CN105754594A - Fluorescent carbon dot/mesoporous molecular sieve composite luminescent material as well as preparation and application of fluorescent carbon dot/mesoporous molecular sieve composite luminescent material - Google Patents
Fluorescent carbon dot/mesoporous molecular sieve composite luminescent material as well as preparation and application of fluorescent carbon dot/mesoporous molecular sieve composite luminescent material Download PDFInfo
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Abstract
The invention belongs to the field of composite luminescent materials and discloses a fluorescent carbon dot/mesoporous molecular sieve composite luminescent material, a preparation method of the composite luminescent material and application of the composite luminescent material in the aspect of oxygen sensing. The preparation method of the composite luminescent material comprises the following steps: (1) preparing silane functionalized fluorescent carbon dots: under a stirring condition, adding anhydrous citric acid into a silane coupling agent and reacting at a constant temperature; purifying to obtain silane functionalized fluorescent quantum dots; (2) preparing the fluorescent carbon dot/mesoporous molecular sieve composite luminescent material: under the condition of taking ethanol as a solvent, taking a mesoporous molecular sieve to react with the silane functionalized fluorescent carbon dots prepared in the step (1) and purifying to obtain the fluorescent carbon dot/mesoporous molecular sieve composite luminescent material. The preparation method is simple, and the raw materials are low in price and have no toxin; the prepared composite luminescent material has high sensitivity and selectivity, stable performance, and quick response, the emission intensity is sensitive to oxygen concentration, and the composite luminescent material is an economical type green and environment-friendly oxygen sensing material.
Description
Technical field
The invention belongs to composite luminescent material field, particularly to a kind of fluorescent carbon point/mesoporous molecular sieve composite luminescent material and preparation thereof and application in oxygen sensor.
Background technology
Along with the progress of science and technology, sensing technology serves pivotal role in various aspects such as environmental conservation, national defense construction, universe explorations.Since first Freeman in 1978 et al. works out chemiluminescence hydrogen peroxide sensor, optical pickocff causes AC and more and more pays close attention to.The luminous intensity of luminescent chemical sensing material, luminous peak position or lifetime of excited state change with surrounding chemical environment change, thus realizing the sensor measuring to determinand.The interference of scattering light background when not having an external excitation source based on luminous sensing and detection method, thus luminescent chemical sensing material has the features such as high sensitivity, high selectivity.The performances such as a lot of luminescent chemical sensing materials and oxygen molecule effect make the luminous intensity of light emitting molecule, lifetime of excited state change, and therefore these materials may be used for the application of research oxygen sensor aspect.
In conventional research, the emitting complexes of the noble metal such as platinum and ruthenium is commonly used for oxygen sensor, but owing to such noble metal price is high, is greatly limited in production application.And fluorescent carbon point preparation is simple, raw material used is cheap and environmental protection, as a kind of advanced luminescent material, not only there is excellent optical property and small size property, and also have good biocompatibility and low cytotoxicity, in bio-imaging, labelling and catalysis, sensory field presents good application prospect.Fluorescent carbon point replaces precious metals complex to be the important trend that oxygen sensor develops.Luminescent chemical sensing material is determined by light emitting molecule and two principal elements of carrier material, and novel carrier exploitation is significant for developing high-performance oxygen sensor material and device further.
Summary of the invention
In order to overcome shortcoming and the deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is in that the preparation method providing a kind of fluorescent carbon point/mesoporous molecular sieve composite luminescent material.
Another object of the present invention is in that the fluorescent carbon point/mesoporous molecular sieve composite luminescent material providing said method to prepare.
Still a further object of the present invention is in that the application providing above-mentioned fluorescent carbon point/mesoporous molecular sieve composite luminescent material in oxygen sensor.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material, it mainly includes step in detail below:
(1) preparation of silane-functionalized fluorescent carbon point: under agitation, adds anhydrous citric acid, isothermal reaction in silane coupler, obtains silane-functionalized fluorescent carbon point after purification；
(2) preparation of fluorescent carbon point/mesoporous molecular sieve composite luminescent material: when ethanol is solvent, take mesopore molecular sieve to react with the silane-functionalized fluorescent carbon point of preparation in step (1), purification, obtains fluorescent carbon point/mesoporous molecular sieve composite luminescent material.
Mesopore molecular sieve described in step (2) is at least one in MCM-41, MCM-48, SBA-15 and ZSM-5.
The mesopore molecular sieve that amount is every 0.4g of silane-functionalized fluorescent carbon quantum dot used in step (2) uses the silane-functionalized fluorescent carbon quantum dot of 0.007～0.2mL.
Reaction described in step (2) is stirring reaction 8h under room temperature, and the speed wherein stirred is 300rpm.
Purification described in step (2) refers to gained reacting liquid filtering, gained precipitation is washed with water 3～5 times, dry, obtains the fluorescent carbon point/mesoporous molecular sieve composite luminescent material after purification.
Silane coupler described in step (1) is KH-602.
Isothermal reaction described in step (1) refers to reaction 3min at 240 DEG C.
Stirring described in step (1) refers to that mixing speed is 300rpm.
The silane coupler that amount is every 1mL of anhydrous citric acid used in step (1) uses the anhydrous citric acid of 0.05g.
Purification described in step (1) refers to and gained reactant liquor is cooled to room temperature, adds petroleum ether extraction, obtains the silane-functionalized fluorescent carbon point after purification.
Operation in step (1) carries out all under nitrogen protection.
A kind of fluorescent carbon point/mesoporous molecular sieve composite luminescent material prepared by said method.
Above-mentioned fluorescent carbon point/mesoporous molecular sieve composite luminescent material is to oxygen sensitive, can as oxygen sensor material, it is fixed in the substrate of printing opacity or is coated in that blue light is inorganic or Organic Light Emitting Diode surface, mixing photodiode and carry out signal detection, oxygen sensor device can be prepared.
The mechanism of the present invention is:
Carbon point has sensing capabilities, and namely assembled material also has sensing capabilities, and the pore passage structure in MCM-41 and SBA-15 is Hexagonal array, mutually isolated between duct；Pore passage structure in MCM-48 is cubic array, is mutually communicated between duct；ZSM-5 has the 3 D pore canal of MFI structure.The present invention by being assembled into silica mesoporous zeolite MCM-41 by fluorescent carbon point, MCM-48, in SBA-15 and ZSM-5 duct, owing to carbon point has sensing capabilities, namely assembled material also has sensing capabilities, carbon point exists with solution, and carbon point is assembled in mesopore molecular sieve and presents pressed powder, better it is applied in real life, and mesopore orbit itself can improve the selectivity of functional molecular, bigger specific surface area can make fluorescent carbon point reach high degree of dispersion state, improve the sensitivity of this functional molecular, therefore adopt mesopore molecular sieve as carrier, can largely improve the oxygen sensor performance of this assembled material.
The present invention, relative to prior art, has such advantages as and beneficial effect:
In the present invention, the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material is simple, consuming time short, prepared material non-toxic inexpensive, environmentally friendly, lower cost basis obtains high yield, it is easy to industrialized production, sensing capabilities aspect sensitivity and selectivity are high, stable performance.
Accompanying drawing explanation
Fig. 1 is carbon point/MCM-41 composite luminescent material emission spectrum under different oxygen concentrations in embodiment 1.
Fig. 2 is carbon point/MCM-48 composite luminescent material emission spectrum under different oxygen concentrations in embodiment 2.
Fig. 3 is carbon point/SBA-15 composite luminescent material emission spectrum under different oxygen concentrations in embodiment 3.
Fig. 4 is carbon point/ZSM-5 composite luminescent material emission spectrum under different oxygen concentrations in embodiment 4.
Fig. 5 is the luminous intensity and the graph of a relation of time that in embodiment 1～4, the fluorescent carbon point/mesoporous molecular sieve composite luminescent material of preparation is measured when periodic transformation pure nitrogen gas and purity oxygen.
Fig. 6 is the typical luminous intensity Stern-Volmer graph of a relation of the fluorescent carbon point/mesoporous molecular sieve composite luminescent material of preparation in embodiment 1～4.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In embodiment, other reagent used all can be buied in market.
Embodiment 1: the preparation of carbon point/MCM-41 composite luminescent material
(1) preparation of silane-functionalized fluorescent carbon point: 30mL silane coupler KH-602 is joined in 100mL there-necked flask, first use nitrogen degassed 10 minutes, and it is heated to 240 DEG C, experiment whole process is connected with nitrogen, 1.5g anhydrous citric acid is rapidly joined in high degree of agitation situation, take out after isothermal reaction 3min and naturally cool to room temperature, after crude product petroleum ether three times final silane-functionalized fluorescent carbon quantum dot；
(2) preparation of inorganic carrier Mesoporous silica MCM 41: can refer to literature method and obtain (C.T.Kresge, M.E.Leonowicz, W.J.Roth, J.C.Vartuli, J.S.Beck, Nature, 1992,359,710；nullJ.S.Beck,J.C.Vartuli,W.J.Roth,M.E.Leonowicz,C.T.Kresge,K.D.Schmitt,C.T.-W.Chu,D.H.Olson,E.W.Sheppard,S.B.McCullen,J.B.Higgins,J.L.Schlenker,J.Am.Chem.Soc.1992,114,10834.)，It concretely comprises the following steps: 36mL strong aqua ammonia and 78mL deionized water are mixed，Cetyl trimethylammonium bromide (CTAB) surfactant of 3.3g is added at 35 DEG C，15mL tetraethyl orthosilicate (TEOS) is added after stirring to clarify，At room temperature transfer in reactor after stirring 10h，Crystallization 48 hours at 100 DEG C，After filtration with deionized water rinsing several times，Dry 6h at 60 DEG C，550 DEG C of calcining 6h，Obtain inorganic carrier Mesoporous silica MCM 41.
(3) weigh 0.4gMCM-41, add 0.007mL silane-functionalized fluorescent carbon point, measure 30mL ethanol in 100mL single port flask, under normal temperature condition, magnetic agitation 8 hours, filters solution, and with distilled water wash 3 times, in 60 DEG C of baking ovens dry 12 hours, namely obtain sample.
Embodiment 2: the preparation of carbon point/MCM-48 composite luminescent material
(1) silane-functionalized fluorescent carbon point is prepared by the method for embodiment 1；
(2) preparation of inorganic carrier mesoporous material MCM-48: can refer to literature method and obtain (D.Zhao, Q.Huo, J.Feng, B.F.Chmelka, G.D.Stucky, J.Am.Chem.Soc.1998,120,6024；J.Xu, Z.H.Luan, L.Kevan, Chem.Mater, 1998,10,3690-3698), it concretely comprises the following steps: according to TEOS:CTAB:NaOH:H2The ratio of O=1:0.6:0.47:65, weigh 10.95g cetyl trimethylammonium bromide (CTAB), it is dissolved in 59.1mL deionized water, it is subsequently adding 0.94gNaOH, and maintenance system constant temperature at 35 DEG C stirs a period of time and makes it dissolve, it is slowly added to 9.7mL tetraethyl orthosilicate (TEOS), continues stirring 4～5h.Move in the reactor of teflon gasket, 100 DEG C of crystallization 48h, filter, with deionized water wash, 60 DEG C of dry 12h.Put into Muffle furnace after drying, be warming up at 550 DEG C with the speed of 1 DEG C/min and calcine 6h, obtain inorganic carrier mesoporous material MCM-48.
(3) weigh 0.4gMCM-48, add 0.077mL silane-functionalized fluorescent carbon point, measure 30mL ethanol in 100mL single port flask, under normal temperature condition, magnetic agitation 8 hours, filters solution, and with distilled water wash 3 times, in 60 DEG C of baking ovens dry 12 hours, namely obtain sample.
Embodiment 3: the preparation of carbon point/SBA-15 composite luminescent material
(1) silane-functionalized fluorescent carbon point is prepared by the method for embodiment 1；
(2) preparation of inorganic carrier mesoporous material SBA-15: (B.F.Lei can be obtained according to literature method, L.Wang, H.R.Zhang, Y.L.Liu, H.W.Dong, M.T.Zheng, X.H.Zhou, SensActuatorsBChem.2016,10,1016), it concretely comprises the following steps: weigh 6gP123 in round-bottomed flask, adds the 225mL mixed liquor of the 2mol/L hydrochloric acid containing 180mL and 45mL deionized water, in 35 DEG C of stirring in water bath uniformly to clarification, and drip 13.8mL tetraethyl orthosilicate, keep 25 DEG C of stirring 24h.Load liner be politef reactor in 100 DEG C of hydrothermal treatment consists 48h, take out after cooling, sucking filtration, and with deionized water cyclic washing 5 times, once, the powder body obtained be in 60 DEG C of oven dryings, stand-by for washing with alcohol.Dried powder body is transferred in clean corundum crucible, calcines 6h in shaft furnace 550 DEG C, heat up with the speed of 1 DEG C/min.Calcining removes surfactant, obtains inorganic carrier mesoporous material SBA-15.
(3) weigh 0.4gSBA-15, add 0.077mL silane-functionalized fluorescent carbon point, measure 30mL ethanol in 100mL single port flask, under normal temperature condition, magnetic agitation 8 hours, filters solution, and with distilled water wash 3 times, in 60 DEG C of baking ovens dry 12 hours, namely obtain sample.
Embodiment 4: the preparation of carbon point/ZSM-5 composite luminescent material
(1) silane-functionalized fluorescent carbon point is prepared by the method for embodiment 1；
(2) preparation of inorganic carrier mesoporous material ZSM-5: can refer to literature method and obtain (M.R.Li, I.N.Oduro, Y.P.Zhou, Y.Huang, Y.M.Fang, MicroporousMesoporousMater.2016,221,108-116.), it concretely comprises the following steps: according to Al2O3:TPABr:Na2O:SiO2:TPOAC:H2The ratio of O=1:9:9:39:1.9:6220.Weigh 0.75gNaAlO27.0g 4-propyl bromide (TPABr) and 2.0gNaOH are dissolved in 337.5g water, under agitation, 21.43g tetraethyl orthosilicate (TEOS) and 3.96g dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride (TPOAC) are added.After at room temperature stirring 2 hours, load liner be politef reactor in 150 DEG C of hydrothermal treatment consists 60h, take out after cooling, sucking filtration, and with deionized water cyclic washing 5 times, once, the powder body obtained be in 60 DEG C of oven dryings, stand-by for washing with alcohol.Dried powder body is transferred in clean corundum crucible, is warming up to 550 DEG C of calcining 5h in shaft furnace with the speed of 1 DEG C/min, obtains inorganic carrier mesoporous material ZSM-5.
(3) weigh 0.4gZSM-5, add 0.2mL silane-functionalized fluorescent carbon point, measure 30mL ethanol in 100mL single port flask, under normal temperature condition, magnetic agitation 8 hours, filters solution, and with distilled water wash 3 times, in 60 DEG C of baking ovens dry 12 hours, namely obtain sample.
Embodiment 5: the test of the oxygen sensor performance of carbon containing point/MCM-41 composite luminescent material
The carbon prepared in embodiment 1 point/MCM-41 composite luminescent material is attached in the sample cell that diameter is 10 millimeters and thickness is 1 millimeter, sample cell is placed in air chamber, by oxygen and nitrogen gas concn in gas flow-control air chamber, utilize Hitachi's F-7000 fluorescence spectrophotometer test emission spectrum of this composite luminescent material under different oxygen concentrations, result is as shown in Figure 1, the excitation wavelength wherein tested is 370nm, and launching wavelength is 454nm, I0/I100=2.83 (I0It is under 100% condition of nitrogen gas, test the fluorescence intensity obtained, I100It is under 100% Oxygen Condition, test the fluorescence intensity obtained).Composite luminescent material luminous intensity and relation of time when periodic transformation pure nitrogen gas and purity oxygen in testing example 1 simultaneously, result is as shown in Figure 5, as can be seen from Figure 5, cancellation degree is 64.66%, response time (arrives required time during 95% of emissive porwer purity oxygen) for 4.98s when being changed to purity oxygen from pure nitrogen gas, the recovery time (rises to the time required during the 95% of peak) for 33.59s when arriving pure nitrogen gas when being changed to pure nitrogen gas from purity oxygen.Illustrate that this composite has good oxygen sensor performance.
Embodiment 6: the oxygen sensor performance test of carbon point/MCM-48 composite luminescent material
The carbon prepared in embodiment 2 point/MCM-48 composite luminescent material is attached in the sample cell that diameter is 10 millimeters and thickness is 1 millimeter, sample cell is placed in air chamber, by oxygen and nitrogen gas concn in gas flow-control air chamber, utilize Hitachi's F-7000 fluorescence spectrophotometer test emission spectrum of this composite luminescent material under different oxygen concentrations, result is as shown in Figure 2, the excitation wavelength wherein tested is 370nm, and launching wavelength is 454nm, I0/I100=5.23 (I0It is under 100% condition of nitrogen gas, test the fluorescence intensity obtained, I100It is under 100% Oxygen Condition, test the fluorescence intensity obtained).Composite luminescent material luminous intensity and relation of time when periodic transformation pure nitrogen gas and purity oxygen in testing example 2 simultaneously, result is shown in Fig. 5, and wherein cancellation degree is 80.88%, and response time is 8.09s, and the recovery time is 45.71s.Illustrate that this composite has good oxygen sensor performance.
Embodiment 7: the oxygen sensor performance test of carbon point/SBA-15 composite luminescent material
The carbon prepared in embodiment 3 point/SBA-15 composite luminescent material is attached in the sample cell that diameter is 10 millimeters and thickness is 1 millimeter, sample cell is placed in air chamber, by oxygen and nitrogen gas concn in gas flow-control air chamber, utilizing Hitachi's F-7000 fluorescence spectrophotometer test emission spectrum of this composite luminescent material under different oxygen concentrations, result is as shown in Figure 3.The excitation wavelength wherein tested is 370nm, and launching wavelength is 454nm, I0/I100=2.58 (I0It is under 100% condition of nitrogen gas, test the fluorescence intensity obtained, I100It is under 100% Oxygen Condition, test the fluorescence intensity obtained), composite luminescent material luminous intensity and relation of time when periodic transformation pure nitrogen gas and purity oxygen in testing example 3 simultaneously, result is shown in Fig. 5, wherein cancellation degree be 61.24%, response time is 8.27s, and the recovery time is 19.55s.Illustrate that this composite has good oxygen sensor performance.
Embodiment 8: the oxygen sensor performance test of carbon point/ZSM-5 composite luminescent material
The carbon prepared in embodiment 4 point/ZSM-5 composite luminescent material is attached in the sample cell that diameter is 10 millimeters and thickness is 1 millimeter, sample cell is placed in air chamber, by oxygen and nitrogen gas concn in gas flow-control air chamber, utilize Hitachi's F-7000 fluorescence spectrophotometer test emission spectrum of this composite luminescent material under different oxygen concentrations, as shown in Figure 4.The excitation wavelength wherein tested is 370nm, and launching wavelength is 465nm, I0/I100=1.98 (I0It is under 100% condition of nitrogen gas, test the fluorescence intensity obtained, I100It is under 100% Oxygen Condition, test the fluorescence intensity obtained), composite luminescent material luminous intensity and relation of time when periodic transformation pure nitrogen gas and purity oxygen in testing example 4 simultaneously, result is shown in Fig. 5, wherein cancellation degree be 49.49%, response time is 4.97s, and the recovery time is 35.14s.Illustrate that this composite has good oxygen sensor performance.
With Demas double; two case model, the luminous intensity data under different oxygen concentrations of the composite luminescent material prepared by embodiment 1～4 are fitted, result as shown in Figure 6, wherein I0For the luminous intensity that oxygen concentration is when 0, I is the luminous intensity under different oxygen concentration.From fig. 6 it can be seen that the double; two case model of DemasComposite luminescent material prepared by embodiment 1～4 all can be carried out good matching.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material, it is characterised in that include step in detail below:
(1) preparation of silane-functionalized fluorescent carbon point: under agitation, adds anhydrous citric acid, isothermal reaction in silane coupler, obtains silane-functionalized fluorescent carbon quantum dot after purification；
(2) preparation of fluorescent carbon point/mesoporous molecular sieve composite luminescent material: when ethanol is solvent, take mesopore molecular sieve to react with the silane-functionalized fluorescent carbon point of preparation in step (1), purification, obtains fluorescent carbon point/mesoporous molecular sieve composite luminescent material.
2. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that:
Mesopore molecular sieve described in step (2) is at least one in MCM-41, MCM-48, SBA-15 and ZSM-5.
3. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that:
The mesopore molecular sieve that amount is every 0.4g of silane-functionalized fluorescent carbon quantum dot used in step (2) uses the silane-functionalized fluorescent carbon quantum dot of 0.007～0.2mL.
4. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that:
Reaction described in step (2) is stirring reaction 8h under room temperature, and the speed wherein stirred is 300rpm.
5. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that:
Purification described in step (2) refers to gained reacting liquid filtering, gained precipitation is washed with water 3～5 times, dry, obtains the fluorescent carbon point/mesoporous molecular sieve composite luminescent material after purification.
6. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that:
Silane coupler described in step (1) is KH-602；
Isothermal reaction described in step (1) refers to reaction 3min at 240 DEG C；
Stirring described in step (1) refers to that mixing speed is 300rpm.
7. the preparation method of fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterised in that: the silane coupler that amount is every 1mL of anhydrous citric acid used in step (1) uses the anhydrous citric acid of 0.05g.
8. fluorescent carbon point/mesoporous molecular sieve composite luminescent material according to claim 1, it is characterized in that: the purification described in step (1) refers to and gained reactant liquor is cooled to room temperature, add petroleum ether extraction, obtain the silane-functionalized fluorescent carbon point after purification.
9. fluorescent carbon point/mesoporous molecular sieve composite luminescent material that the method according to any one of claim 1～8 prepares.
10. fluorescent carbon point/the mesoporous molecular sieve composite luminescent material according to claim 9 application in oxygen sensor.
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