at room temperature, has the advantages that fast good responsiveness, high sensitivity, response and recovery time, favorable reproducibility, selectivity are strong to the acetone of 1-800ppm；And preparation is simple, and production cost is low, and it is environmentally protective, it can be used for the detection to low concentration acetone in environment；It is a kind of flexible member.
Description
Technical field
The present invention relates to a kind of porphyrin naphthalene cyanines double-level-metal complexs and its preparation method and application, belong to organic semiconductor
Material chemistry technical field.
Background technique
Acetone is a kind of industrial and widely used organic solvent in laboratory, has height inflammability, Long Term Contact can be right
Human health causes damages；Meanwhile a kind of product of acetone or animal body metabolism, concentration can reflect organism
Body condition.It can be used for diagnosing and monitoring diabetes and ketoacidosis disease；In the food industry, for monitoring flesh of fish group food institute
The concentration for releasing acetone gas, determines its freshness, and the monitoring of acetone has great importance.Therefore, for disease early stage
Next-generation medical technology is likely to become with the acetone gas sensor of routine diagnosis.Specifically, as detection, monitoring and offer
The important component of related mankind warning, chemical impedance sensor because of simple operations, production cost is low and miniaturization and by
Many concerns.But new equipment must overcome many challenging defects.And the collection of they and the wearable platform of intelligence
At.These new equipments should be light-weight, mechanical flexible, and being capable of longtime running.
In the past few decades, metal oxide semiconductor nano material, such as ZnO, WO3, SnO2And TiO2It is studied
As the chemical type gas sensor sensed for acetone.It significant is lacked however, elevated operating temperature (220-350 DEG C) is one
Point greatly limits this application based on the sensor of metal oxide semiconductor in gas sensing field.Have
Machine semiconductor material, especially Porphyrin and its derivative, numerous characteristics needed for having high-performance chemical sensor are (for example, good
Good electric conductivity, flexibility, low temperature machinability, the chemical property etc. that can easily be accommodated), other sensors can be supplemented not
Foot.Therefore, organic semiconducting materials are synthesized and study its air-sensitive performance with important practical value meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of porphyrin naphthalene cyanines double-level-metal complexs and its preparation method and application.
The invention adopts the following technical scheme:
A kind of porphyrin naphthalene cyanines double-level-metal complex, abbreviation La (TBPP) (TBNc), structural formula, as shown in formula 1:
The preparation method of above-mentioned porphyrin naphthalene cyanines double-level-metal complex, comprising the following steps:
(1) by H2(TBPP), [La (acac)3]·nH2O and 6- tert-butyl -2,3- dinitrile naphthalene is added to equipped with n-octyl alcohol
In the round-bottomed flask of 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, reaction mixture is flowed back 18-20 under a nitrogen
Hour, reaction temperature is 180-190 DEG C；H2(TBPP), [La (acac)3]·nH2O and 6- tert-butyl -2,3- dinitrile naphthalene
Molar ratio is 1.0:2.0-3.0:8.0-9.0；H2(TBPP) and the molar ratio of n-octyl alcohol is 1.0:500.0-550.0；H2(TBPP)
Molar ratio with 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0] is 1.0:6.0-8.0；
(2) after the reaction was completed, n-octyl alcohol is removed at reduced pressure conditions, it is cooling；With the mixed solution of methylene chloride and methanol
Make eluant, eluent to be purified with silicagel column；The volume ratio of methylene chloride and methanol solution is 100:6；
(3) in order to which the purity for improving product uses gained La (TBPP) (TBNc) in step (2) plus chloroform dissolution
Methanol is recrystallized；The volume ratio of chloroform and methanol is 1:6-8；Wherein, chloroform is as readily soluble solvent and methanol
As poor solvent.
The porphyrin naphthalene cyanines double-level-metal complex La (TBPP) (TBNc) is preparing the application in acetone gas sensor.
It is a kind of for detecting the gas sensor element of acetone, including ITO/PET substrate and interdigital electrode, the interdigital electricity
Pole etches in ITO/PET substrate, has La (TBPP) (TBNc) film on interdigital electrode surface.
It is described for detect acetone gas sensor element the preparation method comprises the following steps:
(1) preparation of ITO/PET interdigital electrode: taking ITO/PET material, cleans, dry, then carves ITO/PET substrate
Erosion is ITO interdigital electrode (for the prior art)；
The ITO/PET interdigital electrode handles concrete mode are as follows: ITO/PET interdigital electrode is put into beaker, in ultrasound
It is cleaned by ultrasonic respectively with toluene, acetone, dehydrated alcohol, distilled water in wave washer, every kind of solvent cleans three times, and five points every time
Then clock is dried in vacuo, spare；
(2) La (TBPP) (TBNc) is dissolved with good solvent, the solution of 0.006-0.009mol/L is made；The good solvent
For chloroform or methylene chloride；
(3) solution that step (2) prepares carefully is dripped and is placed in the closed container with vacuum valve in cleaned
In the interdigital electrode in face, while in the closed container with vacuum valve that the beaker for filling chloroform is also put into；
(4) closed container is closed, cock is opened, vacuumizes 3-5 times, each 5-10min, cut-out tap is full of steam
Drying for standby after standing 18-24h, is taken out in closed container space with vacuum valve, i.e., acquisition interdigital electrode surface is La
(TBPP) the metalloporphyrin naphthalene cyanines complex gas sensor element of (TBNc) film.
Further, La (TBPP) (TBNc) solution is added drop-wise to above interdigital electrode using dropper in step (3), is added dropwise
Amount is 0.25-0.50mL, while guaranteeing that La (TBPP) (TBNc) solution does not spill over interdigital electrode.In order to obtain certain pattern,
La (TBPP) (TBNc) film of even distribution should keep the closed container position with vacuum valve motionless, can reduce La in this way
(TBPP) formation of (TBNc) film and disorderly arranged.Therefore, in the present invention, interdigital electrode is put into the close of vacuum valve
After closing in container, then to the mode of dropwise addition La (TBPP) (TBNc) solution above interdigital electrode, it can reduce to the greatest extent to pattern shape
At the disturbance of process.
Further, in step (3), 30-100mL chloroform is housed in beaker.
Further, drying temperature is 50-60 DEG C in step (4), drying time 12-24h.
La obtained by the present invention (TBPP) (TBNc) film gas sensor element, the wherein La on interdigital electrode surface
(TBPP) (TBNc) film is pleated structure, and fold amplitude is 5-10 μm.
La obtained by the present invention (TBPP) (TBNc) film gas sensor element has good gas sensing property to acetone
Can: (1) sensor sheet based on La (TBPP) (TBNc) reveal N-shaped response；(2) when acetone vapor (donor melecules) is adsorbed on
The surface of La (TBPP) (TBNc) and when generating film, acetone molecules can transfer an electron to La (TBPP) (TBNc) molecule immediately
On, cause electric current to increase with the increase of acetone concentration；(3) La (TBPP) (TBNc) film is for being resistant to it when detecting acetone
The interference of his escaping gas.
The present invention also provides the purposes of above-mentioned La (TBPP) (TBNc) film, for detecting acetone.Above-mentioned La (TBPP)
(TBNc) film can carry out low strength range detection to acetone at room temperature；At room temperature to the minimum response concentration of acetone
1ppm；The response time of 1-800ppm acetone is 75s, recovery time 89s.
Advantage of the invention:
(1) substrate of the ITO interdigital electrode used in the present invention is PET, is flexible member；
(2) La (TBPP) (TBNc) method for manufacturing thin film for detecting acetone used in the present invention is simple, and post-processes
Relatively easily；
(3) present invention is effective at room temperature can quickly survey for detecting the gas sensor element advantage of acetone
Determine acetone, and without security risk；To the response concentration of acetone down to 1ppm, response and recovery time are short, and stability is good, anti-interference
Property is strong, has good selectivity；Structure and preparation process are simple, low in cost, are easy to implement industrialization.
Detailed description of the invention
Fig. 1 is the structure chart of acetone gas sensor；
Fig. 2 is the mass spectrogram of gas sensitive in acetone gas sensor；
Fig. 3 is the SEM figure of gas sensitive in acetone gas sensor；
Fig. 4 be gas sensitive in acetone gas sensor electronic (A be La (TBPP) (TBNc) film, B
For La (TBPP) (TBNc) chloroformic solution)；
Fig. 5 be gas sensitive in acetone gas sensor infared spectrum (A be La (TBPP) (TBNc) powder, B La
(TBPP) (TBNc) film)；
Fig. 6 is the XRD diagram of gas sensitive and cell configuration schematic diagram in acetone gas sensor；
Fig. 7 is the curve (room temperature condition) of the current-voltage of acetone gas sensor；
Fig. 8 is acetone gas sensor bending property curve (room temperature condition) at 5V；
Fig. 9 is the curve (room temperature condition) of the current-vs-time of acetone gas sensor；
Figure 10 be the reproducibility of acetone gas sensor and in 120 days to the linearity curve steady in a long-term of 500ppm acetone
(room temperature condition)；
Figure 11 is response-concentration curve (room temperature condition) of the acetone gas sensor to various concentration gas；
Figure 12 is selectivity curve (room temperature condition) of the acetone gas sensor to 500ppm difference test gas；
Figure 13 is bending property test curve (room temperature condition) of the acetone gas sensor under 500ppm acetone.
Absorption is translated into absorbance, and wavelength is translated into wavelength, and intensity is translated into intensity,
Transmittance is translated into light transmittance, and it is electric current that current, which is translated into Chinese, and voltage is translated into voltage, and time is translated into Chinese and is
Time, S indicate the sensitivity of gas sensor, and response is translated into responsiveness, number of repeated bending
Tests is translated into alternating bending test number, and acetone is translated into acetone, and ethanol is translated into ethyl alcohol, and formaldehyde is translated into first
Aldehyde, methanol are translated into methanol, NH3It is translated into ammonia, CO is translated into carbon monoxide, NO2It is translated into nitrogen dioxide.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Content described in book describes other advantages and effect of the invention easily, and the present invention can also pass through in addition different tools
Body embodiment is embodied or practiced, and the various details in this specification can also not had based on different viewpoints and application
Various modifications or alterations are carried out under spirit of the invention.
It should be noted that in the absence of conflict, the feature in following embodiment and embodiment can be combined with each other.Also
It should be appreciated that term used in present example is in order to describe specific specific embodiment, rather than in order to limit this
The protection scope of invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or according to
Condition proposed by each manufacturer.
When the numberical range that embodiment provides, it should be appreciated that except non-present invention is otherwise noted, two of each numberical range
Any one numerical value between endpoint and two endpoints can be selected.Unless otherwise defined, all skills used in the present invention
The grasp and record of the invention of art and scientific term and those skilled in the art to the prior art, can also use with
Any method, equipment and the material of the similar or equivalent prior art of method described in the embodiment of the present invention, equipment, material come
Realize the present invention.
Instrument used by performance test in the present invention are as follows: German Bruker company MALDI-TOF-MS mass spectrograph, Germany
Bruker company Vertex70 infrared spectrometer, JEOL company, Japan JEOL JSM-6700F scanning electron microscope, Germany
Bruker company D/max- γ Type B X-ray diffractometer, Shimadzu, Japan's Hitachi U-4100 UV, visible light are divided light
Degree meter, auspicious company, the regular senior middle school Agilent B2900 Agilent air-sensitive tester in Shenzhen.
The specific embodiment of the invention is further described with reference to the accompanying drawing.
The preparation method of embodiment 1La (TBPP) (TBNc)
1.1
(1) by H2(TBPP) (0.05mmol), [La (acac)3]·nH2O (0.10mmol) and 6- tert-butyl -2,3- dintrile
Base naphthalene (0.40mmol) is added to equipped with 11 carbon -7- alkene of 4mL n-octyl alcohol and 0.05mL 1,8- diazabicyclo [5.4.0]
In round-bottomed flask, reaction mixture is flowed back under a nitrogen 18 hours, reaction temperature is 180 DEG C；
(2) after the reaction was completed, n-octyl alcohol is removed at reduced pressure conditions, it is cooling；With the mixed solution of methylene chloride and methanol
Make eluant, eluent to be purified with silicagel column；The volume ratio of methylene chloride and methanol solution is 100:6；
(3) in order to improve the purity of product, gained La (TBPP) (TBNc) plus 2mL chloroform in step (2) is molten
Solution, is recrystallized with 12mL methanol；Wherein, chloroform is as readily soluble solvent and methanol as poor solvent；
(4) mass spectrogram of resulting La (TBPP) (TBNc) is as shown in Fig. 2, mass spectra peak is 1911.322, with La (TBPP)
(TBNc) calculated value is similar, theoretical value 1913.230.
1.2
(1) by H2(TBPP) (0.05mmol), [La (acac)3]·nH2O (0.15mmol) and 6- tert-butyl -2,3- dintrile
Base naphthalene (0.45mmol) is added to equipped with 11 carbon -7- alkene of 5mL n-octyl alcohol and 0.06mL 1,8- diazabicyclo [5.4.0]
In round-bottomed flask, reaction mixture is flowed back under a nitrogen 20 hours, reaction temperature is 190 DEG C；
(2) after the reaction was completed, n-octyl alcohol is removed at reduced pressure conditions, it is cooling；With the mixed solution of methylene chloride and methanol
Make eluant, eluent to be purified with silicagel column；The volume ratio of methylene chloride and methanol solution is 100:6；
(3) in order to improve the purity of product, gained La (TBPP) (TBNc) plus 2mL chloroform in step (2) is molten
Solution, is recrystallized with 16mL methanol；Wherein, chloroform is as readily soluble solvent and methanol as poor solvent；
(4) mass spectrogram of resulting La (TBPP) (TBNc) is as shown in Fig. 2, mass spectra peak is 1911.322, with La (TBPP)
(TBNc) calculated value is similar, calculated value 1913.230.
The preparation of 2 acetone gas sensor element of embodiment
2.1
(1) preparation of ITO/PET interdigital electrode: taking ITO/PET material, cleans, dry, then carves ITO/PET substrate
Erosion is ITO interdigital electrode (for the prior art)；
The ITO/PET interdigital electrode handles concrete mode are as follows: ITO/PET interdigital electrode is put into beaker, in ultrasound
It is cleaned by ultrasonic respectively with toluene, acetone, dehydrated alcohol, distilled water in wave washer, every kind of solvent cleans three times, and five points every time
Then clock is dried in vacuo, spare；
(2) La (TBPP) (TBNc) is dissolved in chloroform, La (TBPP) (TBNc) solution, 0.006 mol/L is made；
(3) solution that step (2) prepares carefully is dripped and is placed in the closed container with vacuum valve in cleaned
In the interdigital electrode in face, dripping quantity 0.25mL, while the beaker for filling 30mL chloroform is also put into vacuum valve
In closed container；
(4) closed container is closed, cock is opened, vacuumizes 3 times, each 5min, cut-out tap, is full of steam with true
Drying for standby after standing for 24 hours, is taken out in the closed container space of empty valve, and drying temperature is 60 DEG C, drying time 12h is obtained
Interdigital electrode surface is the metalloporphyrin naphthalene cyanines complex gas sensor element of La (TBPP) (TBNc) film；
(5) characterized comprehensively to obtained product: observing its external pattern using scanning electron microscope (SEM) is pleat
Wrinkle structure, fold amplitude are 5-10 μm；By electronic it can be seen that when La (TBPP) (TBNc) is assembled into film,
All bands all obviously broaden；Become La (TBPP) (TBNc) by the group that infrared spectroscopy confirms film；Pass through X-ray diffraction
Confirm the macromolecule orderly character of La (TBPP) (TBNc) film.
2.2
(1) preparation of ITO/PET interdigital electrode: taking ITO/PET material, cleans, dry, then carves ITO/PET substrate
Erosion is ITO interdigital electrode (for the prior art)；
The ITO/PET interdigital electrode handles concrete mode are as follows: ITO/PET interdigital electrode is put into beaker, in ultrasound
Respectively with the solvent toluene of opposed polarity, acetone, dehydrated alcohol, distilled water ultrasonic cleaning, every kind of solvent cleaning in wave washer
Three times, it every time five minutes, is then dried in vacuo, it is spare；
(2) La (TBPP) (TBNc) is dissolved in methylene chloride, La (TBPP) (TBNc) solution, 0.009 mol/L is made；
(3) solution that step (2) prepares carefully is dripped and is placed in the closed container with vacuum valve in cleaned
In the interdigital electrode in face, dripping quantity 0.25mL, while the beaker for filling 50mL chloroform is also put into vacuum valve
In closed container；
(4) closed container is closed, cock is opened, vacuumizes 5 times, each 10min, cut-out tap, steam is full of and has
Drying for standby after standing 18h, is taken out in the closed container space of vacuum valve, and drying temperature is 50 DEG C, and drying time is for 24 hours, that is, to obtain
Obtain the metalloporphyrin naphthalene cyanines complex gas sensor element that interdigital electrode surface is La (TBPP) (TBNc) film；
(5) characterized comprehensively to obtained solid product: result is consistent with 2.1.
The electrical property of embodiment 3La (TBPP) (TBNc) film measures
Choose the test that La (TBPP) (TBNc) film obtained in embodiment 2 carries out I-V performance and bending property, test
As a result as Figure 7-8, the conductivity that La (TBPP) (TBNc) film can be calculated from Fig. 7 is 1.62 × 10-6S·cm-1, illustrate La prepared by the present invention (TBPP) (TBNc) film gas sensor element conduction property with higher；From Fig. 8
It can be seen that La (TBPP) (TBNc) film gas sensor original part can manual bending to 60 ° and restore rectilinear form and at 60 °
After being bent lower 500 circulations, the output signal of electric current is stable.
The performance measurement of 4 acetone gas sensor of embodiment
La (TBPP) (TBNc) the film building air-sensitive test device obtained in embodiment 2 is chosen, it is real to carry out air-sensitive test
It tests.Air-sensitive test process is in a comparatively gentle environment (under room temperature, external atmosphere pressure and dry air) and two electrodes
Between the air-sensitive performance that carries out under fixed-bias transistor circuit 5V.Use test equipment: Agilent B290a precision source/measuring unit.Wherein, it adopts
With embodiment 2 prepare each La (TBPP) (TBNc) film preparation at gas sensor tested respectively, test result one
It causes；As described and depicted in figs. 9-13.As shown in figure 9, La (TBPP) (TBNc) film gas sensor has the acetone of 1-800ppm
Good response, detection line can achieve 1ppm, and response/recovery time is respectively 75s and 89s；As shown in Figure 10, La
(TBPP) stability of (TBNc) the film gas sensor element to 500ppm acetone duplicate responses and in 120 days basic one
It causes, illustrates that the stability of the gas sensor is fine；As shown in figure 11, La (TBPP) (TBNc) thin film gas sensor element
Acetone concentration and response sensitivity are in good linear relationship in 1-800ppm concentration range；As shown in figure 12, La (TBPP)
(TBNc) film gas sensor element includes acetone, ethyl alcohol, formaldehyde, methanol, ammonia, carbon monoxide and titanium dioxide to 500ppm
Gas with various including nitrogen carries out air-sensitive test, it can be seen that La (TBPP) (TBNc) film is to third in various test gases
Ketone shows peak response, has good selectivity to acetone；As shown in figure 13, the gas of La (TBPP) (TBNc) film
Bending property of the sensor element under 500ppm acetone is tested, and sensor is not shown after 500 bend cycles
The significant changes of Opposed Current.
In summary, La (TBPP) (TBNc) film gas sensor has responsiveness good, sensitive in acetone at room temperature
Degree is high, response and recovery time are fast, favorable reproducibility, selective strong advantage, is suitable as acetone gas sensor, this makes this
Kind method can be widely used in actual life and industrial production.
Above-described embodiment is merely exemplary to illustrate the principle of the present invention and its effect, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of porphyrin naphthalene cyanines double-level-metal complex, abbreviation La (TBPP) (TBNc), structural formula, as shown in Equation 1:
2. the preparation method of La (TBPP) (TBNc) described in claim 1, which comprises the following steps:
(1) by H2(TBPP), [La (acac)3]·nH2O and 6- tert-butyl -2,3- dinitrile naphthalene is added to equipped with n-octyl alcohol and 1,
In the round-bottomed flask of 11 carbon -7- alkene of 8- diazabicyclo [5.4.0], reaction mixture is flowed back under a nitrogen 18-20 hours,
Reaction temperature is 180-190 DEG C；H2(TBPP), [La (acac)3]·nH2The molar ratio of O and 6- tert-butyl -2,3- dinitrile naphthalene
For 1.0:2.0-3.0:8.0-9.0；H2(TBPP) and the molar ratio of n-octyl alcohol is 1.0:500.0-550.0；H2(TBPP) and 1,8-
The molar ratio of 11 carbon -7- alkene of diazabicyclo [5.4.0] is 1.0:6.0-8.0；
(2) after the reaction was completed, n-octyl alcohol is removed at reduced pressure conditions, it is cooling；It is washed with the mixed solution of methylene chloride and methanol
De- agent is purified with silicagel column；The volume ratio of methylene chloride and methanol is 100:6；
(3) in order to which gained La (TBPP) (TBNc) in step (2) plus chloroform dissolution are used methanol by the purity for improving product
It is recrystallized；The volume ratio of chloroform and methanol is 1:6-8；Wherein, chloroform is as readily soluble solvent and methanol as bad
Solvent.
3. a kind of for detecting the gas sensor element of acetone, it is characterised in that: including ITO/PET substrate and interdigital electrode,
La (TBPP) (TBNc) film is arranged in ITO/PET substrate, on interdigital electrode surface in the interdigital electrode etching.
4. the preparation method of La (TBPP) (TBNc) film gas sensor element as claimed in claim 3, which is characterized in that packet
Include following steps:
(1) ITO/PET interdigital electrode is put into beaker, in ultrasonic cleaner respectively with toluene, acetone, dehydrated alcohol,
Distilled water ultrasonic cleaning, every kind of solvent cleaning three times, five minutes every time, is then dried in vacuo, spare；
(2) La (TBPP) (TBNc) is dissolved with good solvent, the solution of 0.006-0.009mol/L is made；The good solvent is three
Chloromethanes or methylene chloride；
(3) solution that step (2) prepares carefully is dripped and is placed on inside the closed container with vacuum valve in cleaned
In interdigital electrode, while the beaker for filling chloroform is also put into the closed container with vacuum valve；
(4) closed container is closed, cock is opened, vacuumizes 3-5 times, each 5-10min, cut-out tap, steam is full of and has
Drying for standby after standing 18-24h, is taken out in the closed container space of vacuum valve, i.e., acquisition interdigital electrode surface is La (TBPP)
(TBNc) the metalloporphyrin naphthalene cyanines complex gas sensor element of film.
5. according to the method described in claim 4, it is characterized in that, what is also included the following features is any one or more:
A. La (TBPP) (TBNc) solution is added drop-wise to above interdigital electrode using dropper in step (3), dripping quantity 0.25-
0.50mL；
B., 30-100mL chloroform is housed in beaker in step (3)；
C. drying temperature is 50-60 DEG C in step (4), drying time 12-24h.
6. La (TBPP) (TBNc) film according to claim 4 or 5, which is characterized in that be pleated structure, fold amplitude
It is 5-10 μm.
7. La (TBPP) (TBNc) film according to claim 6, which is characterized in that at room temperature to the inspection of acetone gas
It surveys.
8. the purposes of La (TBPP) (TBNc) film according to claim 7, which is characterized in that the minimum response to acetone
Concentration is 1ppm.
9. the purposes of La (TBPP) (TBNc) film according to claim 7, which is characterized in that 1-800ppm acetone
Response time and recovery time are respectively 75s and 89s.
10. a kind of gas sensor assembled using La (TBPP) (TBNc) film described in claim 3-9 any one
Application of the element in terms of preparing the gas sensing for measuring acetone.
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