CN104557948A - Method for preparing monodispersed porphyrin molecule particles by water droplet templating method - Google Patents
Method for preparing monodispersed porphyrin molecule particles by water droplet templating method Download PDFInfo
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- CN104557948A CN104557948A CN201310466855.9A CN201310466855A CN104557948A CN 104557948 A CN104557948 A CN 104557948A CN 201310466855 A CN201310466855 A CN 201310466855A CN 104557948 A CN104557948 A CN 104557948A
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The invention relates to a method for preparing monodispersed porphyrin molecule particles by a water droplet templating method. The method comprises the following steps: firstly dissolving porphyrin molecules in a good solvent which has good dissolvability of porphyrin molecules so as to obtain a porphyrin solution, and dispersing the porphyrin solution in a poor solvent to obtain a porphyrin molecule suspension; dispersing the porphyrin molecule suspension on a water droplet template, drying in an environment with a certain temperature and humidity, and letting the porphyrin molecules in the porphyrin molecule suspension aggregate and assemble on the surface of the water droplet template so as to finally form the monodispersed porphyrin molecule particles (which are shaped as solid or hollow spheres, solid or hollow hemispheres and jars or petals, etc.). The obtained monodispersed porphyrin molecule particles can be further assembled to form porphyrin molecule photonic crystals with Bragg diffraction performance. Due to close packing of the water droplet template, an ordered arrangement structure is formed, and finally aggregation of the monodispersed porphyrin molecule particles is realized to form an ordered arrangement structure which shows the Bragg diffraction performance, namely photonic crystal performance.
Description
Technical field
The present invention relates to the controllable method for preparing of Porphyrin Molecule aggregation structure, in particular to utilizing water droplet template to the size of Porphyrin Molecule aggregation structure and morphology control, realize the gathering of Porphyrin Molecule, prepare single dispersing Porphyrin Molecule particle, and be assembled into Porphyrin Molecule photonic crystal further.
Background technology
Porphyrin (Porphyrin) take pyrrole ring as the pigment general name of basic structure, and its basic chemical structure is the macromole heterogeneous ring compound connecting 4 pyrrole rings by 4 methylene bridges (CH=) and formed.Porphyrin ring has 26 π-electrons, is the system of a height conjugation.These supramolecular structures be made up of porphyrin ring have very many application in electronics, information storage, light-energy transformation and catalyst system, and the accumulation shape of Porphyrin Molecule is very large on the impact of its final photoelectric properties.By designing the structure of Porphyrin Molecule, the inner and intermolecular conjugation assembling effect of regulatory molecule, thus regulate and control the assembling of its molecule, preparing the Porphyrin Molecule aggregation structure with definite shape, size and pattern and device is research theme in recent years.1996, the people such as Schenning, A achieved the preparation (JACS, 1996,118 (36), 8549-8552) of Porphyrin Molecule annular aggregation structure.1997, the people such as Komatsu achieved the preparation (JACS, 1997,119,11660) of Porphyrin Molecule imitated vesicle structure.2004, the people such as Wang prepared Porphyrin Molecule sheet aggregation structure (JACS, 2004,126 (49), 15954-15955).2005, tubulose and the bar-shaped aggregation structure of Porphyrin Molecule were also produced (JACS, 2005,127 (48), 17090-17095).2009, the good preparation (Advanced Materials2009,21 (17), 1721) waiting people to achieve the spherical of Porphyrin Molecule and Y tube aggregation structure of Institute of Chemistry, Academia Sinica Li Yu.2010, Institute of Chemistry, Academia Sinica Liu Ming China waited people to achieve the preparation (JACS 2010,132 (28), 9644-9652) of the bat shape aggregation structure of Porphyrin Molecule.In the same year, Shelnutt seminar, by introducing negatively charged ion and positively charged ion at Porphyrin Molecule end group, has prepared the quatrefoil shape aggregation structure (JACS, 2010,132 (23), 8194-8201) of Porphyrin Molecule.In the CN201310308655.0 of applicant in this case, by the drying temperature of regulation and control Porphyrin Molecule suspension on base material, achieve the controlled synthesis of Porphyrin Molecule aggregation structure.The present invention has developed by utilizing water droplet as the method for template, induction Porphyrin Molecule suspension is in the gathering of water droplet template surface, thus realizing the controlled synthesis of single dispersing Porphyrin Molecule particle, the shape of involved single dispersing Porphyrin Molecule particle comprises that (hollow) is spherical, (hollow) semisphere, doliform or petal etc.Under the effect of water droplet template, the single dispersing Porphyrin Molecule particle assembling prepared is become to have the Porphyrin Molecule photonic crystal of photonic crystal performance by the present invention further.Method of the present invention provides new approaches for the controlled synthesis of the aggregation structure of Porphyrin Molecule and other conjugated molecule.
Summary of the invention
An object of the present invention is to provide that a kind of preparation method is simple, cost is low, the water droplet template that utilizes of easy operation, easily mass-producing regulates and controls the state of aggregation of Porphyrin Molecule; thus realize the gathering of Porphyrin Molecule, the method for controlled synthesis single dispersing Porphyrin Molecule particle.
Two of object of the present invention is to provide the single dispersing Porphyrin Molecule particle prepared by object one.
Three of the object of this aspect is to provide a kind of Porphyrin Molecule photonic crystal formed by the single dispersing Porphyrin Molecule particle assembling prepared.
The present invention utilizes water droplet template method, take water droplet as template, with Porphyrin Molecule suspension for raw material, drying is carried out in the environment of certain temperature and humidity, assembled by the Porphyrin Molecule in Porphyrin Molecule suspension on the surface of water droplet template and assemble, final gathering forms single dispersing Porphyrin Molecule particle (shape of single dispersing Porphyrin Molecule particle is solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or petal etc.); When the relative humidity of system is greater than 60%, due to the orderly close packed array structure of water droplet template, finally realize multiple single dispersing Porphyrin Molecule particle formed of assembling and there is orderly arrangement architecture.Gained single dispersing Porphyrin Molecule particle can assemble the Porphyrin Molecule photonic crystal (Porphyrin Molecule photonic crystal is that solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or the single dispersing Porphyrin Molecule particle ordered fabrication such as petal obtain by shape) being formed and have photonic crystal performance, and the multiple Porphyrin Molecule photonic crystals with photonic crystal performance formed by multiple single dispersing Porphyrin Molecule particle assembling also have the structure of ordered arrangement.Preparation method of the present invention is simple, cost is low, easily control, for the aggregation structure of regulation and control Porphyrin Molecule and the application of development Porphyrin Molecule in high performance photoelectric device significant.
Of the present inventionly utilize the method for water droplet template synthesis single dispersing Porphyrin Molecule particle: be dissolved in by Porphyrin Molecule to have in the good solvent of good solubility Porphyrin Molecule and obtain porphyrin solution, by the porphyrin Solution Dispersion that obtains in the poor solvent poor to Porphyrin Molecule solvability, obtain Porphyrin Molecule suspension, the Porphyrin Molecule suspension obtained is disperseed (comprise dripping and be coated with, spraying or spraying dispersion etc.) water droplet template on solid substrate surface surface on and dry, or water droplet template is disperseed (comprise dripping and be coated with, spraying or spraying dispersion etc.) Porphyrin Molecule suspension on solid substrate surface surface on and dry, or Porphyrin Molecule suspension is disperseed (comprise dripping and be coated with, spraying or spraying dispersion etc.) water droplet template on solid substrate surface surface on after, again water droplet template is disperseed (to comprise dripping and be coated with, spraying or spraying dispersion etc.) also dry on Porphyrin Molecule suspension, in the process of drying, along with the evaporation of the good solvent in water and Porphyrin Molecule suspension and poor solvent, Porphyrin Molecule can be template with water droplet, assembles and is assembled in the surface of water droplet template, assembling and form single dispersing Porphyrin Molecule particle.Due to the arrangement in good order of water droplet template, multiple single dispersing Porphyrin Molecule particle formed of assembling can be caused to have orderly arrangement architecture.
The formation of the water droplet template on described solid substrate surface solid substrate is placed in the environment of less than 8 DEG C, and then moved to by solid substrate in room temperature (as 25 DEG C) environment, obtains water droplet on the surface of solid substrate; Or by spraying vaporific water to the surface of solid substrate, obtain water droplet on the surface of solid substrate; Or be ink with water, by the method for spray ink Printing, obtain water droplet on the surface of solid substrate.
The shape of the single dispersing Porphyrin Molecule particle that method of the present invention prepares regulates and controls with the change of the volume ratio of the porphyrin solution in Porphyrin Molecule suspension and poor solvent; The size dimension of preparation-obtained single dispersing Porphyrin Molecule particle is determined by the size dimension of water droplet template.
The concentration of described porphyrin solution is 1 μM ~ 1M.
Described porphyrin solution and the volume ratio of poor solvent are 1:5 ~ 3:1.
Dry on the described surface Porphyrin Molecule suspension obtained being dispersed in the water droplet template on solid substrate surface, after the good solvent in water and Porphyrin Molecule suspension and poor solvent evaporate completely, can cause assembling the single dispersing Porphyrin Molecule particle formed and form globosity, obtain the single dispersing Porphyrin Molecule particle of spherical aggregation structure, wherein: the porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and the concentration of porphyrin solution is when being 1M, obtain the single dispersing Porphyrin Molecule particle of solid spherical aggregation structure; Porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and when the concentration of porphyrin solution is 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow ball shape aggregation structure.Contact part due to water droplet template and solid substrate hinders Porphyrin Molecule and is gathered in this place, thus can cause assembling the single dispersing Porphyrin Molecule particle formed and form gap structure, thus assemble formation doliform structure, finally can prepare the single dispersing Porphyrin Molecule particle of doliform aggregation structure, wherein: when the volume ratio of described porphyrin solution and poor solvent is 1:5< volume ratio <1:1, and the concentration of described porphyrin solution is when being 1 μM ~ 1M, obtain the single dispersing Porphyrin Molecule particle of doliform aggregation structure.
Dry on described surface water droplet template being dispersed in the Porphyrin Molecule suspension on solid substrate surface, because the evaporation of the good solvent in Porphyrin Molecule suspension and poor solvent can cause temperature to reduce, dew condensation can be caused thus on the surface of Porphyrin Molecule suspension, Porphyrin Molecule in Porphyrin Molecule suspension can assemble the surface being dispersed in water droplet template, thus forms the single dispersing Porphyrin Molecule particle of hollow ball shape, solid spherical, hollow hemispheric, solid hemi-spherical aggregation structure.Wherein: the porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and when the concentration of described porphyrin solution is 1M, obtain the single dispersing Porphyrin Molecule particle of solid spherical aggregation structure; Porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and when the concentration of described porphyrin solution is 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow ball shape aggregation structure; When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <1:1, and the concentration of described porphyrin solution is when being 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow hemispheric aggregation structure; When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <1:1, and when the concentration of described porphyrin solution is 1M, obtain the single dispersing Porphyrin Molecule particle of solid hemi-spherical aggregation structure.
After on described surface Porphyrin Molecule suspension being dispersed in the water droplet template on solid substrate surface, then water droplet template is dispersed on Porphyrin Molecule suspension also dry, due to the effect of water droplet template, and due to the evaporation of the good solvent in Porphyrin Molecule suspension and poor solvent, temperature can be caused to reduce, the water droplet on Porphyrin Molecule suspension two sides can be caused thus to be condensate in the two sides of Porphyrin Molecule suspension respectively, the surface that Porphyrin Molecule in Porphyrin Molecule suspension can assemble the condensing drip being dispersed in Porphyrin Molecule suspension two sides forms a lot of single dispersing Porphyrin Molecule particles, and these single dispersing Porphyrin Molecule particles formed merge accumulation mutually, thus form the single dispersing Porphyrin Molecule particle of petal aggregation structure, wherein: when the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <3:1, and the concentration of described porphyrin solution is when being 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of petal aggregation structure.
The bore of the single dispersing Porphyrin Molecule particle of described doliform aggregation structure diminishes with the increase of used solid substrate surface contact angle; Or with the volume ratio of the Porphyrin Molecule in porphyrin solution and good solvent increase and reduce.And the length-to-diameter ratio of the single dispersing Porphyrin Molecule particle of described hollow hemispheric, solid hemi-spherical aggregation structure is only subject to the reduction of the volume ratio of the Porphyrin Molecule in porphyrin solution and good solvent and reduces.
The temperature of described drying is preferably-10 ~ 30 DEG C.Described dry time relative humidity be 5% ~ 95%.
The single dispersing Porphyrin Molecule particle of above-mentioned different aggregation structure, because water droplet template is closely piled up in order, under the effect of water droplet template, when the relative humidity of single dispersing Porphyrin Molecule particle when drying that described gathering is formed is 60% ~ 95%, assembles the single dispersing Porphyrin Molecule particle formed and can assemble the Porphyrin Molecule photonic crystal being formed and there is photonic crystal performance.
Described Porphyrin Molecule is selected from a class and macromole heterogeneous ring compound (as: the naphthalene porphyrin ethyl butyrate zinc that formed interconnected by methyne bridge (=CH-) by the alpha-carbon atom of four pyroles subunits, 5-is to ethyl butyrate Oxy-1 0,15,20-tri-naphthyl porphyrin, iron porphyrin etc.) in one.
Described good solvent is selected from one or more in chloroform, methylene dichloride, toluene, dimethylbenzene etc.
Described poor solvent is selected from one or more in Virahol, ethanol, propyl alcohol, glycerol hexanaphthene, normal hexane etc.
Described solid substrate be have hydrophobic low-adhesiveness solid substrate, there is the super-hydrophobic and solid substrate of low-adhesiveness.
The described solid substrate with hydrophobic low-adhesiveness is poly tetrafluoroethylene or PDMS membrane; Or through the solid substrate of silicon fluoride process, the described solid substrate through silicon fluoride process is that the baking oven with the silicon fluoride atmosphere solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours, and the solid substrate of its cleaning is preferably selected from common glass sheet, polymeric film (described polymeric film is selected from the one in Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film, PET film), quartz plate, copper sheet, aluminium flake, silicon chip a kind of.
Described have super-hydrophobic and the solid substrate of low-adhesiveness is by the solid substrate of clean and coarse solid substrate through silicon fluoride process; The described solid substrate through silicon fluoride process is by selected cleaning and the baking oven with silicon fluoride atmosphere that coarse solid substrate is placed in 80 DEG C obtains for 3 ~ 8 hours, and this has super-hydrophobic and the surface of the solid substrate of low-adhesiveness and water contact angle is 150 ~ 160 °; Described coarse solid substrate solid substrate is placed in the SiO that concentration is 0.8 ~ 5wt%
2soak in aqueous dispersions and obtain for 1 ~ 3 minute, its solid substrate is preferably selected from common glass sheet, polymeric film (described polymeric film is selected from the one in poly tetrafluoroethylene, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, PDMS membrane, polyethylene film, polychloroethylene film, PET film), quartz plate, copper sheet, aluminium flake, silicon chip a kind of.
The equipment of described spray ink Printing is piezoelectric ink jet printer or industrial sites colloid system etc., and the aperture of their shower nozzle is preferably 10 μm, 20 μm, 50 μm or 150 μm.
The present invention take water droplet as template, is first dissolved in by Porphyrin Molecule to have in the good solvent of good solubility Porphyrin Molecule to obtain porphyrin solution, then porphyrin Solution Dispersion is obtained Porphyrin Molecule suspension in the poor solvent poor to Porphyrin Molecule solvability; Subsequently, prepared Porphyrin Molecule suspension is disperseed (comprise dripping and be coated with, spraying or spraying dispersion etc.) on the surface of the water droplet template on solid substrate surface, or water droplet template is distributed on the surface of the Porphyrin Molecule suspension on solid substrate surface, or above-mentioned two kinds of methods are combined; Then solid substrate is placed in the environment of certain temperature and relative humidity and carries out drying; Evaporation conditions (the mainly vaporization temperature of Porphyrin Molecule suspension during by regulating and controlling drying, evaporating moisture), Porphyrin Molecule suspension is along with the carrying out of evaporative process, the evaporation convection effect that good solvent wherein and poor solvent produce when evaporating can induce Porphyrin Molecule wherein to take water droplet as template, water droplet template surface aggregation and be assembled in the surface of water droplet template, form single dispersing Porphyrin Molecule particle, and formed the Porphyrin Molecule photonic crystal with photonic crystal performance further by single dispersing Porphyrin Molecule particle assembling.Due to the orderly close packed array structure of water droplet template, multiple single dispersing Porphyrin Molecule particle formed of assembling finally can be caused to have orderly arrangement architecture; Simultaneously different according to the ratio of each component in the concentration of Porphyrin Molecule suspension and Porphyrin Molecule suspension, finally assemble the single dispersing Porphyrin Molecule particle that the single dispersing Porphyrin Molecule particle formed is solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or the shape such as petal; And the multiple Porphyrin Molecule photonic crystals with photonic crystal performance formed by multiple single dispersing Porphyrin Molecule particle assembling also have the structure of ordered arrangement, the Porphyrin Molecule photonic crystal with photonic crystal performance is also obtained by the single dispersing Porphyrin Molecule particle assembling of solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or the shape such as petal.Preparation method of the present invention is simple, cost is low, easily operate, easily batch preparation.The present invention for regulation and control Porphyrin Molecule aggregation structure and provide new approaches for the packaging assembly of Porphyrin Molecule and other conjugated polymers molecule, and for the application of development Porphyrin Molecule in high performance photoelectric device significant.
Accompanying drawing explanation
Fig. 1 a. is of the present invention utilizes water droplet template, dry on surface Porphyrin Molecule suspension being dispersed in the water droplet template on solid substrate surface, assembles the schematic diagram of the single dispersing Porphyrin Molecule particle formed.
Fig. 1 b. is of the present invention utilizes water droplet template, dry on surface water droplet template being dispersed in the Porphyrin Molecule suspension on solid substrate surface, assembles the schematic diagram of the single dispersing Porphyrin Molecule particle formed.
Fig. 2. the stereoscan photograph of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the doliform aggregation structure that the embodiment of the present invention 1 prepares, wherein a is the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of single doliform aggregation structure, and b is the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of multiple doliform aggregation structure.
Fig. 3. the stereoscan photograph of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the preparation-obtained hollow ball shape aggregation structure of the embodiment of the present invention 1.Wherein a is high magnification photo, and b is low range photo.
Fig. 4. the stereoscan photograph of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the preparation-obtained petal aggregation structure of the embodiment of the present invention 3; Wherein a is the full face of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of petal aggregation structure, and b is back side photo.
Fig. 5. the stereoscan photograph of the large-area single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the preparation-obtained petal aggregation structure of the embodiment of the present invention 3.
Embodiment
Embodiment 1.
Shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl butyrate zinc is dissolved in chloroform, obtain the naphthalene porphyrin ethyl butyrate zinc chloroformic solution of 1mM, prepared naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) respectively, ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1), in propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and propyl alcohol is 2:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:4), obtain four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid respectively, the above-mentioned four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained are dripped on the surface of the water droplet template on each the solid substrate surface being coated in sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and the PET film with hydrophobic low-adhesiveness respectively, then gained sample is placed in temperature respectively and is-10 DEG C, relative humidity is place in the climatic chamber of 95% to carry out drying in 24 hours, and to be placed in temperature be respectively 30 DEG C, relative humidity is place in the climatic chamber of 10% to carry out drying in 24 hours.Above-mentioned water droplet template described each solid substrate with hydrophobic low-adhesiveness is placed in temperature be-10 DEG C, relative humidity is condensation in the environment of 95%, and then is moved in room temperature (as 25 DEG C) environment by described each solid substrate with hydrophobic low-adhesiveness and obtain; The solid substrate that above-mentioned each has a hydrophobic low-adhesiveness is that the baking oven with the silicon fluoride atmosphere solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours.
Dry found that is carried out at temperature is-10 DEG C and temperature is 30 DEG C, the gathering shape of naphthalene porphyrin ethyl butyrate zinc has nothing to do with temperature time dry and relative humidity, only becomes with the change of the volume ratio of the naphthalene porphyrin ethyl butyrate zinc chloroformic solution in naphthalene porphyrin ethyl butyrate zinc suspension liquid and poor solvent Virahol, ethanol, propyl alcohol or glycerol used.
Carry out drying at temperature is-10 DEG C and temperature is 30 DEG C after, be dissolved in by naphthalene porphyrin ethyl butyrate zinc the naphthalene porphyrin ethyl butyrate zinc chloroformic solution prepared in chloroform and be dispersed in the naphthalene porphyrin ethyl butyrate zinc suspension liquid prepared in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) and propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and propyl alcohol is 2:1) respectively, drip the sheet glass being coated in and there is hydrophobic low-adhesiveness respectively, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, on the surface of the water droplet template on each solid substrate surface of polychloroethylene film and PET film, all can at sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and PET film obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of hollow ball shape aggregation structure.Be dissolved in by naphthalene porphyrin ethyl butyrate zinc the naphthalene porphyrin ethyl butyrate zinc chloroformic solution prepared in chloroform and be dispersed in the naphthalene porphyrin ethyl butyrate zinc suspension liquid prepared in ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:4) respectively, drip the sheet glass being coated in and there is hydrophobic low-adhesiveness respectively, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, on the surface of the water droplet template on each solid substrate surface of polychloroethylene film and PET film, all can at sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and PET film obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of doliform aggregation structure, and the bore of doliform with the volume ratio of the naphthalene porphyrin ethyl butyrate zinc in naphthalene porphyrin ethyl butyrate zinc chloroformic solution wherein and chloroform increase and reduce.
Fig. 2 is that naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in the naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained in ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1), drip on the surface of the water droplet template be coated on the silicon chip surface with hydrophobic low-adhesiveness, and be placed in temperature and be-10 DEG C, relative humidity is the stereoscan photograph of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the doliform aggregation structure obtained after placement carries out drying in 24 hours in the climatic chamber of 95%, and wherein the mouth of doliform is wide close to 1.5 microns.A in Fig. 2 is the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of single doliform aggregation structure, and b is the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of multiple doliform aggregation structure.
Fig. 3 is that naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in the naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained in propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and propyl alcohol is 2:1), dripping is coated on the surface of the water droplet template had on the Polystyrene Film surface of hydrophobic low-adhesiveness, and be placed in temperature and be-10 DEG C, relative humidity is the stereoscan photograph of the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of the hollow ball shape aggregation structure obtained after placement carries out drying in 24 hours in the climatic chamber of 95%, the single dispersing naphthalene porphyrin ethyl butyrate zinc particles which show the multiple hollow ball shape aggregation structures prepared has arrangement architecture in good order, and show these single dispersing naphthalene porphyrin ethyl butyrate zinc particles with the hollow ball shape aggregation structure of arrangement architecture in good order there is photonic crystal performance.A in Fig. 3 is high magnification photo, and b is low range photo.
Embodiment 2.
Shown in Fig. 1 b, at room temperature, naphthalene porphyrin ethyl butyrate zinc is dissolved in chloroform, obtain the naphthalene porphyrin ethyl butyrate zinc chloroformic solution of 1mM, prepared naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) respectively, ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1), in propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc solution and propyl alcohol is 2:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc solution and glycerol is 1:3), obtain four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid respectively, the above-mentioned four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained are dripped the sheet glass being coated onto and having hydrophobic low-adhesiveness respectively, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, on each solid substrate of polychloroethylene film and PET film (solid substrate that above-mentioned each has a hydrophobic low-adhesiveness is that the baking oven with the silicon fluoride atmosphere solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours), water droplet is sprayed by spray ink Printing, water droplet is dispersed in above-mentioned each have on the surface of the naphthalene porphyrin ethyl butyrate zinc suspension liquid on the solid substrate surface of hydrophobic low-adhesiveness, then gained sample being placed in respectively temperature is 30 DEG C, and relative humidity is place in the climatic chamber of 95% to carry out drying in 24 hours, and to be placed in temperature be respectively 30 DEG C, relative humidity is place in the climatic chamber of 10% to carry out drying in 24 hours, after sample drying, in sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and PET film, obtain the hollow ball shape of naphthalene porphyrin ethyl butyrate zinc or the aggregation structure of hollow hemispheric respectively.The gathering shape that found that naphthalene porphyrin ethyl butyrate zinc has nothing to do with temperature time dry and relative humidity, only must change with the volume ratio of the naphthalene porphyrin ethyl butyrate zinc chloroformic solution in naphthalene porphyrin ethyl butyrate zinc suspension liquid and poor solvent Virahol, ethanol, propyl alcohol or glycerol used and becomes.
Water droplet is dispersed in above-mentioned sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, being dissolved in by naphthalene porphyrin ethyl butyrate zinc the naphthalene porphyrin ethyl butyrate zinc chloroformic solution prepared in chloroform and being dispersed on the surface of the naphthalene porphyrin ethyl butyrate zinc suspension liquid prepared in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) and propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and propyl alcohol is 2:1) respectively on polychloroethylene film and PET film surface, all obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of hollow ball shape aggregation structure.
Water droplet is dispersed in above-mentioned sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, being dissolved in by naphthalene porphyrin ethyl butyrate zinc the naphthalene porphyrin ethyl butyrate zinc chloroformic solution prepared in chloroform and being dispersed on the surface of the naphthalene porphyrin ethyl butyrate zinc suspension liquid prepared in ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:3) respectively on polychloroethylene film and PET film surface, all obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of hollow hemispheric aggregation structure, and the length-to-diameter ratio of hollow hemispheric with the volume ratio of the naphthalene porphyrin ethyl butyrate zinc in naphthalene porphyrin ethyl butyrate zinc chloroformic solution wherein and chloroform increase and increase.
Embodiment 3.
Shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl butyrate zinc is dissolved in chloroform, obtain the naphthalene porphyrin ethyl butyrate zinc chloroformic solution of 1mM, prepared naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) respectively, ethanol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and ethanol is 0.9:1), in propyl alcohol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and propyl alcohol is 2:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:3), obtain four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid respectively, the above-mentioned four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained are dripped on the surface of the water droplet template on each the solid substrate surface being coated onto sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and the PET film with hydrophobic low-adhesiveness respectively, obtains the sample having naphthalene porphyrin ethyl butyrate zinc suspension liquid at the Dispersion on surface of water droplet template, above-mentioned water droplet template described each solid substrate with hydrophobic low-adhesiveness is placed in temperature be-10 DEG C, relative humidity is condensation in the environment of 95%, and then is moved in room temperature (as 25 DEG C) environment by described each solid substrate with hydrophobic low-adhesiveness and obtain.And then water droplet template is dispersed in each solid substrate surface above-mentioned water droplet template surface on naphthalene porphyrin ethyl butyrate zinc suspension liquid on, this water droplet template is 5 DEG C by gained sample being placed in temperature, relative humidity is, after placing in the climatic chamber of 60%, dew condensation is obtained on the surface of naphthalene porphyrin ethyl butyrate zinc suspension liquid.Then it is 30 DEG C that sample gained being respectively water droplet template on the two sides of naphthalene porphyrin ethyl butyrate zinc suspension liquid is placed in temperature respectively, and relative humidity is place in the climatic chamber of 95% to carry out drying in 24 hours; And to be placed in temperature be respectively 30 DEG C, relative humidity is place in the climatic chamber of 10% to carry out drying in 24 hours.After sample drying, in sheet glass, quartz plate, silicon chip, copper sheet, aluminium flake, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film and PET film, all obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of petal aggregation structure respectively.
The solid substrate that above-mentioned each has a hydrophobic low-adhesiveness is that the baking oven with the silicon fluoride atmosphere solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours.
Found that the petal aggregation structure of naphthalene porphyrin ethyl butyrate zinc and the temperature and humidity of system have nothing to do, only become with the change of the volume ratio of the naphthalene porphyrin ethyl butyrate zinc chloroformic solution in naphthalene porphyrin ethyl butyrate zinc suspension liquid and poor solvent Virahol, ethanol, propyl alcohol or glycerol used.When the ratio of the naphthalene porphyrin ethyl butyrate zinc chloroformic solution in system is less, the petal number of the particle obtained is more.
Fig. 4,5 shows the result being dissolved in the petal obtained after the naphthalene porphyrin ethyl butyrate zinc chloroformic solution prepared in chloroform is dispersed in the suspension drying that Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 3:1) obtains by naphthalene porphyrin ethyl butyrate zinc.
Embodiment 4.
Shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl butyrate zinc is dissolved in methylene dichloride, obtain the naphthalene porphyrin ethyl butyrate zinc chloroformic solution of 1mM, prepared naphthalene porphyrin ethyl butyrate zinc chloroformic solution is dispersed in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 0.9:1) respectively, hexanaphthene (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and hexanaphthene is 1.1:5), in normal hexane (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and normal hexane is 2:1) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:3), obtain four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid respectively, the above-mentioned four kinds of naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained are sprayed to respectively on the surface of the water droplet template on the PDMS membrane and poly tetrafluoroethylene surface with hydrophobic low-adhesiveness, and spray to the common glass sheet of the cleaning through silicon fluoride process, silicon chip, copper sheet, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, (described through silicon fluoride process on the surface of the water droplet template on each solid substrate surface of polyethylene film and polychloroethylene film, that the baking oven with the silicon fluoride atmosphere above-mentioned solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours), wherein water droplet template sprays vaporific water droplet to obtain.Then gained sample is placed in temperature respectively and is-10 DEG C, relative humidity is carry out drying in the climatic chamber of 5%, after sample drying, be dissolved in by naphthalene porphyrin ethyl butyrate zinc the naphthalene porphyrin ethyl butyrate zinc chloroformic solution obtained in methylene dichloride and be dispersed in Virahol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and Virahol is 0.9:1) respectively, the naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained in hexanaphthene (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and hexanaphthene is 1.1:5) and glycerol (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and glycerol is 1:3) spray to respectively above-mentioned there is hydrophobic low-adhesiveness PDMS membrane and poly tetrafluoroethylene surface on water droplet template surface on, and spray on the surface of the water droplet template on the surface of each solid substrate described in cleaning through silicon fluoride process, the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of doliform aggregation structure is all obtained after drying.Wherein the bore of doliform increases with the ratio reduction of naphthalene porphyrin ethyl butyrate zinc dichloride dichloromethane in suspension.
And by naphthalene porphyrin ethyl butyrate zinc chloroformic solution be dispersed in the naphthalene porphyrin ethyl butyrate zinc suspension liquid obtained in normal hexane (volume ratio of naphthalene porphyrin ethyl butyrate zinc chloroformic solution and normal hexane is 2:1) spray to respectively above-mentioned there is hydrophobic low-adhesiveness PDMS membrane and poly tetrafluoroethylene surface on water droplet template surface on, and spray on the surface of the water droplet template on the surface of each solid substrate described in cleaning through silicon fluoride process, all obtain the single dispersing naphthalene porphyrin ethyl butyrate zinc particles of hollow ball shape aggregation structure after drying.
Embodiment 5.
Shown in Fig. 1 a, at room temperature, by 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin is dissolved in toluene, obtain the 5-of 1M to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin toluene solution, by prepared 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin toluene solution is dispersed in Virahol respectively, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and Virahol is 2:1), (5-is to ethyl butyrate Oxy-1 0 for hexanaphthene, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and hexanaphthene is 1:3), (5-is to ethyl butyrate Oxy-1 0 for normal hexane, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and normal hexane is 2:1) and glycerol (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and glycerol is 1:3) in, obtain four kinds of 5-respectively to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin suspension, by above-mentioned four kinds of 5-of obtaining to ethyl butyrate Oxy-1 0,15,20-tri-naphthyl porphyrin suspension is respectively as ink-jet printing ink, each ink-jet printing ink in obtain four kinds of ink-jet printing inks is loaded in the print cartridge of 4 ink-jet printers respectively (aperture of inkjet printer head is respectively 10 μm, 20 μm, 50 μm, 150 μm), then described ink-jet printing ink is ejected into respectively and there is the super-hydrophobic and common glass sheet of low-adhesiveness, quartz plate, copper sheet, aluminium flake, silicon chip, Polystyrene Film, polymethyl methacrylate film, on the surface of the water droplet template on each solid substrate upper surface of polyvinyl acetate (PVA) film and PDMS membrane (having treatment process that is super-hydrophobic and the above-mentioned solid substrate of low-adhesiveness is: by selected cleaning and the baking oven with silicon fluoride atmosphere that coarse solid substrate is placed in 80 DEG C within 3 ~ 8 hours, obtain, this has super-hydrophobic and the surface of the solid substrate of low-adhesiveness and water contact angle is 150 ~ 160 °, described coarse solid substrate solid substrate is placed in the SiO that concentration is 0.8 ~ 5wt%
2soak in aqueous dispersions and obtain for 1 ~ 3 minute), in this experiment, water droplet template has super-hydrophobic and each solid substrate of low-adhesiveness is placed in temperature is-10 DEG C by described, relative humidity is condensation in the environment of 95%, and then has super-hydrophobic and each solid substrate of low-adhesiveness and move in room temperature (as 25 DEG C) environment by described and obtain.Then gained sample is placed in temperature respectively and is-5 DEG C, relative humidity is carry out drying in the climatic chamber of 10%; And to be placed in temperature be respectively 0 DEG C, relative humidity is carry out drying in the climatic chamber of 80%.
After sample drying, by 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin toluene solution is dispersed in Virahol, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and Virahol is 2:1), (5-is to ethyl butyrate Oxy-1 0 for normal hexane, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and normal hexane is 2:1) in the 5-that obtains to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin suspension, respectively spray ink Printing to above-mentioned have super-hydrophobic and on the surface of water droplet template on each solid substrate surface of low-adhesiveness, all obtain having the 5-of solid spherical aggregation structure after drying to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin particle.
By 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin toluene solution is dispersed in hexanaphthene, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and hexanaphthene is 1:3) and glycerol (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin toluene solution and glycerol is 1:3) in the 5-that obtains to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin suspension, respectively spray ink Printing to above-mentioned have super-hydrophobic and on the surface of water droplet template on each solid substrate surface of low-adhesiveness, all obtain having the 5-of doliform aggregation structure after drying to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin particle.
Embodiment 6.
Shown in Fig. 1 b, at room temperature, by 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin is dissolved in dimethylbenzene, obtain the 5-of 1M to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin xylene solution, by prepared 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin xylene solution is dispersed in Virahol respectively, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and Virahol is 2:1), (5-is to ethyl butyrate Oxy-1 0 for hexanaphthene, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and hexanaphthene is 1:3), (5-is to ethyl butyrate Oxy-1 0 for normal hexane, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and normal hexane is 2:1) and glycerol (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and glycerol is 1:3) in, obtain four kinds of 5-respectively to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl Porphyrin Molecule suspension, by above-mentioned four kinds of 5-of obtaining to ethyl butyrate Oxy-1 0,15,20-tri-naphthyl porphyrin suspension is respectively as ink-jet printing ink, each ink-jet printing ink in obtain four kinds of ink-jet printing inks is loaded in the print cartridge of 4 industrial sites colloid systems respectively (aperture of its shower nozzle is respectively 10 μm, 20 μm, 50 μm, 150 μm), then ink-jet printing ink to be ejected into respectively on each solid substrate of the sheet glass with hydrophobic low-adhesiveness of silicon fluoride process, quartz plate, aluminium flake and silicon chip (described through silicon fluoride process, to be that the baking oven with the silicon fluoride atmosphere above-mentioned solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours), and then spray vaporific water droplet to above-mentioned each there is 5-on the solid substrate surface of hydrophobic low-adhesiveness on the surface of ethyl butyrate Oxy-1 0,15,20-tri-naphthyl porphyrin suspension.Then gained sample being placed in respectively temperature is 5 DEG C, and relative humidity is carry out drying in the climatic chamber of 10%; And to be placed in temperature be respectively 10 DEG C, relative humidity is carry out drying in the climatic chamber of 5%; After sample drying, on sheet glass, quartz plate, aluminium flake and silicon chip, obtain the aggregation structure of 5-to ethyl butyrate Oxy-1 0,15,20-tri-naphthyl porphyrin respectively.
Wherein by 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin xylene solution is dispersed in Virahol respectively, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and Virahol is 2:1), (5-is to ethyl butyrate Oxy-1 0 for normal hexane, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and normal hexane is 2:1) in the 5-that obtains to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl Porphyrin Molecule suspension, ink-jet has each solid substrate of hydrophobic low-adhesiveness on the surface to above-mentioned respectively, again water droplet template is ejected into 5-to ethyl butyrate Oxy-1 0, 15, on the surface of 20-tri-naphthyl Porphyrin Molecule suspension, the 5-of solid spherical aggregation structure is all obtained to ethyl butyrate Oxy-1 0 after drying, 15, 20-tri-naphthyl porphyrin particle.
And by 5-to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl porphyrin xylene solution is dispersed in hexanaphthene respectively, and (5-is to ethyl butyrate Oxy-1 0, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and hexanaphthene is 1:3), (5-is to ethyl butyrate Oxy-1 0 for glycerol, 15, the volume ratio of 20-tri-naphthyl porphyrin xylene solution and glycerol is 1:3) in the 5-that obtains to ethyl butyrate Oxy-1 0, 15, 20-tri-naphthyl Porphyrin Molecule suspension, ink-jet to above-mentioned each solid substrate with hydrophobic low-adhesiveness on the surface respectively, again water droplet template is ejected into 5-to ethyl butyrate Oxy-1 0, 15, on the surface of 20-tri-naphthyl Porphyrin Molecule suspension, the 5-of solid hemi-spherical aggregation structure is all obtained to ethyl butyrate Oxy-1 0 after drying, 15, 20-tri-naphthyl porphyrin particle.
Claims (10)
1. utilize a method for water droplet template synthesis single dispersing Porphyrin Molecule particle, it is characterized in that: Porphyrin Molecule is dissolved in good solvent and obtains porphyrin solution, by the porphyrin Solution Dispersion that obtains in poor solvent, obtain Porphyrin Molecule suspension; Dry on the surface Porphyrin Molecule suspension obtained being dispersed in the water droplet template on solid substrate surface, or it is dry on surface water droplet template being dispersed in the Porphyrin Molecule suspension on solid substrate surface, or on surface Porphyrin Molecule suspension being dispersed in the water droplet template on solid substrate surface after, then water droplet template to be dispersed on Porphyrin Molecule suspension and dry; Obtain assembling the single dispersing Porphyrin Molecule particle formed;
The concentration of described porphyrin solution is 1 μM ~ 1M;
Described porphyrin solution and the volume ratio of poor solvent are 1:5 ~ 3:1;
Described good solvent is selected from one or more in chloroform, methylene dichloride, toluene, dimethylbenzene;
Described poor solvent is selected from one or more in Virahol, ethanol, propyl alcohol, glycerol hexanaphthene, normal hexane.
2. method according to claim 1, is characterized in that: the single dispersing Porphyrin Molecule particle that multiple described gathering is formed has orderly arrangement architecture.
3. method according to claim 1 and 2, is characterized in that: the shape of the single dispersing Porphyrin Molecule particle that described gathering is formed is solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or petal.
4. method according to claim 3, it is characterized in that: dry on the described surface Porphyrin Molecule suspension obtained being dispersed in the water droplet template on solid substrate surface, wherein: the porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and the concentration of porphyrin solution is when being 1M, obtain the single dispersing Porphyrin Molecule particle of solid spherical aggregation structure; Porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and when the concentration of porphyrin solution is 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow ball shape aggregation structure; When the volume ratio of described porphyrin solution and poor solvent is 1:5< volume ratio <1:1, and when the concentration of described porphyrin solution is 1 μM ~ 1M, obtain the single dispersing Porphyrin Molecule particle of doliform aggregation structure;
Dry on described surface water droplet template being dispersed in the Porphyrin Molecule suspension on solid substrate surface, wherein: the porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and the concentration of described porphyrin solution is when being 1M, obtain the single dispersing Porphyrin Molecule particle of solid spherical aggregation structure; Porphyrin solution in described Porphyrin Molecule suspension and the volume ratio of poor solvent are 1:1 ~ 3:1, and when the concentration of described porphyrin solution is 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow ball shape aggregation structure; When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <1:1, and the concentration of described porphyrin solution is when being 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of hollow hemispheric aggregation structure; When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <1:1, and when the concentration of described porphyrin solution is 1M, obtain the single dispersing Porphyrin Molecule particle of solid hemi-spherical aggregation structure;
After on described surface Porphyrin Molecule suspension being dispersed in the water droplet template on solid substrate surface, then water droplet template is dispersed on Porphyrin Molecule suspension also dry; Wherein: when the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio <3:1, and the concentration of described porphyrin solution is when being 1 μM≤concentration <1M, obtain the single dispersing Porphyrin Molecule particle of petal aggregation structure.
5. the method according to claim 1 or 4, is characterized in that: the temperature of described drying is-10 ~ 30 DEG C; Described dry time relative humidity be 5% ~ 95%.
6. the method according to claim 1 or 4, is characterized in that: described Porphyrin Molecule is selected from a class and one in the macromole heterogeneous ring compound that formed interconnected by methyne bridge by the alpha-carbon atom of four pyroles subunits.
7. method according to claim 1, is characterized in that: described solid substrate be have hydrophobic low-adhesiveness solid substrate or there is the super-hydrophobic and solid substrate of low-adhesiveness.
8. method according to claim 7, is characterized in that: the described solid substrate with hydrophobic low-adhesiveness is poly tetrafluoroethylene or PDMS membrane; Or through the solid substrate of silicon fluoride process, the described solid substrate through silicon fluoride process is that the baking oven with the silicon fluoride atmosphere solid substrate of selected cleaning being placed in 80 DEG C obtains for 3 ~ 8 hours; The solid substrate of the cleaning selected by it is selected from common glass sheet, polymeric film, quartz plate, copper sheet, aluminium flake, silicon chip a kind of; Described polymeric film is selected from the one in Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, polyethylene film, polychloroethylene film, PET film;
Described have super-hydrophobic and the solid substrate of low-adhesiveness is by the solid substrate of clean and coarse solid substrate through silicon fluoride process; The described solid substrate through silicon fluoride process is by selected cleaning and the baking oven with silicon fluoride atmosphere that coarse solid substrate is placed in 80 DEG C obtains for 3 ~ 8 hours, and this has super-hydrophobic and the surface of the solid substrate of low-adhesiveness and water contact angle is 150 ~ 160 °; Described coarse solid substrate solid substrate is placed in the SiO that concentration is 0.8 ~ 5wt%
2soak in aqueous dispersions and obtain for 1 ~ 3 minute, its solid substrate is selected from common glass sheet, polymeric film, quartz plate, copper sheet, aluminium flake, silicon chip a kind of; Described polymeric film is selected from the one in poly tetrafluoroethylene, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, PDMS membrane, polyethylene film, polychloroethylene film, PET film.
9. method according to claim 1 and 2, it is characterized in that: when the relative humidity of single dispersing Porphyrin Molecule particle when drying that described gathering is formed is 60% ~ 95%, assemble the single dispersing Porphyrin Molecule particle formed and can assemble the Porphyrin Molecule photonic crystal being formed and there is photonic crystal performance.
10. method according to claim 9, is characterized in that: the described shape with the Porphyrin Molecule photonic crystal of photonic crystal performance is solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or petal.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892773A (en) * | 2018-05-07 | 2018-11-27 | 河南大学 | A kind of porphyrin polymer nano material, preparation method and application |
| CN108892773B (en) * | 2018-05-07 | 2020-06-12 | 河南大学 | Porphyrin polymer nano material, preparation method and application thereof |
| CN111205476A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation method of spherical porphyrin |
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