CN104028308A - Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst - Google Patents
Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst Download PDFInfo
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- CN104028308A CN104028308A CN201410280394.0A CN201410280394A CN104028308A CN 104028308 A CN104028308 A CN 104028308A CN 201410280394 A CN201410280394 A CN 201410280394A CN 104028308 A CN104028308 A CN 104028308A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of the nanometer photo-catalyst. The catalyst is a nanocomposite which is formed by taking a one-dimensional organic semiconductor nanofiber as a framework, coating the surface of the framework with an inorganic semiconductor titanium dioxide nanolayer and uniformly loading platinum nanoparticles, wherein the organic semiconductor nanofiber is prepared by self-assembling super molecules of perylene diimide and cycle-expanding derivatives, naphthalene diimide derivatives or hexabenzobenzene diimide derivatives with the photochemical stability, D-A structures and visible light response, then titanium dioxide is directly loaded in situ in a body phase organic solution and platinum is reduced and deposited through ultraviolet light in a photo-catalysis aqueous solution system. The catalyst is novel in structure, low in cost and available; the preparation process of the catalyst is simple, environmentally-friendly, low in energy consumption and suitable for preparation in scales; the catalyst is capable of decomposing water in the visible light to prepare the hydrogen, has the actual and wide application prospects in preparation of the hydrogen through decomposing the water in solar light and provides a novel idea and an important reference for forming an efficient photo-catalyst responding to the visible light.
Description
Technical field
The invention belongs to solar energy photocatalytic hydrogen preparation field, particularly a kind of have visible light-responded photocatalytic hydrogen production by water decomposition nano composite material and a purposes.
Background technology
Hydrogen energy source is efficient green energy resource; how the hydrogen making of high efficiency, low cost scale is a key factor of its application of restriction; in numerous hydrogen producing technologies, utilizing the direct photocatalysis Decomposition water generates of inexhaustible solar energy hydrogen is the most cheap environmental protection and the most promising approach.Therefore since occurring the seventies in last century, be subject to showing great attention to of the developed countries such as Japan, the U.S., European Union always, correlative study paper and patent are thousands of, and how obtaining the photochemical catalyst that efficient stable is cheap is the core that academia and industrial quarters are paid close attention to design photocatalysis system and relevant theoretical research.Up to now, although the Nano semiconductor photochemical catalyst taking titanium dioxide as representative obtains the most extensively and the most deep research, but owing to being difficult to take into account the factors such as visible ray (account for solar spectrum 43%) absorption, photochemical stability and light quantum transformation efficiency, this field still has very large distance apart from practical commercialization application, therefore in recent years, modification to conventional semiconductors photochemical catalyst and the design construction of composite, with efficiently separating of realizing visible light-responded and light induced electron and hole, transfer, transmission, become the main research direction in this field.
For current most important semiconductor light-catalyst titanium dioxide, dye sensitization is a kind of simple visible light-responded method of modifying, but traditional sensitization or composite pathway need high temperature more, the participation of higher boiling organic reagent or concentrated acid concentrated base, neither environmental protection and energy saving are also dangerous, and dye molecule exists and easily comes off in the absorption of titanium dioxide surface, defect is many, a series of defects such as carrier transport is not smooth, the preferably sensitizer of having reported mostly in addition is the complex of rare metal (as ruthenium etc.), their preparation process own are complicated and expensive, be unsuitable for applying, therefore find cheap and easy to get, photochemical stable, visible light-responded good and efficient dye sensitizing agent, and design novel compound system and seem very urgent and necessary.
The invention provides a kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst, there is excellent light based on a class, heat, the molecule organic semiconductor of chemical stability, dexterously by their supermolecule self assembly advantage and electron donor-electron acceptor (D-A) type Molecular Design theory, with conventional semiconductors photochemical catalyst titanium dioxide and the typical effective combination of promoter metal platinum, build a kind of new visible light-responded 1-dimention nano semiconductor fiber composite, using this as photochemical catalyst, successfully realize the application in photocatalytic hydrogen production by water decomposition field.
Summary of the invention
The object of the present invention is to provide a kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst, this catalyst is taking one dimension organic semiconductor nanofiber (4) as skeleton, surface coated inorganic semiconductor nano layer (2), and the nano-complex building after uniform load metal nanoparticle (3).Wherein organic semiconductor nanofiber is by photochemical stable and have D-A structure and visible light-responded perylene diimides and ring expansion derivative thereof, the supermolecule self assembly preparation of benzene-naphthalene diimide derivative or coronene diimide derivative, then directly at body phase organic solution situ carried titanium dioxide, and at photocatalysis water solution system medium ultraviolet photo-reduction deposition platinum, successfully sacrifice visible light catalytic hydrogen production by water decomposition in reagent water solution system.This catalyst structure novelty, the simple environmental protection power consumption of cheap and easy to get, preparation process are low, be suitable for scale preparation, for current solar energy photocatalytic water decomposition hydrogen preparation field provides a kind of new nano-photocatalyst material construction method and structure, there is reality and wide application prospect, provide new thinking and important reference for building visible light-responded high efficiency photocatalyst, to improve the poor sunshine utilization of conventional semiconductor material and sensitizer inefficiency problem simultaneously.
Another object of the present invention is the purposes of this visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst in photocatalysis hydrogen production.Catalyst of the present invention is sacrificing in the aqueous solution of reagent methyl alcohol or triethanolamine, using xenon lamp as light source, successfully for the lower decomposition water hydrogen making of visible ray (1).
The visible light-responded water decomposition hydrogen manufacturing of one of the present invention nano-photocatalyst, this photochemical catalyst is taking one dimension organic semiconductor nanofiber (4) as skeleton, surface coated inorganic semiconductor nano layer (2), and the nano-complex building after uniform load metal nanoparticle (3).
Described one dimension organic semiconductor nanofiber (4) skeleton is taking pi-conjugated organic molecule as raw material, anhydrous chloroform and absolute methanol, and absolute ethyl alcohol or anhydrous n-hexane are solvent, adopt the preparation of body phase supermolecule self-assembling method.
Described pi-conjugated organic molecule Wei perylene diimides, perylene diimides ring expansion derivative, benzene-naphthalene diimide derivative or coronene diimide derivative.
Suo Shu perylene diimides derivative is N-dodecyl-N '-dimethyl amido-p-phenyl-perylene diimides, N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides, N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides, N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides, N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides, N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides, N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides, N-3, 5,-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides, N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides, N, N '-dimethyl amido-p-phenyl-perylene diimides, N, N '-dimethyl amido-p-benzyl-perylene diimides, N, N '-pyridine radicals-p-benzyl-perylene diimides or N, N '-piperidyl-p-benzyl-perylene diimides, the perylene diimides ring expansion derivative that spreads out is N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivatives or N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivatives, benzene-naphthalene diimide derivative is N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide, N, N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide, N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide or N, N '-piperidyl-p-benzyl-benzene-naphthalene diimide, coronene diimide derivative is N-dodecyl-N '-dimethyl amido-p-benzyl-coronene imidodicarbonic diamide or N-dodecyl-N '-piperidyl-p-benzyl-coronene imidodicarbonic diamide.
Suo Shu perylene diimides, perylene diimides ring expansion derivative, benzene-naphthalene diimide derivative or coronene diimide derivative are the molecules with supplied for electronic-electrophilic structure, and wherein electron donating group is dimethyl amido-p-phenyl, dimethyl amido-p-benzyl, pyridine radicals-p-phenyl, pyridine radicals-p-benzyl, piperidyl-p-phenyl or piperidyl-p-benzyl.
Inorganic semiconductor in described inorganic semiconductor nanometer layer (2) is titanium dioxide, is that isopropyl oxygen base titanium in-situ hydrolysis method is coated on one dimension organic semiconductor nanofiber surface by organic titanium source.
Metal in described metal nanoparticle (3) is platinum, loads on titanium dioxide surface by chloroplatinic acid photo-reduction method original position.
Described visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst is in the aqueous solution of sacrifice reagent methyl alcohol or triethanolamine, and visible ray (1) is the purposes of decomposition water hydrogen making down.
The preparation method of a kind of visible light-responded water decomposition hydrogen manufacturing photochemical catalyst of the present invention, follows these steps to carry out:
Preparing one dimension organic semiconductor nanofiber (4) is skeleton:
The self assembly of organic pi-conjugated semiconductor molecule, adopt the method for body phase solvent pairs exchange, be that in anhydrous chloroform soln, slow injection poor solvent is absolute methanol, absolute ethyl alcohol or anhydrous n-hexane to the good solvent of molecule organic semiconductor, leave standstill after 6-24 hour, realize the orderly self assembly of molecule organic semiconductor, obtain regular one dimension semiconductor nanofiber (nanobelt or nano wire), and can be in mixed solvent system stable existence, molecule organic semiconductor Wei perylene diimides and ring expansion (vertical or horizontal) derivative thereof, benzene-naphthalene diimide derivative or coronene diimide derivative, the feature of this derivative is in substituting group, to comprise a kind of group with supplied for electronic character, as dimethyl amido phenyl, dimethyl amido benzyl, pyridine radicals phenyl, pyridine radicals benzyl, piperidyl phenyl, piperidyl benzyl etc., with electron deficient perylene and ring expansion thereof, the molecule of naphthalene nucleus or coronene ring element composition supplied for electronic-electrophilic (D-A) structure type, the position of substitution is in imido N-position, other substituting group can be above electron-donating group or chain alkyl, ether, carboxyl, need meet the stacking balance of molecule solubility and π-π, to realize the orderly self assembly of molecule,
Surface cladding titanium dioxide inorganic semiconductor nanometer layer (2):
Under nitrogen protection, to in the nanofiber organic solvent dispersion system obtaining, add the chloroform soln that contains isopropyl oxygen base titanium, flat speed stirs 2-6 hour, ensures the two effective contact and effect, and then dropwise slowly adding volumetric concentration is 90% methanol aqueous solution, in 1-2 hour, drip completely, and continue to stir after 12 hours, filter, by methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the organic semiconductor nanofiber of surperficial cladding titanium dioxide;
Carried metal Pt nanoparticle (3):
The organic semiconductor nanofiber of the coated by titanium dioxide obtaining is again scattered in and is contained in the aqueous solution of sacrificing reagent (as the electron donor that consumes photohole) methyl alcohol or triethanolamine, add the aqueous solution of chloroplatinic acid, pre-stirring after 30 minutes, after high voltage mercury lamp radiation 0.5-2 hour, suction filtration, washing, dry, obtain visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst.
The application of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst:
It is in the aqueous solution of methyl alcohol or triethanolamine that the visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst obtaining is scattered in to 10% sacrifice reagent again, be placed in photocatalytic reaction device, emptying twice, adopt xenon lamp (configuration 400 nanometers or 420 nanometer band pass filters) to irradiate, carry out the photocatalytic hydrogen production by water decomposition reaction under radiation of visible light, the gas that produces uses online gas-chromatography to test and calculate content.
Visible light-responded water decomposition hydrogen manufacturing photochemical catalyst of the present invention, in this catalyst, the structural formula of organic pi-conjugated semiconductor molecule is:
Wherein 1 Wei perylene diimides; 2 is the horizontal ring expansion of 1 perylene ring perylene diimides ring expansion derivative; 3 is the longitudinal ring expansion of 1 perylene ring perylene diimides ring expansion derivative; 4 is benzene-naphthalene diimide; 5 is coronene imidodicarbonic diamide.
In this catalyst, the substituent structure formula of organic pi-conjugated semiconductor molecule is:
Comprise typical electron donating group: 1 is that dimethyl amido-p-phenyl, 2 is dimethyl amido-p-benzyl, 3 is that pyridine radicals-p-phenyl, 4 is that pyridine radicals-p-benzyl, 5 is that piperidyl-p-phenyl, 6 is piperidyl-p-benzyl, with other substituted radical: 7 is dodecyl, 8 is 3-ethyl-heptyl, 9 is 3,5,-dioxy heptyl, 10 is propionate, the position of substitution all with on N-or the N '-position of perylene diimides, perylene diimides ring expansion derivative, benzene-naphthalene diimide or coronene imidodicarbonic diamide molecular structure.
The advantage of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst of the present invention is: the molecule organic semiconductor calorifics adopting and photochemical stability excellence, visible absorption performance are outstanding, synthetic route simple gentle, raw material is cheap and easy to get, product purity good and output is high, can be by substituent structure, the change of quantity and position is dissolubility and the photoelectric property of regulatory molecule easily, further realize the body phase self assembly of scale by exchange of solvent method, obtain compound with regular structure, there is crystalline 1-dimention nano fiber; The similar recrystallization of self assembling process, can obtain the nanostructured of single component, and impurity defect is less, and tens microns and even millimetre-sized long-range order are beneficial to the transmission of photo-generated carrier; Organic semiconductor nanofiber has larger specific area simultaneously, is suitable for doing carrier, if be prepared into membrane electrode, further forms three dimensional network structure; Imidodicarbonic diamide quasi-molecule can be by the noncovalent interactions such as substituent selection and hydrogen bond and amphipathic titanium dioxide effect; Original position self assembly load semiconductor and metal promoters simple to operate, can a step realize controllable load amount and uniformity; The D-A structure of molecule organic semiconductor self and and titanium dioxide between preferably energy level mate, and the synergy of co-catalyst, has promoted generation, transfer, separation and the transmission of photo-generated carrier; In addition, after this composite uses, available good solvent dissolves and reclaims molecule organic semiconductor, thereby further realizes recycling of organic material on titanium dioxide and the less basis of platinum consumption, significantly cost-saving; After platinum carried titanium dioxide/organic semiconductor nanofiber, also can directly carry out photocatalysis hydrogen production experiment without separating containing the solution system of visible-light response nano photochemical catalyst, save the time and reduced the consumption of organic solvent; Finally realize the application of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst hydrogen production by water decomposition under visible ray condition, and further provide important reference for designing the nano-photocatalyst of novel and high-efficiency more.The present invention not only provides a kind of new mentality of designing for solar energy photocatalytic hydrogen manufacturing but also for photocatalysis in the application in the fields such as degradation of contaminant.
Brief description of the drawings
Fig. 1 is basic block diagram of the present invention, and wherein 1 is visible ray; 2 is coated by titanium dioxide layer; 3 is Pt nanoparticle; 4 is organic semiconductor 1-dimention nano fiber;
Fig. 2 is that N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides molecules of the present invention are respectively good solvent and poor solvent with chloroform and methyl alcohol, the stereoscan photograph of the one dimension organic semiconductor nanofiber that the method for employing body phase self assembly prepares
Fig. 3 is the stereoscan photograph after N-dodecyl-N '-dimethyl amido-p-benzyl nano-fibre supported 5wt.% titanium dioxide of-perylene diimides organic semiconductor of the present invention and 0.5wt.% platinum.
Detailed description of the invention
Below by the drawings and specific embodiments, the present invention is further described, but content of the present invention is not limited to given example below.
Embodiment 1:
Select N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete steps are as follows:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 2:
Select N-dodecyl-N '-dimethyl amido-p-phenyl-perylene diimides as pi-conjugated organic molecule, wherein dimethyl amido-p-phenyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-phenyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-phenyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido-p-phenyl-perylene diimides nanofibers of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 3:
Select N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides as pi-conjugated organic molecule, wherein pyridine radicals-p-phenyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-pyridine radicals-p-phenyl-perylene diimides nanofibers of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 4:
Select N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides as pi-conjugated organic molecule, wherein pyridine radicals-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-pyridine radicals-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 5:
Select N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides as pi-conjugated organic molecule, wherein piperidyl-p-phenyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl-p-phenyl-perylene diimides nanofibers of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 6:
Select N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides as pi-conjugated organic molecule, wherein piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, specifically make step and undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 7:
Select N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-3-ethyl-heptyl-N '-dimethyl amido-p-benzyl-perylene diimides of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 8:
Select N-3,5 ,-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides is as pi-conjugated organic molecule, and wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N-3,5, in the beaker of the chloroform soln of-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N-3,5, the dispersion liquid of-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N-3 of coated by titanium dioxide, 5,-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides nanofiber,
Carried metal Pt nanoparticle 3:
Again by the N-3 of coated by titanium dioxide; 5;-dioxy heptyl-N '-dimethyl amido-p-benzyl-perylene diimides is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter, when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour, suction filtration; 100 DEG C of vacuum drying ovens are dried 12 hours, obtain visible light-responded nano-photocatalyst.
Embodiment 9:
Select N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides nanofibers of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-propionate-N '-dimethyl amido-p-benzyl-perylene diimides of coated by titanium dioxide are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 10:
Select N, N '-dimethyl amido-p-phenyl-perylene diimides are as pi-conjugated organic molecule, wherein dimethyl amido-p-phenyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-dimethyl amido-p-phenyl-perylene diimides, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-dimethyl amido-p-phenyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-dimethyl amido-p-phenyl-perylene diimides nanofibers;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-dimethyl amido-p-phenyl-perylene diimides are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 11:
Select N, N '-dimethyl amido-p-benzyl-perylene diimides are as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-dimethyl amido-p-benzyl-perylene diimides, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-dimethyl amido-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-dimethyl amido-p-benzyl-perylene diimides nanofibers;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-dimethyl amido-p-benzyl-perylene diimides are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 12:
Select N, N '-pyridine radicals-p-benzyl-perylene diimides are as pi-conjugated organic molecule, wherein pyridine radicals-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-pyridine radicals-p-benzyl-perylene diimides, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-pyridine radicals-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-pyridine radicals-p-benzyl-perylene diimides nanofibers;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-pyridine radicals-p-benzyl-perylene diimides are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 13:
Select N, N '-piperidyl-p-benzyl-perylene diimides are as pi-conjugated organic molecule, wherein piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-piperidyl-p-benzyl-perylene diimides, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-piperidyl-p-benzyl-perylene diimides nanofibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-piperidyl-p-benzyl-perylene diimides nanofibers;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-piperidyl-p-benzyl-perylene diimides are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 14:
Select the derivative of N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivatives as the horizontal ring expansion of Qi Zhong perylene diimides ring expansion derivative of pi-conjugated organic molecule Wei perylene diimides perylene ring, dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivative, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivates nanometer fibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivates nanometer fibers of coated by titanium dioxide,
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido-p-benzyl of coated by titanium dioxide-perylene diimides ring expansion derivatives are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 15:
Select the derivative of N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivatives as the longitudinal ring expansion of Qi Zhong perylene diimides ring expansion derivative of pi-conjugated organic molecule Wei perylene diimides perylene ring, dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivative, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivates nanometer fibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-perylene diimides ring expansion derivates nanometer fibers of coated by titanium dioxide,
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido-p-benzyl of coated by titanium dioxide-perylene diimides ring expansion derivatives are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 16:
Select the derivative of N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivatives as the horizontal ring expansion of Qi Zhong perylene diimides ring expansion derivative of pi-conjugated organic molecule Wei perylene diimides perylene ring, piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivative, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivates nanometer fibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivates nanometer fibers of coated by titanium dioxide,
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl-p-benzyl of coated by titanium dioxide-perylene diimides ring expansion derivatives are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 17:
Select the derivative of N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivatives as the longitudinal ring expansion of Qi Zhong perylene diimides ring expansion derivative of pi-conjugated organic molecule Wei perylene diimides perylene ring, piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivative, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivates nanometer fibers, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain N-dodecyl-N '-piperidyl-p-benzyl-perylene diimides ring expansion derivates nanometer fibers of coated by titanium dioxide,
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl-p-benzyl of coated by titanium dioxide-perylene diimides ring expansion derivatives are scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 18:
Select N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide nanofiber of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide of coated by titanium dioxide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 19:
Select N, N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide is as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide nanofiber;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-dimethyl amido-p-benzyl-benzene-naphthalene diimide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 20:
Select N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide as pi-conjugated organic molecule, wherein piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide nanofiber of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl-p-benzyl-benzene-naphthalene diimide of coated by titanium dioxide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 21:
Select N, N '-piperidyl-p-benzyl-benzene-naphthalene diimide is as pi-conjugated organic molecule, wherein piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing 0.025 gram of N, in the beaker of the chloroform soln of N '-piperidyl-p-benzyl-benzene-naphthalene diimide, slowly inject 500 ml methanol, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain stable N, the dispersion liquid of N '-piperidyl-p-benzyl-benzene-naphthalene diimide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain the N of coated by titanium dioxide, N '-piperidyl-p-benzyl-benzene-naphthalene diimide nanofiber;
Carried metal Pt nanoparticle 3:
Again by the N of coated by titanium dioxide; N '-piperidyl-p-benzyl-benzene-naphthalene diimide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 22:
Select N-dodecyl-N '-dimethyl amido-p-benzyl-coronene imidodicarbonic diamide as pi-conjugated organic molecule, wherein dimethyl amido-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-dimethyl amido-p-benzyl-coronene imidodicarbonic diamide, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-dimethyl amido-p-benzyl-coronene imidodicarbonic diamide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, dry 6 hours of 100 DEG C of vacuum drying ovens of temperature, obtain N-dodecyl-N '-dimethyl amido-p-benzyl-coronene imidodicarbonic diamide nanofiber of coated by titanium dioxide,
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-dimethyl amido of coated by titanium dioxide-p-benzyl-coronene imidodicarbonic diamide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 23:
Select N-dodecyl-N '-piperidyl-p-benzyl-coronene imidodicarbonic diamide as pi-conjugated organic molecule, wherein piperidyl-p-benzyl is electron-donating group, taking chloroform as good solvent and methyl alcohol be poor solvent, concrete operation step is undertaken by embodiment 1:
Prepare 1-dimention nano fiber 4 for skeleton:
To fill 100 milliliters containing slowly injecting 500 ml methanol in the beaker of the chloroform soln of 0.025 gram of N-dodecyl-N '-piperidyl-p-benzyl-coronene imidodicarbonic diamide, leave standstill 24 hours with sealed membrane sealing and in 20 DEG C of environment of constant temperature, finally obtain the dispersion liquid of stable N-dodecyl-N '-piperidyl-p-benzyl-coronene imidodicarbonic diamide nanofiber, wherein chloroform used and methyl alcohol are to adopt the refining anhydrous solvent of solvent distilling apparatus;
Surface cladding titanium dioxide inorganic semiconductor nanometer layer 2:
Under nitrogen protection and magnetic agitation, 1 milliliter of anhydrous chloroform soln of 0.46 microlitre isopropyl oxygen base titanium will be dripped in chloroform/methyl alcohol dispersion of the nanofiber obtaining, in 1 hour, dropwise, and continue to stir 2 hours, dropwise add again 20 milliliter of 90% methanol aqueous solution, dropwising rear continuation stirs 12 hours, finally adopt 0.45 micron of organic membrane filtration, methanol wash, 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain N-dodecyl-N '-piperidyl-p-benzyl-coronene imidodicarbonic diamide nanofiber of coated by titanium dioxide;
Carried metal Pt nanoparticle 3:
Again N-dodecyl-N '-piperidyl of coated by titanium dioxide-p-benzyl-coronene imidodicarbonic diamide is scattered in again containing in 100 ml deionized water solution of 10% triethanolamine; under nitrogen protection; add the chloroplatinic acid aqueous solution of 3.33 milliliters 0.1 gram every liter; when magnetic agitation, adopt 350 watts of high voltage mercury lamp radiations 1 hour; suction filtration; dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, obtain visible light-responded nano-photocatalyst.
Embodiment 24
Any one visible-light response nano photochemical catalyst described in embodiment 1-embodiment 23 all be can be used for to 1 time hydrogen production by water decomposition of visible ray, and the basic embodiment of photocatalysis experiment is as follows:
The visible-light response nano photochemical catalyst obtaining is scattered in the 100 ml water solution that concentration is 10% triethanolamine or methyl alcohol, be placed in light-catalyzed reaction still, emptying twice, adopt 400 watts of xenon lamps (configuration 400 nanometer band pass filters) to irradiate, carry out the photocatalytic hydrogen production by water decomposition reaction under visible ray 1, the gas that produces uses online gas-chromatography test, and result shows:
As can be seen from the table: visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst of the present invention hydrogen production by water decomposition under visible ray condition, provides new thinking and important reference for building visible light-responded high efficiency photocatalyst.
Claims (8)
1. a visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst, it is characterized in that this photochemical catalyst is taking one dimension organic semiconductor nanofiber (4) as skeleton, surface coated inorganic semiconductor nano layer (2), and the nano-complex building after uniform load metal nanoparticle (3).
2. according to the catalyst described in right 1, it is characterized in that described one dimension organic semiconductor nanofiber (4) skeleton is taking pi-conjugated organic molecule as raw material, anhydrous chloroform and absolute methanol, absolute ethyl alcohol or anhydrous n-hexane are solvent, adopt the preparation of body phase supermolecule self-assembling method.
3. catalyst according to claim 2, is characterized in that described pi-conjugated organic molecule Wei perylene diimides, perylene diimides ring expansion derivative, benzene-naphthalene diimide derivative or coronene diimide derivative.
4. catalyst according to claim 3, it is characterized in that Suo Shu perylene diimides derivative be N-dodecyl-N '-dimethyl amido-
p-phenyl-perylene diimides, N-dodecyl-N '-dimethyl amido-
p-benzyl-perylene diimides, N-dodecyl-N '-pyridine radicals-
p-phenyl-perylene diimides, N-dodecyl-N '-pyridine radicals-
p-benzyl-perylene diimides, N-dodecyl-N '-piperidyl-
p-phenyl-perylene diimides, N-dodecyl-N '-piperidyl-
p-benzyl-perylene diimides, N-3-ethyl-heptyl-N '-dimethyl amido-
p-benzyl-perylene diimides, N-3,5 ,-dioxy heptyl-N '-dimethyl amido-
p-benzyl-perylene diimides, N-propionate-N '-dimethyl amido-
p-benzyl-perylene diimides, N, N '-dimethyl amido-
p-phenyl-perylene diimides, N, N '-dimethyl amido-
p-benzyl-perylene diimides, N, N '-pyridine radicals-
p-benzyl-perylene diimides or N, N '-piperidyl-
p-benzyl-perylene diimides; Perylene diimides spread out ring expansion derivative be N-dodecyl-N '-dimethyl amido-
p-benzyl-perylene diimides ring expansion derivatives or N-dodecyl-N '-piperidyl-
p-benzyl-perylene diimides ring expansion derivatives; Benzene-naphthalene diimide derivative be N-dodecyl-N '-dimethyl amido-
p-benzyl-benzene-naphthalene diimide, N, N '-dimethyl amido-
p-benzyl-benzene-naphthalene diimide, N-dodecyl-N '-piperidyl-
p-benzyl-benzene-naphthalene diimide or N, N '-piperidyl-
p-benzyl-benzene-naphthalene diimide; Coronene diimide derivative be N-dodecyl-N '-dimethyl amido-
p-benzyl-coronene imidodicarbonic diamide or N-dodecyl-N '-piperidyl-
p-benzyl-coronene imidodicarbonic diamide.
5. catalyst according to claim 3, it is characterized in that Suo Shu perylene diimides, perylene diimides ring expansion derivative, benzene-naphthalene diimide derivative or coronene diimide derivative are the molecules with supplied for electronic-electrophilic structure, wherein electron donating group be dimethyl amido-
p-phenyl, dimethyl amido-
p-benzyl, pyridine radicals-
p-phenyl, pyridine radicals-
p-benzyl, piperidyl-
p-phenyl or piperidyl-
p-benzyl.
6. catalyst according to claim 1, it is characterized in that the inorganic semiconductor in described inorganic semiconductor nanometer layer (2) is titanium dioxide, is that isopropyl oxygen base titanium in-situ hydrolysis method is coated on one dimension organic semiconductor nanofiber surface by organic titanium source.
7. catalyst according to claim 1, is characterized in that the metal in described metal nanoparticle (3) is platinum, loads on titanium dioxide surface by chloroplatinic acid photo-reduction method original position.
8. a visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst claimed in claim 1 is in the aqueous solution of sacrifice reagent methyl alcohol or triethanolamine, and visible ray (1) is the purposes of decomposition water hydrogen making down.
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