CN105176517B - A kind of optical oxygen sensing composite material without heavy metal element and preparation method thereof - Google Patents
A kind of optical oxygen sensing composite material without heavy metal element and preparation method thereof Download PDFInfo
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Abstract
Optical oxygen sensing composite material being made up of the invention provides one kind the organo-silicon compound shown in formula (I) and the molecular sieves of MCM 41 and preparation method thereof.The composite that the present invention is made up of organo-silicon compound and the molecular sieves of MCM 41 (10mg/g) is free of heavy metal element, the luminous strength ratio [I (N in pure nitrogen gas and purity oxygen2)/I(O2)=6.3] reach and PtTPyP/MCM 41 (40mg/g) composite [I (N containing heavy metal element in the prior art2)/I(O2) ≈ 7.0] close level.
Description
Technical field
The invention belongs to optical oxygen sensing Material Field, and in particular to a kind of optical oxygen sensing without heavy metal element is answered
Condensation material and preparation method thereof.
Background technology
With urbanization and industrialized fast development, especially for meeting Code in Hazardous Special Locations and the urgent of environment measuring is essential
Will, oxygen concentration is detected using Winkler methods and the method such as Clark dissolved oxygen electrodes method and optical oxygen sensing method.
Wherein, the optical oxygen sensing method that principle is set up is quenched to luminescent dye based on oxygen, with many other sides
The irreplaceable advantage of method：One to be in response to speed fast；Two be that sensitivity is high；Three be easy to operate.Therefore, it biology, chemical industry,
The fields such as aviation, military affairs have extensive development prospect.
By the retrieval discovery to prior art, 2005 the 31st in Journal of Materials Chemistry
Phase page 3181 entitled " Oxygen sensing materials based on mesoporous silica MCM-41and
(" oxygen based on mesoporous siliceous MCM-41 and Pt (II)-metalloporphyrin complex is passed Pt (II)-porphyrin complexes "
Sense material ") document mention, duct in mesoporous silicon oxide allows solvent and other small molecules or ion in meso-porous titanium dioxide
The inside of silicon is transmitted.And topic of page 1883 of the 16th phase in 2006 in Advanced Functional Materials
For " Mesostructured Silica Chemically Doped with RuII as a Superior Optical
Oxygen Sensor " (" chemical doping RuIIMesoporous silicon oxide is used as super Luminescence based Oxygen Sensor ") document mention, a lot
Luminescent material has been attempted as oxygen pickup probe.Wherein light-emitting transition metal complex, especially many pyridine rutheniums (II) are matched somebody with somebody
Compound, due to stronger triplet state phosphorescence quenching effect, good stability (photochemistry, optical physics and heat) and longer
Phosphorescent lifetime (Microsecond grade) etc. is often used as optics oxygen-sensitive material.
However, transient metal complex is not only expensive, and heavy metal element is likely to result in environmental pollution, it is difficult to full
An urgent demand of sufficient developing low-cost, free of contamination optical oxygen sensing material, it is necessary to development environment close friend's, without heavy metal
The luminescent material of element, reduces the cost of optical oxygen sensing material, reduces pollution of the heavy metal to environment.Organo-silicon compound by
In having the advantages that resistance to high/low temperature, resistance to ozone, nontoxic corrosion-free and physiological inertia, aviation, sophisticated technology, military affairs are had become
The special material of engineering department.Organo-silicon compound are combined with mesoporous silicon oxide, prepare by organo-silicon compound with
The optical oxygen sensing composite material of MCM-41 molecular sieves composition, gives full play to the advantage of two kinds of material properties, to improving material
Sensing capabilities have extremely important meaning, and there is presently no the report of the research on this respect.
The content of the invention
In formula (I), R1For C1-10 alkyl, aryl or-H, preferably-CH3Or phenyl；
R2, R3And R4Independently selected from C1-10 alkyl or aryls, preferably-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-
(CH2)3CH3Or phenyl.
In consideration of it, the present invention is directed to, transition metal phosphorescent complexes are expensive and heavy metal element easily causes environment dirt
The problems such as dye, there is provided a kind of optical oxygen sensing composite material being made up of organo-silicon compound and MCM-41 molecular sieves and its preparation
Shown in the molecular structure of method, wherein organo-silicon compound such as formula (I).Obtained composite is relative to existing transition metal phosphorus
Light complex, which has, is free of heavy metal element, and preparation method is simple, and the susceptibility that change to oxygen concentration of luminous intensity with
By the metal complex advantage close with the susceptibility for the composite that MCM-41 molecular sieves are constituted.
The technical scheme that the present invention is proposed to achieve the above object comprises the following steps：(a) tetraalkyl silane is prepared
[SiR2R3R4(4-BrPh)]：Under inert gas shielding, it is added dropwise successively just to the tetrahydrofuran cryogenic fluid dissolved with Isosorbide-5-Nitrae-dibromobenzene
Butyl lithium and trialkyl chlorosilane SiR2R3R4Cl, pyroreaction adds deionized water and reaction, dichloromethane extraction is quenched afterwards completely
Take, [SiR is obtained after ethyl alcohol recrystallization, drying2R3R4(4-BrPh)] white powder or weak yellow liquid；(b) prepare siliconated
Compound：Under inert gas shielding, to dissolved with tetraalkyl silane [SiR2R3R4(4-BrPh)] tetrahydrofuran cryogenic fluid in successively
Add n-BuLi and 1,10- phenanthroline or its derivative (including 4,7- diaryl -1,10- phenanthroline and 4,7- dimethyl -
1,10- phenanthroline), pyroreaction adds deionized water and reaction, dichloromethane extraction, manganese dioxide, warp is quenched afterwards completely
Silica gel column chromatography, is recrystallized to give organo-silicon compound yellow solid powder；(c) organo-silicon compound/MCM-41 is prepared to be combined
Material：Through filtering after the organo-silicon compound, MCM-41 molecular sieves and the dichloromethane that are prepared in (b) are stirred at 25 DEG C, washing
Faint yellow solid powder organo-silicon compound/MCM-41 composites are obtained with vacuum drying.Wherein, organo-silicon compound/
Luminous strength ratio [I (N of MCM-41 (10mg/g) composite in pure nitrogen gas and purity oxygen2)/I(O2)=6.3] it can reach
With entitled " Oxygen sensing of page 3181 of the 31st phase in 2005 in Journal of Materials Chemistry
materials based on mesoporous silica MCM-41and Pt(II)-porphyrin complexes”
The PtTPyP/ that the document of (" the oxygen sensing material based on mesoporous siliceous MCM-41 and Pt (II)-metalloporphyrin complex ") is mentioned
MCM-41 (40mg/g) composite [I (N2)/I(O2) ≈ 7.0] close level.
In the step (a), (b), inert gas used is nitrogen or argon gas, preferably nitrogen；N-BuLi is concentration
For 2.2mol/L hexane solution, the time for adding of n-BuLi is 0.5~2.0 hour, preferably 1.0 hours；Isosorbide-5-Nitrae-dibromo
Concentration of the benzene in tetrahydrofuran solvent is 0.10mol/L~0.50mol/L, preferably 0.25mol/L；The pyroreaction time is 10
~36 hours, preferably 24 hours.
In the step (b), manganese dioxide is using activation is preceding needed, and activation temperature is 90~170 DEG C, preferably 135
DEG C, soak time is 3~12 hours, preferably 8 hours；The manganese dioxide time is 2~18 hours, preferably 12 hours；Silica gel
Column chromatography eluent is：(volume ratio is 1/1~1/10, preferably 1/3) for ethyl acetate and petroleum ether.
In the step (c), the mass ratio of organo-silicon compound and MCM-41 molecular sieve used is 0.1/99.9~10/
90, preferably 1/99；Methylene chloride is 5~30mL, preferably 10mL；Mixing time is 10~36 hours, preferably 24 hours；Light
Learn RF-5301PC types fluophotometer (self-control sample room and gas distribution system that oxygen sensing property is produced by Japanese Shimadzu Corporation
System) measure.
Present invention additionally comprises application of the organo-silicon compound/MCM-41 composites as optical oxygen sensing material.
The advantage of the invention is that：Obtained composite is free of heavy metal element, and preparation method is simple, and lights
Susceptibility and the susceptibility for the composite being made up of metal complex and MCM-41 molecular sieves that intensity changes to oxygen concentration
It is close.
Brief description of the drawings
Fig. 1 is the obtained Si-1/MCM-41 composites of embodiments of the invention in different proportion N2/O2Hair under environment
Penetrate spectrogram.
Fig. 2 is the obtained Si-2/MCM-41 composites of embodiments of the invention in different proportion N2/O2Hair under environment
Penetrate spectrogram.
Fig. 3 is the obtained Si-3/MCM-41 composites of embodiments of the invention in different proportion N2/O2Hair under environment
Penetrate spectrogram.
Fig. 4 is the obtained Si-4/MCM-41 composites of embodiments of the invention in different proportion N2/O2Hair under environment
Penetrate spectrogram.
Embodiment
The invention provides a kind of optical oxygen sensing composite material being made up of organo-silicon compound and MCM-41 molecular sieves
And preparation method thereof, wherein shown in the structure of organo-silicon compound such as formula (I)：
In structure formula (I), R1For C1-10 alkyl, aryl or-H, preferably-CH3Or phenyl；
R2, R3And R4Independently selected from C1-10 alkyl or aryls, preferably-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-
(CH2)3CH3Or phenyl.
Content for a better understanding of the present invention, makees further with reference to specific examples below and accompanying drawing to the present invention
Describe in detail, agents useful for same is commercially available in embodiment.But the protection content of the present invention is not limited to following examples.Implement this
Process, condition, reagent, test method of invention etc., are generally knowing for this area in addition to the following content specially referred to
Know, content is not particularly limited in the present invention.
Embodiment 1：Organo-silicon compound Si-1 synthesis in structure formula (I)
At (1) 25 DEG C, Isosorbide-5-Nitrae-dibromobenzene (1.18g, 5.0mmol) and 20mL THF solutions are added under nitrogen protection
In 100mL round-bottomed flasks, system is cooled to -120~10 DEG C, preferably -78 DEG C, 2.50mL normal-butyls are slowly added dropwise into flask
Lithium/hexane solution (2.2M, 5.5mmol), time for adding is 0.5~2.0 hour, preferably 1.0 hours.Three are added into flask
Methylchlorosilane (0.63mL, 5.0mmol), 70 DEG C are continued to stir, and mixing time is 10~36 hours, preferably 24 hours.Spend
Reaction is quenched in ionized water, and dichloromethane extraction, organic phase removes under reduced pressure after anhydrous sodium sulfate drying and trimethyl is produced after solvent
(4- bromophenyls) silane weak yellow liquid.Yield：60.0%.
(2) trimethyl (4- bromophenyls) silane (0.50g, 2.2mmol) and 20mL THF prepared in step (1) is weighed to add
Enter into 100mL round-bottomed flasks, system is cooled to -120~10 DEG C, preferably -78 DEG C.1.00mL is slowly added dropwise into flask just
Butyl lithium/hexane solution (2.2M, 2.2mmol), time for adding is 0.5~2.0 hour, preferably 1.0 hours.After completion of dropping
Stirring 0.5~2.0 hour, preferably 1.0 hours.Added into flask 4,7- diphenyl -1,10- phenanthroline (0.66g,
Continue stirring after 2.0mmol) at 70 DEG C, mixing time is 10~36 hours, preferably 24 hours.Reaction is quenched with deionized water,
Dichloromethane is extracted, and organic phase is aoxidized after anhydrous sodium sulfate drying with activated manganese dioxide (1.91g, 22mmol), during oxidation
Between be 2~18 hours, preferably 12 hours, filtering removed after solvent, crude on silica gel column chromatography that (eluent is acetic acid under reduced pressure
Ethyl ester and petroleum ether, volume ratio are 1/1~1/10, preferably 1/3) are recrystallized again with ether/n-hexane mixed solvent, ether/just
The ratio of hexane is 2/1~1/4, preferably 1/1.Si-1 yellow powders are obtained through said process.Yield：48.0%.1H NMR
(CDCl3, 400MHz, ppm)：9.718 (s, 1H), 8.174 (s, 2H), 8.223 (s, 1H), 8.017 (s, 1H), 7.909 (d,
2H), 7.786 (d, 2H), 7.593 (m, 10H), 0.331 (s, 9H).
Embodiment 2：Organo-silicon compound Si-2 synthesis in structure formula (I)
At (1) 25 DEG C, Isosorbide-5-Nitrae-dibromobenzene (1.18g, 5.0mmol) and 20mL THF solutions are added under nitrogen protection
In 100mL round-bottomed flasks.System is cooled to -120~10 DEG C, preferably -78 DEG C, 2.50mL normal-butyls are slowly added dropwise into flask
Lithium/hexane solution (2.2M, 5.5mmol), time for adding is 0.5~2.0 hour, preferably 1.0 hours.Two are added into flask
Continue stirring after aminomethyl phenyl chlorosilane (0.84mL, 5.0mmol) at 70 DEG C, mixing time is 16~32 hours, and preferably 24 is small
When.Reaction is quenched with deionized water, dichloromethane extraction, organic phase is removed under reduced pressure after solvent after anhydrous sodium sulfate drying and produced
3,5-dimethylphenyl (4- bromophenyls) silane weak yellow liquid.Yield：54.2%.
(2) 3,5-dimethylphenyl (4- bromophenyls) silane (0.64g, 2.2mmol) and 20mL prepared in step (1) is weighed
THF is added in 100mL round-bottomed flasks, and system is cooled into -120~10 DEG C, preferably -78 DEG C.It is slowly added dropwise into flask
1.00mL n-BuLis/hexane solution (2.2M, 2.2mmol), time for adding is 0.5~3.0 hour, preferably 1 hour.It is added dropwise
Stirred 0.5~2.0 hour, preferably 1 hour after finishing.Added into flask 4,7- diphenyl -1,10- phenanthroline (0.66g,
2.0mmol), 70 DEG C are continued to stir, and mixing time is 16~32 hours, preferably 24 hours.Reaction, dichloro are quenched with deionized water
Methane is extracted, and organic phase is aoxidized after anhydrous sodium sulfate drying with activated manganese dioxide (1.91g, 22mmol), and oxidization time is 2
~18 hours, preferably 12 hours, filtering, remove under reduced pressure after solvent, crude on silica gel column chromatography (eluent be ethyl acetate and
Petroleum ether, volume ratio is 1/1~1/10, preferably 1/3) is recrystallized again with ether/n-hexane mixed solvent, ether/n-hexane
Ratio is 2/1~1/4, preferably 1/1.Si-2 yellow powders are obtained through said process.Yield：44.2%.1H NMR(CDCl3,
400MHz, ppm)：9.479 (s, 1H), 8.510 (s, 1H), 8.123 (tetra, 1H), 8.129 (s, 1H), 7.923 (m, 21H),
7.717 (m, 2H), 7.567-7.498 (m, 12H), 7.375-7.328 (m, 5H), 0.612 (s, 6H).
Embodiment 3：Organo-silicon compound Si-3 synthesis in structure formula (I)
At (1) 25 DEG C, Isosorbide-5-Nitrae-dibromobenzene (1.18g, 5.0mmol) and 20mL THF solutions are added under nitrogen protection
In 100mL round-bottomed flasks.System is cooled to -120~10 DEG C, preferably -78 DEG C, 2.50mL normal-butyls are slowly added dropwise into flask
Lithium/hexane solution (2.2M, 5.5mmol), time for adding is 0.5~2.0 hour, preferably 1.0 hours.First is added into flask
Base diphenyl chlorosilane (1.05mL, 5.0mmol), 70 DEG C are continued to stir, and mixing time is 10~36 hours, preferably 24 hours.
Reaction is quenched with deionized water, dichloromethane extraction, organic phase removes solvent, gained solid under reduced pressure after anhydrous sodium sulfate drying
Methyldiphenyl base (4- bromophenyls) silane white solid powder is recrystallized to give with absolute ethyl alcohol.Yield：65.0%.
(2) methyldiphenyl base (4- bromophenyls) silane (0.78g, 2.2mmol) and 20mL prepared in step (1) is weighed
THF is added in 100mL round-bottomed flasks, and system is cooled into -120~0 DEG C, preferably -78 DEG C.It is slowly added dropwise into flask
1.00mL n-BuLis/hexane solution (2.2M, 2.2mmol), time for adding is 0.5~3.0 hour, preferably 1.0 hours.Drop
Add and stirred 0.5~2.0 hour, preferably 1.0 hours after finishing.4,7- diphenyl -1,10- phenanthrolines are added into flask
Continue stirring after (0.66g, 2.0mmol) at 70 DEG C, mixing time is 10~36 hours, preferably 24 hours.Quenched with deionized water
Go out reaction, dichloromethane extraction, organic phase is aoxidized after anhydrous sodium sulfate drying with activated manganese dioxide (1.91g, 22mmol),
Oxidization time is 2~18 hours, and preferably 12 hours, filtering removed (eluent after solvent, crude on silica gel column chromatography under reduced pressure
For ethyl acetate and petroleum ether, volume ratio is 1/1~1/10, preferably 1/3) is recrystallized again with ether/n-hexane mixed solvent, second
The ratio of ether/n-hexane is 2/1~1/4, preferably 1/1.Si-3 yellow powders are obtained through said process.Yield：50.5%.1H
NMR(CDCl3, 400MHz, ppm)：9.504 (s, 1H), 8.534 (d, 2H), 8.129 (s, 1H), 7.943 (d, 1H), 7.869
(d, 1H), 7.752 (d, 3H), 7.565 (m, 16H), 7.385 (tetra, 7H), 0.896 (s, 3H).
Embodiment 4：Organo-silicon compound Si-4 synthesis in structure formula (I)
At (1) 25 DEG C, Isosorbide-5-Nitrae-dibromobenzene (1.18g, 5.0mmol) and 20mL THF solutions are added under nitrogen protection
In 100mL round-bottomed flasks.2.50mL n-BuLis/hexane solution (2.2M, 5.5mmol) is slowly added dropwise into flask, is added dropwise
Time is 0.5~2.0 hour, preferably 1.0 hours.Into flask add tri-phenyl chloride (1.48g, 5.0mmol), 70 DEG C after
Continuous stirring, mixing time is 10~36 hours, preferably 24 hours.Reaction, dichloromethane extraction, organic phase are quenched with deionized water
Remove solvent under reduced pressure after anhydrous sodium sulfate drying, it is white that gained solid is recrystallized to give triphenyl (4- bromophenyls) with absolute ethyl alcohol
Color solid powder.Yield：69.8%.
(2) triphenyl (4- bromophenyls) silane (0.91g, 2.2mmol) and 20mL THF prepared in step (1) is weighed to add
Enter into 100mL round-bottomed flasks.System is cooled to -120~10 DEG C, preferably -78 DEG C.1.00mL is slowly added dropwise into flask just
Butyl lithium/hexane solution (2.2M, 2.2mmol), time for adding is 0.5~3.0 hour, preferably 1.0 hours.After completion of dropping
Stirring 0.5~2.0 hour, preferably 1.0 hours.Added into flask 4,7- diphenyl -1,10- phenanthroline (0.66g,
Continue stirring after 2.0mmol) at 70 DEG C, mixing time is 10~36 hours, preferably 24 hours.Reaction is quenched with deionized water,
Dichloromethane is extracted, and organic phase is aoxidized after anhydrous sodium sulfate drying with activated manganese dioxide (1.91g, 22mmol), during oxidation
Between be 2~18 hours, preferably 12 hours, filtering removed after solvent, crude on silica gel column chromatography that (eluent is acetic acid under reduced pressure
Ethyl ester and petroleum ether, volume ratio are 1/1~1/10, preferably 1/3) are recrystallized again with ether/n-hexane mixed solvent, ether/just
The ratio of hexane is 2/1~1/4, preferably 1/1.Si-4 yellow powders are obtained through said process.Yield：48.4%.1H NMR
(CDCl3, 400MHz, ppm)：9.372 (s, 1H), 8.436 (d, 2H), 8.085 (s, 1H), 7.875 (tetra, 2H), 7.782
(d, 2H), 7.628 (d, 8H), 7.551 (d, 11H), 7.426 (m, 10H), 7.255 (s 2H).
Embodiment 5：The preparation of Si-1/MCM-41 composites and optical oxygen sensing property
At 25 DEG C, 1.0mg Si-1 and 99.0mg MCM-41 molecular sieves are stirred 24 hours in 10mL dichloromethane.
Filtering, washing, vacuum drying obtains faint yellow solid powder Si-1/MCM-41 composites, and vacuum drying temperature is 30~70
DEG C, preferably 60 DEG C, drying time is 6~24 hours, preferably 12 hours.The optical oxygen sensing of Si-1/MCM-41 composites
The RF-5301PC types fluophotometer (self-control sample room and gas distributing system) that matter is produced by Japanese Shimadzu Corporation is measured, should
Composite is in different proportion N2/O2Emission spectrum under environment is shown in Fig. 1.Si-1/MCM-41 (10mg/g) composite is in purity nitrogen
Luminous strength ratio [I (N in gas and purity oxygen2)/I(O2)] it is 3.17.
Embodiment 6：The preparation of Si-2/MCM-41 composites and optical oxygen sensing property
At 25 DEG C, 1.0mg Si-2 and 99.0mg MCM-41 molecular sieves are stirred 24 hours in 10mL dichloromethane.
Filtering, washing, vacuum drying obtains faint yellow solid powder Si-2/MCM-41 composites, and vacuum drying temperature is 30~70
DEG C, preferably 60 DEG C, drying time is 6~24 hours, preferably 12 hours.The optical oxygen sensing of Si-2/MCM-41 composites
The RF-5301PC types fluophotometer (self-control sample room and gas distributing system) that matter is produced by Japanese Shimadzu Corporation is measured, should
Composite is in different proportion N2/O2Emission spectrum under environment is shown in Fig. 2.Si-2/MCM-41 (10mg/g) composite is in purity nitrogen
Luminous strength ratio [I (N in gas and purity oxygen2)/I(O2)] it is 3.06.
Embodiment 7：The preparation of Si-3/MCM-41 composites and optical oxygen sensing property
At 25 DEG C, 1.0mg Si-3 and 99.0mg MCM-41 molecular sieves are stirred 24 hours in 10mL dichloromethane.
Filtering, washing, vacuum drying obtains faint yellow solid powder Si-3/MCM-41 composites, and vacuum drying temperature is 30~70
DEG C, preferably 60 DEG C, drying time is 6~24 hours, preferably 12 hours.The optical oxygen sensing of Si-3/MCM-41 composites
The RF-5301PC types fluophotometer (self-control sample room and gas distributing system) that matter is produced by Japanese Shimadzu Corporation is measured, should
Composite is in different proportion N2/O2Emission spectrum under environment is shown in Fig. 3.Si-3/MCM-41 (10mg/g) composite is in purity nitrogen
Luminous strength ratio [I (N in gas and purity oxygen2)/I(O2)] it is 6.32.
Embodiment 8：The preparation of Si-4/MCM-41 composites and optical oxygen sensing property
At 25 DEG C, 1.0mg Si-4 and 99.0mg MCM-41 molecular sieves are stirred 24 hours in 10mL dichloromethane.
Filtering, washing, vacuum drying obtains faint yellow solid powder Si-4/MCM-41 composites, and vacuum drying temperature is 30~70
DEG C, preferably 60 DEG C, vacuum drying time is 6~24 hours, preferably 12 hours.The optics oxygen of Si-4/MCM-41 composites is passed
The RF-5301PC types fluophotometer (self-control sample room and gas distributing system) that perceptual matter is produced by Japanese Shimadzu Corporation is surveyed
, the composite is in different proportion N2/O2Emission spectrum under environment is shown in Fig. 4.Si-4/MCM-41 (10mg/g) composite
Luminous strength ratio [I (N in pure nitrogen gas and purity oxygen2)/I(O2)] it is 2.92.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of optical oxygen sensing composite material being made up of the organo-silicon compound shown in formula (I) and MCM-41 molecular sieves, its
The composite construction that there are the composite organo-silicon compound to be entrained in MCM-41 molecular sieves is characterised by, without heavy metal member
Element,
In formula (I), R1For C1-10 alkyl, aryl or-H；
R2, R3And R4Independently selected from C1-10 alkyl or aryls.
2. a kind of preparation method of composite as claimed in claim 1, it is characterised in that comprise the following steps：
(1) using Isosorbide-5-Nitrae-dibromobenzene as initiation material, using THF as solvent, under conditions of n-BuLi presence, with trialkyl chlorine silicon
Alkane (SiR2R3R4Cl) react, filter, recrystallization obtains tetraalkyl silane [SiR after drying2R3R4(4-BrPh)] white solid powder
End or weak yellow liquid；
(2) the tetraalkyl silane [SiR for preparing step (1)2R3R4(4-BrPh)] white solid powder or weak yellow liquid exist
After being sufficiently stirred in THF solvents with n-BuLi at -78 DEG C, then mix with 1,10- phenanthrolines or its derivative, and 70
Further it is sufficiently stirred at DEG C, reaction, dichloromethane extraction, manganese dioxide, through silicagel column most is quenched through deionized water afterwards
Organosilicon yellow solid powder is obtained after chromatography, recrystallization；
(3) the organosilicon yellow solid powder prepared in step (2) and MCM-41 molecular sieves are added in dichloromethane solvent,
Stirring, is filtered, and is washed, vacuum drying, obtains the composite that faint yellow organo-silicon compound are constituted with MCM-41.
3. preparation method according to claim 2, it is characterised in that：Mixing time of the reaction system at 70 DEG C be 16~
32 hours, manganese dioxide was using activation is preceding needed, and activation temperature is 90~170 DEG C, and soak time is 3~10 hours.
4. a kind of composite as claimed in claim 1 is in the application in optical oxygen sensing field, the composite is in pure nitrogen gas
With the luminous strength ratio [I (N in purity oxygen2)/I(O2)] it is 2.9~6.3.
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| CN101143875A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院化学研究所 | Pyrenes derivative, preparation method and application thereof |
| CN101717629A (en) * | 2009-07-06 | 2010-06-02 | 中国科学院长春光学精密机械与物理研究所 | Optical oxygen sensing composite material and preparation method thereof |
| CN101935529A (en) * | 2010-07-13 | 2011-01-05 | 中国科学院长春光学精密机械与物理研究所 | Multifunctional nano-composite having up-conversion luminescence, oxygen sensing and biological connectivity and preparation method thereof |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621486A (en) * | 2004-10-19 | 2005-06-01 | 吉林大学 | Ruthenium complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing |
| CN101143875A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院化学研究所 | Pyrenes derivative, preparation method and application thereof |
| CN101717629A (en) * | 2009-07-06 | 2010-06-02 | 中国科学院长春光学精密机械与物理研究所 | Optical oxygen sensing composite material and preparation method thereof |
| CN101935529A (en) * | 2010-07-13 | 2011-01-05 | 中国科学院长春光学精密机械与物理研究所 | Multifunctional nano-composite having up-conversion luminescence, oxygen sensing and biological connectivity and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Mesostructured Silica Chemically Doped with RuII as a Superior Optical Oxygen Sensor;Bingfu Lei 等;《Adv. Funct. Mater.》;20060808;第16卷;1883-1891 * |
| Phenanthroline ligands with divergent pyridine units;Myroslav o. Vysotsky;《JOURNAL OF CHEMICAL RESEARCH》;20090331;133-136 * |
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