CN105368444B - Converting system on a kind of efficient green dim light based on protonic solvent - Google Patents
Converting system on a kind of efficient green dim light based on protonic solvent Download PDFInfo
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Abstract
The invention belongs to nonlinear optical material field, converting system on a kind of efficient green dim light based on protonic solvent is specifically disclosed, can be by aprotic medium come the raising sensitizer triplet of simple and efficient.In low power density green glow（532 nm, 60 mWcm‑2) excite down, PdTPP/DPA/ propyl alcohol/ethylene glycol (v/v, 1/2)（Protonic solvent）Obtain blue up-conversion luminous in system, upper conversion efficiency（ΦUC）Up to 29.1%.There is provided one easily thinking bury in oblivion upper conversion efficiency to improve triplet state triplet state, using solvent Micro-environmental effects, so as to avoid the complexity of common organic synthesis method and be unfavorable for ecological environmental protection.The present invention can be used for PhotoelectrochemicalSystem System for Hydrogen Production, have potential application value in fields such as photovoltaic field, solar energy photocatalytic and environmental photochemistry technologies.
Description
Technical field
The invention belongs to nonlinear optical material field, and in particular to one kind is using protonic solvent as medium, containing certain
Converting system on the sensitising agent of ratio and the efficient dim light of luminous agent.
Background technology
Upper conversion based on organic photon material is to absorb low-energy light using organic molecule then to launch high-energy light
Process, so just simply realize the process that the light from long wavelength is changed to the light of short wavelength.At present, turn on organic photon
Two kinds of technologies are changed：One kind is changed in two-photon absorption（Two-Photon-Absorption Upconversion, TPA-
UC）, it is another, it is to be changed in triplet state-triplet state annihilation（Triplet-Triplet-Annihilation
Upconversion, TTA-UC）.Because TPA-UC fluorescence and TTA-UC fluorescence its intensity with excitating light strength are in quadratic power
Relation, therefore TPA-UC and TTA-UC show nonlinear optical properties.Wherein, TPA-UC（Changed in two-photon absorption）Need
Very strong excitation source is excited, and its optical intensity density is up to MW-GM/cm2, it is more than 1,000,000 times of sunlight intensity（Earth's surface
Solar radiation energy is 0.1 W × cm-2）, so sunshine can not as this technology excitation source；And TPA-UC
（Changed in two-photon absorption）It is inefficient（Much smaller than 20%）.These reasons result in the application changed in two-photon absorption
It is restricted.Changed relative on two-photon（TPA-UC）, change in triplet state-triplet state annihilation（TTA-UC）With following excellent
Gesture：The energy density of exciting light as needed for TTA-UC is low（Usually less than 100mW/cm2, close to sunshine earth's surface radiation energy
Amount）, therefore, TTA-UC technologies are in field of solar energy utilization（Such as photovoltaic and photocatalysis）With extremely tempting application prospect.Together
When, sensitising agent and luminous agent needed for TTA-UC are relatively easy to compounding, easily realize that excitation wavelength and the tunable of launch wavelength are obtained
Obtain the upper conversion of different-waveband.It can be seen that, due to TTA-UC materials with technology in field of solar energy utilization（As photovoltaic cell, light are urged
Change, light compositing and light degradation）, three-dimensional mangement, fluorescence molecule biomarker and the high-tech area performance such as photodynamics is for cancer
Go out good application prospect and high additive value, research TTA-UC materials and the hair that switch technology is changed to improve on TTA thereon
Light efficiency turns into the study hotspot of current scientific research circle.
At present, the upper conversion efficiency of TTA-UC materials in the solution is higher, far above the upper conversion efficiency of solid-state material（It is low
In 1%）, therefore, the TTA-UC materials based on solution state have application value with technology.However, usual organic up-conversion is only
It is dissolved in organic solvent（Such as benzene, toluene, DMF, dichloromethane, acetonitrile）, these organic solvent toxicities and volatility are greatly, serious to limit
Its application is made.On the other hand, in order to obtain converting system on efficient TTA-, current researchers are directed to researching and developing high triplet
The new sensitizer of energy level, however, these new sensitizer molecules synthesis steps are multiplied, cost is high, cost performance is low, be unfavorable for ring
Border.Therefore, develop the upper conversion medium of green, the technology for the triplet for improving sensitizer found, to obtain efficient green
The upper converting systems of TTA-, have and its important environment protection significance and application value.
The content of the invention
It is uniform solution system, the dim light it is an object of the invention to provide converting system on a kind of efficient green dim light
Upper converting system is in relatively low exciting power（Energy density is 60 mW/cm2）Energy upconversion, upper conversion can still occur under irradiation
Efficiency high is especially environment-friendly up to 29.1%（Low toxicity and non-volatile）, there is application prospect in terms of photovoltaic, photocatalysis.
To achieve the above object of the invention, the technical solution adopted by the present invention is：It is a kind of efficient weak based on protonic solvent
Converting system on light, including sensitising agent, luminous agent and protonic solvent；
The chemical structure of general formula of the sensitising agent is as follows：
Wherein substituent R is hydrogen, methyl, bromine or hydroxyl；M is palladium or platinum；
The chemical structure of general formula of the luminous agent is as follows：
Wherein substituent R1For phenyl, 4- methylbenzenes or naphthyl；
The protonic solvent is the mixed solvent of propyl alcohol and ethylene glycol.
It is preferred that technical scheme in, in the chemical structure of general formula of the sensitising agent, R be hydrogen or methyl, M is palladium；It is described
In the chemical structure of general formula of luminous agent, R1For phenyl.In relatively low exciting power（Energy density is 60 mW/cm2）Still may be used under irradiation
Generation Energy upconversion, upper conversion efficiency is up to 29.1%, achieves unexpected technique effect.
In above-mentioned technical proposal, the mol ratio of the sensitising agent and luminous agent is 1: (1~350), it is preferably in a proportion of 1:
300。
In above-mentioned technical proposal, on the efficient dim light in converting system, the concentration of luminous agent is 8 × 10-6~2.8 ×
10-3Mol/L, preferred concentration is 2.4 × 10-3 mol/L。
In above-mentioned technical proposal, in the protonic solvent, the volume ratio of propyl alcohol and ethylene glycol is（0.5~2）∶1；It is preferred that
0.5.The good solvent of stable homogeneous state, and modest viscosity can be formed；It is advantageously implemented triplet state and buries in oblivion upper conversion, it is upper to turn
Efficiency high is changed up to 29.1%, unexpected technique effect is achieved.
It is preferred that, on the efficient dim light in converting system, concentration is additionally added for 0~3.0 mM, and not β-ring paste for 0
Essence.Beta-schardinger dextrin can form stable aprotic medium with propyl alcohol/ethylene glycol protonic solvent, further improve conversion effect
Rate, up to 35.86%.
The invention also discloses the preparation method of converting system on the above-mentioned efficient dim light based on protonic solvent, including with
Lower step：Photosensitizing agent solution and luminous agent solution are added in container；Add a small amount of protonic solvent；It is ultrasonically treated；Finally drip
Protonation solvent constant volume, so as to obtain converting system on the efficient dim light based on protonic solvent.To make solute preferably molten
Solution, the present invention first plus after the processing of a small amount of solvent supersonic adds solvent constant volume again, it is to avoid because material is difficult when solvent once is added
It is molten and complete defect can not be dissolved.
In above-mentioned technical proposal, the photosensitizing agent solution, the concentration of luminous agent solution are respectively 1 × 10-4~2 × 10-3
mol/L、1×10-3~8 × 10-2 mol/L.In the present invention, dissolving sensitising agent, the solvent of luminous agent are not selected especially, can
Solvent is CHCl in excellent dissolution, such as described photosensitizing agent solution3；Solvent is DMF in the luminous agent solution.The present invention
Upper conversion is buried in oblivion for triplet state as new effective medium using protonic solvent first, the medium is respectively not consubstantiality
The mixed solvent of propyl alcohol/ethylene glycol of product ratio, by sensitising agent and luminous agent formation solution in a solvent scattered by a certain percentage
Conversion compound system is obtained, in relatively low exciting power（Energy density is 60 mW/cm2）Can still occur to turn on energy under irradiation
Change, upper conversion efficiency is up to 29.1%, achieve unexpected technique effect.
It is preferred that, add after protonic solvent；It is ultrasonically treated, then add beta-schardinger dextrin；Protic is finally added dropwise molten
Agent constant volume.Beta-schardinger dextrin can improve the efficiency of the upper converting system in part, but be influenceed very big by the dielectric material in system, than
Such as toluene system, conversion efficiency in reverse effect, reduction will be obtained；The present invention adds beta-schardinger dextrin, with propyl alcohol/ethylene glycol
Homogeneous aprotic medium is formed, conversion efficiency is further improved, achieves unexpected technique effect.
It is including following the invention also discloses a kind of method that sensitising agent triplet is improved by aprotic medium effect
Step, photosensitizing agent solution is added in container；Then protonic solvent is added；It is ultrasonically treated；Complete sensitising agent triplet state energy
The raising of level；The chemical structure of general formula of the sensitising agent is as follows：
Wherein substituent R is hydrogen, methyl, bromine or hydroxyl；M is palladium or platinum；
The protonic solvent is the mixed solvent of propyl alcohol and ethylene glycol.
In above-mentioned technical proposal, the photosensitizing agent solution concentration is 1 × 10-4~2 × 10-3 mol/L；The luminous agent is molten
Liquid concentration is 1 × 10-3~8 × 10-2 mol/L；In the protonic solvent, the volume ratio of propyl alcohol and ethylene glycol is（0.5~2）∶
1.By the inventive method simple process, sensitising agent triplet can reach 1.725eV, significantly larger than existing photosensitizing agent solution
System.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
1st, the first public a kind of efficient dim light of sensitising agent/luminous agent by medium of protonic solvent of the present invention
Upper converting system, it dissolves in sensitising agent and luminous agent using protonic solvent as medium according to proportioning；It is micro- by improving
Environmental effect obtains the raising of conversion efficiency on dim light, and the upper high conversion efficiency of sensitising agent, reachable in protonic solvent
29.1%；
2nd, converting system on the first public efficient dim light based on protonic solvent of the present invention, in low power density green glow
（532 nm, 60 mWcm-2) excite down, with propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent as medium, changed on dim light
System PdTPP/DPA is obtained and changed in blueness, and its efficiency is up to 29.1%；By adding beta-schardinger dextrin, with propyl alcohol/ethylene glycol
Homogeneous aprotic medium is formed, conversion efficiency is further improved, green wood is provided for the application in terms of photovoltaic, photocatalysis
Material；
3rd, sensitising agent triplet simple and easy method is improved with aprotic medium the invention discloses one kind, passes through proton
The use of medium, greatly improved the triplet of sensitizer（ET1It can reach 1.725eV）, extend the sensitizer triplet state longevity
Order (tP2), accelerate the energy transfer (k of triplet stateq), it is final to obtain efficiently upper converting system；Far above existing photosensitizing agent solution body
System, overcome prior art still can not effectively improve the defect of sensitising agent triplet by complicated organic synthesis；
4th, converting system is prepared simply, without complicated mistake on the efficient dim light disclosed by the invention based on protonic solvent
Journey, upper high conversion efficiency specifically avoid poisonous and hazardous organic solvent, such as the use of benzene kind solvent, safety and environmental protection is applicable
In industrialized production.
Brief description of the drawings
Ultravioletvisible absorption and luminescent spectrum figure that accompanying drawing 1 is PdTPP in different protonic solvents；
The phosphorescent lifetime figure that accompanying drawing 2 is PdTPP in different protonic solvents；
The up-conversion luminescence spectrogram that accompanying drawing 3 is PdTPP/DPA in different protonic solvents；
The up-conversion luminescence spectrogram that accompanying drawing 4 is beta-schardinger dextrin/PdTPP/DPA in propyl alcohol/ethylene glycol solvent；
The up-conversion luminescence spectrogram that accompanying drawing 5 is PdMeTPP/DPA in different protonic solvents.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
In embodiment monopropylene glycol/ethylene glycol (v/v, 2/1) on PdTPP/DPA converting system preparation
Metalloporphyrins in the present embodiment for sensitising agent are PdTPP, and molecular structural formula is：
The substitution anthracene derivants of 9,10- bis- in the present embodiment for luminous agent are DPA, and molecular structural formula is：
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 2/1) mixed solvent and then careful vibration mixing are added, is surpassed
Sonication, is finally slowly added dropwise propyl alcohol/ethylene glycol (v/v, 2/1) mixed solvent constant volume, is configured to 5mL sensitising agent and lights
The molar ratio of agent is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is
60 mW×cm-2）Blue up-converted fluorescence can be obtained, its efficiency is up to 22.9%.
In two propyl alcohol of embodiment/ethylene glycol (v/v, 1/1) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/1) mixed solvent and then careful vibration mixing are added, is surpassed
Sonication, is finally slowly added dropwise propyl alcohol/ethylene glycol (v/v, 1/1) mixed solvent constant volume, is configured to 5mL sensitising agent and lights
The molar ratio of agent is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is
60 mW×cm-2）Blue up-converted fluorescence can be obtained, its efficiency is up to 25.4%.
In three propyl alcohol of embodiment/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing are added, is surpassed
Sonication, is finally slowly added dropwise propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent constant volume, is configured to 5mL sensitising agent and lights
The molar ratio of agent is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is
60 mW×cm-2）Blue up-converted fluorescence can be obtained, its efficiency is up to 29.1%.
Accompanying drawing 1 is above-mentioned sensitising agent PdTPP in protonic solvent propyl alcohol/ethylene glycol (v/v, 2/1), propyl alcohol/ethylene glycol
Ultraviolet-visible absorption spectroscopy and luminescent spectrum in (v/v, 1/1) and propyl alcohol/ethylene glycol (v/v, 1/2).PdTPP is in not homogeneity
Absorption peak position in sub- property solvent is more similar, and simply absorbability is slightly different；With the increase of solvent polarity, PdTPP's
The obvious blue shift of luminous peak position, phosphorescence luminous intensity is significantly increased.
Accompanying drawing 2 is above-mentioned sensitising agent PdTPP in protonic solvent propyl alcohol/ethylene glycol (v/v, 2/1), propyl alcohol/ethylene glycol
Phosphorescent lifetime in (v/v, 1/1) and propyl alcohol/ethylene glycol (v/v, 1/2), PdTPP phosphorescent lifetimes are long, and phosphor-decay is slow, after
And triplet excited state life-span and triplet emittance are improved, it is beneficial to sensitising agent and transits to triplet state.
Accompanying drawing 3 be above-mentioned upper conversion component PdTPP/DPA at protonic solvent propyl alcohol/ethylene glycol (v/v, 2/1), propyl alcohol/
Up-conversion luminescence spectrum in ethylene glycol (v/v, 1/1) and propyl alcohol/ethylene glycol (v/v, 1/2), it can be seen that body of the invention
It is that Up-conversion Intensity is big, upper high conversion efficiency, up to 29.1%.
In example IV beta-schardinger dextrin/propyl alcohol/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing, ultrasound are added
Processing, adds 400 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, be finally slowly added dropwise propyl alcohol/ethylene glycol (v/v,
1/2) mixed solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:100 upper conversion mixed solution.
In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, it is imitated
Rate is up to 31.63%.
In five beta-schardinger dextrins of embodiment/propyl alcohol/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing, ultrasound are added
Processing, adds 800 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, be finally slowly added dropwise propyl alcohol/ethylene glycol (v/v,
1/2) mixed solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:200 upper conversion mixed solution.
In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, it is imitated
Rate is up to 34.22%.
In six beta-schardinger dextrins of embodiment/propyl alcohol/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing, ultrasound are added
Processing, adds 1000 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, be finally slowly added dropwise propyl alcohol/ethylene glycol (v/v,
1/2) mixed solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:250 upper conversion mixed solution.
In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, it is imitated
Rate is up to 35.48%.
In seven beta-schardinger dextrins of embodiment/propyl alcohol/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing, ultrasound are added
Processing, adds 1200 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, be finally slowly added dropwise propyl alcohol/ethylene glycol (v/v,
1/2) mixed solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:300 upper conversion mixed solution.
In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, it is imitated
Rate is up to 35.89%.
In eight beta-schardinger dextrins of embodiment/propyl alcohol/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing, ultrasound are added
Processing, adds 1400 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, be finally slowly added dropwise propyl alcohol/ethylene glycol (v/v,
1/2) mixed solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:350 upper conversion mixed solution.
In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, it is imitated
Rate is up to 35.83%.
Accompanying drawing 4 for above-mentioned upper conversion component beta-schardinger dextrin/PdTPP/DPA protonic solvent propyl alcohol/ethylene glycol (v/v,
1/2) up-conversion luminescence spectrogram, it can be seen that system of the invention is in the presence of beta-schardinger dextrin, Up-conversion Intensity
Enhancing, upper conversion efficiency is improved, up to 35.89%.
The size of the triplet of sensitising agent in the solution is extremely important, and the triplet energy level of sensitising agent and luminous agent will
Ask and be mutually matched, the triplet energy level of wherein sensitising agent need the triplet energy level higher than luminous agent can occur triplet-
Triplet energies are shifted, and luminous agent is reached triplet excited state, carry out T-T annihilation, so as to produce conversion hair
Light.
Table 1, table 2 are respectively the characterize data of sensitising agent, sensitising agent/luminous agent in different medium, ET(30) it is solvent
Polarity parameters；lphors(nm) it is phosphorescence peak position；ET1For lowest triplet state energy level；Fp (%) is relative phosphorescent quantum yield；tp
(ms) it is phosphorescent lifetime；k q(109 M-1×s-1) it is Triplet energy transfer efficiency；FUC (%) is the upper transfer of bicomponent system
Efficiency.As can be seen that the medium system of the present invention effectively increases the triplet of sensitising agent, by existing toluene
1.610eV improve to 1.725eV.
The sensitising agent of table 1, characterize data of the sensitising agent/luminous agent in present media
The sensitising agent of table 2, characterize data of the sensitising agent/luminous agent in existing medium
Prior art thinks that the small organic solvent of polarity is conducive to improving luminous agent fluorescence quantum efficiency, so as to improve photosensitive
The upper conversion efficiency of agent/luminous agent bi-component；Use propyl alcohol/the ethylene glycol of the invention is obtained as decentralized medium
More than 22%, reach as high as 29.1% upper conversion efficiency, add after beta-schardinger dextrin（Embodiment seven）, more it is up to 35.86%；Take
Obtained unexpected technique effect.While the medium system stable uniform of the present invention, modest viscosity, volatility are small, no poison ring
Protect, successfully solve the problem of the toxic solvent of long-standing problem this area researcher.
In nine propyl alcohol of embodiment/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 120 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) and then careful vibration mixing are added, is finally slowly added dropwise
Propyl alcohol/ethylene glycol (v/v, 1/2) constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:150 upper conversion
Mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）It can obtain and be changed in blueness
Fluorescence, its efficiency is up to 22.7%.
In ten propyl alcohol of embodiment/ethylene glycol (v/v, 1/2) on PdTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 280 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) and then careful vibration mixing are added, is finally slowly added dropwise
Propyl alcohol/ethylene glycol (v/v, 1/2) solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:350 it is upper
Change mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）It can obtain in blueness
Conversion fluorescence, its efficiency is up to 28.2%.
In ten monopropylene glycols of embodiment/ethylene glycol (v/v, 2/1) on PdMeTPP/DPA converting system preparation
The substitution anthracene derivants of 9,10- bis- in the present embodiment for luminous agent are DPA, and the metalloporphyrin for sensitising agent is matched somebody with somebody
Compound is PdMeTPP, and molecular structural formula is：
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 2/1) mixed solvent and then careful vibration mixing are added, most
After propyl alcohol/ethylene glycol (v/v, 2/1) mixed solvent constant volume is slowly added dropwise, be configured to 5mL sensitising agent and the mol ratio of luminous agent
Example is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）
Blue up-converted fluorescence can be obtained, its efficiency is up to 18.2%.
In 12 propyl alcohol of embodiment/ethylene glycol (v/v, 1/1) on PdMeTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/1) mixed solvent and then careful vibration mixing are added, most
After propyl alcohol/ethylene glycol (v/v, 1/1) mixed solvent constant volume is slowly added dropwise, be configured to 5mL sensitising agent and the mol ratio of luminous agent
Example is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）
Blue up-converted fluorescence can be obtained, its efficiency is up to 24.1%.
In 13 propyl alcohol of embodiment/ethylene glycol (v/v, 1/2) on PdMeTPP/DPA converting system preparation
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing are added, most
After propyl alcohol/ethylene glycol (v/v, 1/1) mixed solvent constant volume is slowly added dropwise, be configured to 5mL sensitising agent and the mol ratio of luminous agent
Example is 1:300 upper conversion mixed solution.In dim light off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）
Blue up-converted fluorescence can be obtained, its efficiency is up to 28.1%.
Accompanying drawing 5 is above-mentioned upper conversion component PdMeTPP/DPA in protonic solvent propyl alcohol/ethylene glycol (v/v, 2/1), third
Up-conversion luminescence spectrum in alcohol/ethylene glycol (v/v, 1/1) and propyl alcohol/ethylene glycol (v/v, 1/2), it can be seen that of the invention
System Up-conversion Intensity is big, upper high conversion efficiency, up to 28.1%.
In 14 beta-schardinger dextrins of embodiment/propyl alcohol/ethylene glycol (v/v, 1/2) on PdMeTPP/DPA converting system system
It is standby
Pipette 40 μ L photosensitizing agent solution（CHCl3, 1 × 10-3mol/L）With 240 μ L luminous agent solution（DMF, 5 × 10- 2mol/L）Into 5mL volumetric flask, propyl alcohol/ethylene glycol (v/v, 1/2) mixed solvent and then careful vibration mixing are added, then
Add 1200 μ L beta-schardinger dextrin solution（DMF, 1 × 10-2mol/L）, propyl alcohol/ethylene glycol (v/v, 1/1) is finally slowly added dropwise and mixes
Bonding solvent constant volume, the molar ratio of the sensitising agent and luminous agent that are configured to 5mL is 1:300 upper conversion mixed solution.In dim light
Off field（Wavelength is 532 nm, and exciting light energy density is 60 mW × cm-2）Blue up-converted fluorescence can be obtained, its efficiency is reachable
34.1%。
Claims (9)
1. converting system on a kind of efficient green dim light based on protonic solvent, it is characterised in that：Conversion body on the dim light
System includes sensitising agent, luminous agent and protonic solvent；
The chemical structure of general formula of the sensitising agent is as follows：
Wherein substituent R is hydrogen, methyl, bromine or hydroxyl；M is palladium or platinum；
The chemical structure of general formula of the luminous agent is as follows：
Wherein substituent R1For phenyl, 4- methylbenzenes or naphthyl；
The protonic solvent is the mixed solvent of propyl alcohol and ethylene glycol；
In the protonic solvent, the volume ratio of propyl alcohol and ethylene glycol is（0.5~2）∶1.
2. converting system on the efficient green dim light based on protonic solvent according to claim 1, it is characterised in that：It is described
In the chemical structure of general formula of sensitising agent, R is hydrogen or methyl, and M is palladium；In the chemical structure of general formula of the luminous agent, R1For benzene
Base.
3. converting system on the efficient green dim light based on protonic solvent according to claim 1, it is characterised in that：It is described
The mol ratio of sensitising agent and luminous agent is 1: (1~350)；On the dim light in converting system, the concentration of luminous agent is 8 × 10-6
~2.8 × 10-3 mol/L。
4. converting system on the efficient green dim light based on protonic solvent according to claim 3, it is characterised in that：It is described
The mol ratio of sensitising agent and luminous agent is 1: 300；On the dim light in converting system, the concentration of luminous agent is 2.4 × 10-3
mol/L。
5. converting system on the efficient green dim light based on protonic solvent according to claim 1, it is characterised in that：It is described
Converting system also includes beta-schardinger dextrin on dim light；On the dim light in converting system, the concentration of beta-schardinger dextrin is 0~3.0 mM,
And be not 0.
6. described in Claims 1 to 4 on any one efficient green dim light based on protonic solvent converting system preparation side
Method, it is characterised in that comprise the following steps：Photosensitizing agent solution and luminous agent solution are added in container；Then protic is added
Solvent；It is ultrasonically treated；Protonic solvent constant volume is finally added dropwise, so as to obtain turning on the efficient green dim light based on protonic solvent
Change system；The photosensitizing agent solution concentration is 1 × 10-4~2 × 10-3 mol/L；The luminous agent solution concentration is 1 × 10-3~
8×10-2 mol/L。
7. according to claim 6 on the efficient green dim light based on protonic solvent converting system preparation method, it is special
Levy and be：Add after protonic solvent；It is ultrasonically treated, then add beta-schardinger dextrin；Protonic solvent constant volume is finally added dropwise.
8. a kind of method that sensitising agent triplet is improved by aprotic medium effect, it is characterised in that comprise the following steps,
Photosensitizing agent solution is added in container；Then protonic solvent is added；It is ultrasonically treated；Complete carrying for sensitising agent triplet
It is high；The chemical structure of general formula of the sensitising agent is as follows：
Wherein substituent R is hydrogen, methyl, bromine or hydroxyl；M is palladium or platinum；
The protonic solvent is the mixed solvent of propyl alcohol and ethylene glycol.
9. the method for sensitising agent triplet is improved by aprotic medium effect according to claim 8, it is characterised in that：
The photosensitizing agent solution concentration is 1 × 10-4~2 × 10-3 mol/L；In the protonic solvent, the volume of propyl alcohol and ethylene glycol
Than for（0.5~2）∶1.
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| CN108997101B (en) * | 2018-06-15 | 2021-10-08 | 苏州科技大学 | Reaction type luminescent agent 9, 10-diphenyl anthracene derivative, preparation method thereof and high-efficiency weak light up-conversion system prepared from same |
| CN109180692B (en) * | 2018-08-26 | 2020-08-25 | 苏州科技大学 | Temperature-sensitive up-conversion system, preparation method thereof and application thereof in preparation of temperature sensor |
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