CN104028308B

CN104028308B - Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst

Info

Publication number: CN104028308B
Application number: CN201410280394.0A
Authority: CN
Inventors: 王传义; 陈帅; 李英宣
Original assignee: Xinjiang Technical Institute of Physics and Chemistry of CAS
Current assignee: Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date: 2014-06-20
Filing date: 2014-06-20
Publication date: 2017-01-18
Anticipated expiration: 2034-06-20
Also published as: CN104028308A

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

A kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst and purposes

Technical field

The invention belongs to solar energy photocatalytic hydrogen preparation field, particularly to a kind of, there is visible light-responded photocatalysis Decomposition Water hydrogen manufacturing nano composite material and purposes.

Background technology

Hydrogen energy source is efficient green energy resource, and how the hydrogen making of high efficiency, low cost scale is the one of its application of restriction Individual key factor, in numerous hydrogen producing technologies, producing hydrogen using inexhaustible solar energy direct photocatalysis Decomposition water is The most cheap environmental protection and the most promising approach.Therefore since the appearance seventies in last century, Japan, the U.S., Europe have been constantly subjected to it The highest attention of Meng Deng developed country, correlational study paper and patent are thousands of, how to obtain the cheap light of efficient stable and urge The theoretical research of agent and design photocatalytic system and correlation is academia and the core of industrial quarters concern.So far, although Nano semiconductor photocatalyst with titanium dioxide as representative obtains the most extensive and in-depth study, but due to being difficult to take into account The factors such as visible ray (accounting for the 43% of solar spectrum) absorption, photochemical stability and light quantum transformation efficiency, this field distance Practical commercialization application still has very big distance, therefore in recent years, modification to conventional semiconductors photocatalyst and composite Design construction, to realize the high efficiency separation of visible light-responded and light induced electron and hole, transfer, transmission, becomes this field main Research direction.

For currently the most important ones semiconductor light-catalyst titanium dioxide, dye sensitization is a kind of simple visible ray Response method of modifying, but needing the participation of high temperature, high boiling point organic reagent or concentrated acid concentrated base traditional sensitization or composite pathway more, Neither environmental protection and energy saving are also dangerous, and in the absorption of titanium dioxide surface, dye molecule has that easy to fall off, defect is many, carrier Transmit a series of defects such as not smooth, in addition the preferably sensitizer of report mostly is the coordination compound of rare metal (as ruthenium etc.), it Preparation process itself complicated and expensive, be unsuitable for popularization and application, therefore find cheap and easy to get, photochemical stable, visible ray and ring Should get well and efficient dye sensitizing agent, and design new compound system and seem very urgent and necessary.

The invention provides a kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst, based on a class have excellent light, Their Supramolecular self assembly advantage and electron donor-electronics are dexterously subject to by heat, the molecule organic semiconductor of chemical stability Body (d-a) type Molecular Design theory, with conventional semiconductors photocatalyst titanium dioxide and typical promoter metal platinum Effectively combine, construct a kind of new visible light-responded 1-dimention nano semiconductor fiber composite, in this, as photocatalyst, It is successfully realized the application in photocatalytic hydrogen production by water decomposition field.

Content of the invention

It is an object of the invention to provide a kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst, this catalyst be with One-dimensional organic semiconductor nanofiber (4) is that skeleton, Surface coating inorganic semiconductor nanometer layer (2), and uniform load metal are received The nano-complex that rice grain (3) builds afterwards.Wherein organic semiconductor nanofiber passes through photochemical stable and has d-a structure With visible light-responded imidodicarbonic diamide and its ring expansion derivant, benzene-naphthalene diimide derivative or coronene imidodicarbonic diamide derive The Supramolecular self assembly preparation of thing, then directly in body phase organic solution situ carried titanium dioxide and water-soluble in photocatalysis Ultraviolet photo-reduction deposition platinum in liquid system, successfully carries out sacrificing visible light catalytic hydrogen production by water decomposition in reagent water solution system.Should Catalyst structure is novel, cheap and easy to get, the simple and environmentally-friendly power consumption of preparation process is low, is suitable to scale preparation, urges for current solar energy Changing water decomposition hydrogen preparation field provides a kind of new nano-photocatalyst material construction method and structure, has real and wide application Prospect, provides new thinking and important reference for building visible light-responded high efficiency photocatalyst simultaneously, to improve tradition half The poor sunlight of conductor material utilizes and sensitizer inefficiency problem.

It is another object of the present invention to this visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst is in photocatalysis hydrogen production Purposes.Catalyst of the present invention is in sacrificing the aqueous solution of reagent methanol or triethanolamine, using xenon lamp as light source, successful For decomposition water hydrogen making under visible ray (1).

A kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst of the present invention, this photocatalyst is that had with one-dimensional Machine semiconductor nano fiber (4) is skeleton, Surface coating inorganic semiconductor nanometer layer (2), and uniform load metal nanoparticle (3) nano-complex building afterwards.

Described one-dimensional organic semiconductor nanofiber (4) skeleton is with pi-conjugated organic molecule as raw material anhydrous three Chloromethanes and absolute methanol, dehydrated alcohol or anhydrous n-hexane are solvent, using the preparation of body phase Supramolecular self assembly method.

Described pi-conjugated organic molecule is diimide derivative, imidodicarbonic diamide ring expansion derivant, naphthalene two acyl Imine derivative or coronene diimide derivative.

Described diimide derivative is n- dodecyl-n '-dimethyl amido-p- phenyl-imidodicarbonic diamide, n- Dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide, n- dodecyl-n '-pyridine radicals-p- phenyl-two acyl is sub- Amine, n- dodecyl-n '-pyridine radicals-p- benzyl-imidodicarbonic diamide, n- dodecyl-n '-piperidyl-p- phenyl-two acyl Imines, n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide, n-3- ethyl-heptyl-n '-dimethyl amido-p- benzyl Base-imidodicarbonic diamide, n-3,5 ,-dioxy heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide, n- propionate-n '-two Methylamino-p- benzyl-imidodicarbonic diamide, n, n '-dimethyl amido-p- phenyl-imidodicarbonic diamide, n, n '-dimethyl amido- P- benzyl-imidodicarbonic diamide, n, n '-pyridine radicals-p- benzyl-imidodicarbonic diamide or n, n '-piperidyl-p- benzyl-two acyl is sub- Amine；Imidodicarbonic diamide ring expansion derivant is n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion derivant Or n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivant；Benzene-naphthalene diimide derivative is n- dodecane Base-n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide, n, n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide, n- dodecane Base-n '-piperidyl-p- benzyl-benzene-naphthalene diimide or n, n '-piperidyl-p- benzyl-benzene-naphthalene diimide；Coronene two acyl is sub- Amine derivative is n- dodecyl-n '-dimethyl amido-p- benzyl-coronene imidodicarbonic diamide or n- dodecyl-n '-piperazine Piperidinyl-p- benzyl-coronene imidodicarbonic diamide.

Described diimide derivative, imidodicarbonic diamide ring expansion derivant, benzene-naphthalene diimide derivative or six benzos Benzene diimide derivative is the molecule 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.

Inorganic semiconductor in described inorganic semiconductor nanometer layer (2) is titanium dioxide, is isopropyl by organic titanium source Base epoxide titanium in-situ hydrolysis method is coated on one-dimensional organic semiconductor nanofiber surface.

Metal in described metal nanoparticle (3) is platinum, is supported on dioxy by chloroplatinic acid photo-reduction method original position Change titanium surface.

Described visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst is sacrificing the water-soluble of reagent methanol or triethanolamine In liquid it is seen that under light (1) decomposition water hydrogen making purposes.

A kind of preparation method of visible light-responded water decomposition hydrogen production photocatalyst of the present invention, follow these steps to into OK:

Preparing one-dimensional organic semiconductor nanofiber (4) is skeleton:

The self assembly of organic pi-conjugated semiconductor molecule, the method being exchanged using body phase solvent pairs, that is, to organic semiconductor The good solvent of molecule is absolute methanol for being slowly injected into poor solvent in anhydrous chloroform soln, dehydrated alcohol or anhydrous just own Alkane, after standing 6-24 hour, realizes the orderly self assembly of molecule organic semiconductor, obtains regular one dimension semiconductor nanofiber (nano belt or nano wire), and can in mixed solvent system stable existence；Molecule organic semiconductor be imidodicarbonic diamide and its Ring expansion (vertical or horizontal) derivant, benzene-naphthalene diimide derivative or coronene diimide derivative, the spy of this derivant Point is to comprise a kind of group with supplied for electronic property in substituent group, such as dimethyl amido phenyl, dimethyl amido benzyl, Pyridinylphenyl, pyridine radicals benzyl, piperidinophenyl, piperidyl benzyl etc., with electron deficiency and its ring expansion, naphthalene nucleus or six benzene And benzene ring units form the molecule of supplied for electronic electrophilic (d-a) structure type, the position of substitution is in imido n- position, Qi Taqu Can be above electron-donating group or chain alkyl, ether, carboxyl for base, the balance of molecule solubility and π-π stacking need to be met, To realize the orderly self assembly of molecule；

Surface coating titanium oxide inorganic semiconductor nano layer (2):

Under nitrogen protection, will add containing isopropyl epoxide titanium in the nanofiber obtaining organic solvent dispersion system Chloroform soln, equals speed stirring 2-6 hour it is ensured that the effective contact of the two and effect, is then dropwise slowly added to volume dense Spend for 90% methanol aqueous solution, in 1-2 hour, Deca completely, and after continuing to stir 12 hours, filters, washed with methanol, temperature 100 DEG C of vacuum drying ovens are dried 6 hours, obtain the organic semiconductor nanofiber of Surface coating titanium dioxide；

Carried metal Pt nanoparticle (3):

The organic semiconductor nanofiber of the coated by titanium dioxide obtaining is scattered in again containing sacrificing reagent (as disappearing The electron donor of consumption photohole) methanol or triethanolamine aqueous solution in, add the aqueous solution of chloroplatinic acid, pre- stirring 30 minutes Afterwards, after high voltage mercury lamp radiation 0.5-2 hour, sucking filtration, washing, it is dried, obtain visible light-responded water decomposition hydrogen manufacturing nano-photo catalytic Agent.

The application of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst:

It is methanol that the visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst obtaining is scattered in 10% sacrifice reagent again Or in the aqueous solution of triethanolamine, be placed in photocatalytic reaction device, emptying twice, (configures 400 nanometers or 420 using xenon lamp Nanometer band pass filter) irradiate, carry out the photocatalytic hydrogen production by water decomposition reaction under radiation of visible light, produced gas is using online Gas chromatogram is tested and is calculated content.

Visible light-responded water decomposition hydrogen production photocatalyst of the present invention, in this catalyst, organic pi-conjugated quasiconductor divides The structure chart of son is:

Wherein 1 is imidodicarbonic diamide；2 is the imidodicarbonic diamide ring expansion derivant of the 1 horizontal ring expansion of ring；3 is 1 ring The imidodicarbonic diamide ring expansion derivant of longitudinal ring expansion；4 is benzene-naphthalene diimide；5 is coronene imidodicarbonic diamide.

In this catalyst, the substituent structure formula of organic pi-conjugated semiconductor molecule is:

Including typical electron donating group: 1 is dimethyl amido-p- phenyl, 2 is dimethyl amido-p- benzyl, and 3 are Pyridine radicals-p- phenyl, 4 be pyridine radicals-p- benzyl, 5 be piperidyl-p- phenyl, 6 be piperidyl-p- benzyl, and other substituent group Group: 7 be dodecyl, 8 be 3- ethyl-heptyl, 9 be 3,5 ,-dioxy heptyl, 10 be propionate, the position of substitution all more than Imidodicarbonic diamide, imidodicarbonic diamide ring expansion derivant, benzene-naphthalene diimide or coronene imidodicarbonic diamide molecular structure n- or n '- Position.

The advantage of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst of the present invention is: organic half being adopted Conductor molecule calorifics and photochemical stability are excellent, visible absorption performance is outstanding, synthetic route is simply gentle, raw material is inexpensively easy , product purity is good and yield height, can be by the structure of substituent group, the dissolving of the change of quantity and position easily regulatory molecule Property and photoelectric property, are realized the body phase self assembly of scale further, obtain compound with regular structure, have crystallization by solvent exchange method The 1-dimention nano fiber of property；Self assembling process is similar to recrystallization, can get the nanostructured of single component, and impurity defect is less, Tens microns or even millimetre-sized long-range order are beneficial to the transmission of photo-generated carrier；Organic semiconductor nanofiber has relatively simultaneously Big specific surface area, is suitable for doing carrier, if being prepared into membrane electrode, then forms three dimensional network structure further；Two acyls are sub- Amine molecule can pass through the noncovalent interactions such as selection and the hydrogen bond of substituent group and act on amphipathic titanium dioxide；Primary reconstruction Load quasiconductor and metal promoters simple to operate, can a step realize, controllable load amount and uniformity；Organic semiconductor The d-a structure of molecule itself and its and titanium dioxide between preferable level-density parameter, and the synergism of promoter, promote The generation of photo-generated carrier, transfer, separation and transmission；In addition, after this composite uses, available good solvent dissolving is reclaimed organic Semiconductor molecule, thus realize recycling of organic material further, greatly on the basis of titanium dioxide and platinum consumption are less Cost-effective；The solution of visible-light response nano photocatalyst is contained after platinum carried titanium dioxide/organic semiconductor nanofiber System also can directly carry out photocatalysis hydrogen production experiment without isolation, save the time and decrease 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 light conditions, and be further The nano-photocatalyst of design more novel and high-efficiency provides important reference.The present invention be only solar energy photocatalytic hydrogen manufacturing and Provide a kind of new mentality of designing for the application in fields such as degradation of contaminant for the photocatalysis.

Brief description

Fig. 1 is the basic block diagram of the present invention, and wherein 1 is visible ray；2 is coated by titanium dioxide layer；3 is platinum nanometer Grain；4 is organic semiconductor 1-dimention nano fiber；

Fig. 2 be n- dodecyl-n ' of the present invention-dimethyl amido-p- benzyl-imidodicarbonic diamide molecule with chloroform and Methanol is respectively good solvent and poor solvent, the one-dimensional organic semiconductor Nanowire preparing using the method for body phase self assembly The stereoscan photograph of dimension

Fig. 3 is n- dodecyl-n ' of the present invention-dimethyl amido-p- benzyl-imidodicarbonic diamide organic semiconductor Nanowire Stereoscan photograph after dimension load 5wt.% titanium dioxide and 0.5wt.% platinum.

Specific embodiment

Below by the drawings and specific embodiments, the present invention is further described, but present disclosure is not limited to In example given below.

Embodiment 1:

Select n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide as pi-conjugated organic molecule, its Middle dimethyl amido-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete steps are such as Under:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain the three of 0.025 gram of n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide It is slowly injected into 500 ml methanol, standing is 24 little with sealing film phonograph seal and in 20 DEG C of environment of constant temperature in the beaker of chloromethanes solution When, finally give the dispersion liquid of stable n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber, Chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber Again it is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliters 0.1 gram Every liter of chloroplatinic acid aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum are dried Case is dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 2:

Select n- dodecyl-n '-dimethyl amido-p- phenyl-imidodicarbonic diamide as pi-conjugated organic molecule, its Middle dimethyl amido-p- phenyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operations walk Suddenly carry out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain the three of 0.025 gram of n- dodecyl-n '-dimethyl amido-p- phenyl-imidodicarbonic diamide It is slowly injected into 500 ml methanol, standing is 24 little with sealing film phonograph seal and in 20 DEG C of environment of constant temperature in the beaker of chloromethanes solution When, finally give the dispersion liquid of stable n- dodecyl-n '-dimethyl amido-p- phenyl-imidodicarbonic diamide nanofiber, Chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-dimethyl amido-p- phenyl-imidodicarbonic diamide nanofiber Again it is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliters 0.1 gram Every liter of chloroplatinic acid aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum are dried Case is dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 3:

Select n- dodecyl-n '-pyridine radicals-p- phenyl-imidodicarbonic diamide as pi-conjugated organic molecule, wherein pyrrole Piperidinyl-p- phenyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of three chloromethanes containing 0.025 gram of n- dodecyl-n '-pyridine radicals-p- phenyl-imidodicarbonic diamide will be filled It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, in the beaker of alkane solution Obtain the dispersion liquid of stable n- dodecyl-n '-pyridine radicals-p- phenyl-imidodicarbonic diamide nanofiber eventually, wherein used three Chloromethanes and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Pyridine radicals-p- phenyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-pyridine radicals-p- phenyl-imidodicarbonic diamide nanofiber again It is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopt 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum drying ovens are done Dry 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 4:

Select n- dodecyl-n '-pyridine radicals-p- benzyl-imidodicarbonic diamide as pi-conjugated organic molecule, wherein pyrrole Piperidinyl-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of three chloromethanes containing 0.025 gram of n- dodecyl-n '-pyridine radicals-p- benzyl-imidodicarbonic diamide will be filled It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, in the beaker of alkane solution Obtain the dispersion liquid of stable n- dodecyl-n '-pyridine radicals-p- benzyl-imidodicarbonic diamide nanofiber eventually, wherein used three Chloromethanes and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Pyridine radicals-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-pyridine radicals-p- benzyl-imidodicarbonic diamide nanofiber again It is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopt 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum drying ovens are done Dry 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 5:

Select n- dodecyl-n '-piperidyl-p- phenyl-imidodicarbonic diamide as pi-conjugated organic molecule, wherein piperazine Piperidinyl-p- phenyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of three chloromethanes containing 0.025 gram of n- dodecyl-n '-piperidyl-p- phenyl-imidodicarbonic diamide will be filled It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, in the beaker of alkane solution Obtain the dispersion liquid of stable n- dodecyl-n '-piperidyl-p- phenyl-imidodicarbonic diamide nanofiber eventually, wherein used three Chloromethanes and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Piperidyl-p- phenyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-piperidyl-p- phenyl-imidodicarbonic diamide nanofiber again It is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopt 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum drying ovens are done Dry 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 6:

Select n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide as pi-conjugated organic molecule, wherein piperazine Piperidinyl-p- benzyl is electron-donating group, with chloroform as good solvent with methanol is as poor solvent, specifically makees step by embodiment 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of three chloromethanes containing 0.025 gram of n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide will be filled It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, in the beaker of alkane solution Obtain the dispersion liquid of stable n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide nanofiber eventually, wherein used three Chloromethanes and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Piperidyl-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n- dodecyl-n ' of coated by titanium dioxide-piperidyl-p- benzyl-imidodicarbonic diamide is again scattered in and contains In 100 ml deionized water solution of 10% triethanolamine, under nitrogen protection, add the chloroplatinic acid of 3.33 milliliter of 0.1 gram per liter Aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 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-imidodicarbonic diamide as pi-conjugated organic point Son, wherein dimethyl amido-p- benzyl are electron-donating group, with chloroform as good solvent with methanol is as poor solvent, specifically Operating procedure is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n-3- ethyl-heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 in 20 DEG C of environment of constant temperature in the beaker of chloroform soln Hour, finally give dividing of stable n-3- ethyl-heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber Dispersion liquid, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n-3- ethyl-heptyl of coated by titanium dioxide- N '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n-3- ethyl-heptyl-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-imidodicarbonic diamide is divided again Dissipate in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum drying ovens are dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 8:

Select n-3,5 ,-dioxy heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide is as pi-conjugated organic point Son, wherein dimethyl amido-p- benzyl are electron-donating group, with chloroform as good solvent with methanol is as poor solvent, specifically Operating procedure is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n-3,5 ,-dioxy heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide The beaker of chloroform soln in be slowly injected into 500 ml methanol, with sealing film phonograph seal and in 20 DEG C of environment of constant temperature stand 24 hours, finally give stable n-3,5 ,-dioxy heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber Dispersion liquid, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtains the n-3 of coated by titanium dioxide, and 5 ,-dioxepin Base-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n-3,5 of coated by titanium dioxide ,-dioxy heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide is again It is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopt 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum drying ovens are done Dry 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 9:

Select n- propionate-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide as pi-conjugated organic molecule, wherein Dimethyl amido-p- benzyl is electron-donating group, with chloroform as good solvent with methanol is as poor solvent, concrete operation step Carry out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of trichlorines containing 0.025 gram of n- propionate-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide will be filled It is slowly injected into 500 ml methanol in the beaker of dichloromethane, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, Finally give the dispersion liquid of stable n- propionate-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber, wherein institute It is the anhydrous solvent being refined using solvent distilling apparatus with chloroform and methanol；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- propionate-n '-two of coated by titanium dioxide Methylamino-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n- propionate-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-imidodicarbonic diamide is scattered in again In the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add the chlorine platinum of 3.33 milliliter of 0.1 gram per liter Aqueous acid, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum drying ovens of temperature are dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 10:

Select n, n '-dimethyl amido-p- phenyl-imidodicarbonic diamide is as pi-conjugated organic molecule, wherein dimethyl Amido-p- phenyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the chloroform soln of n '-dimethyl amido-p- phenyl-imidodicarbonic diamide Beaker in be slowly injected into 500 ml methanol, with sealing film phonograph seal and in 20 DEG C of environment of constant temperature stand 24 hours, finally give The dispersion liquid of stable n, n '-dimethyl amido-p- phenyl-imidodicarbonic diamide nanofiber, chloroform wherein used and first Alcohol is the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n of coated by titanium dioxide, n '-dimethyl amine Base-p- phenyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n of coated by titanium dioxide, n '-dimethyl amido-p- phenyl-imidodicarbonic diamide is scattered in again containing 10% 3 In 100 ml deionized water solution of ethanolamine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, 350 watts of high voltage mercury lamp radiations are adopted 1 hour while magnetic agitation, sucking filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, that is, Obtain visible light-responded nano-photocatalyst.

Embodiment 11:

Select n, n '-dimethyl amido-p- benzyl-imidodicarbonic diamide is as pi-conjugated organic molecule, wherein dimethyl Amido-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the chloroform soln of n '-dimethyl amido-p- benzyl-imidodicarbonic diamide Beaker in be slowly injected into 500 ml methanol, with sealing film phonograph seal and in 20 DEG C of environment of constant temperature stand 24 hours, finally give The dispersion liquid of stable n, n '-dimethyl amido-p- benzyl-imidodicarbonic diamide nanofiber, chloroform wherein used and first Alcohol is the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n of coated by titanium dioxide, n '-dimethyl amine Base-p- benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n of coated by titanium dioxide, n '-dimethyl amido-p- benzyl-imidodicarbonic diamide is scattered in again containing 10% 3 In 100 ml deionized water solution of ethanolamine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, 350 watts of high voltage mercury lamp radiations are adopted 1 hour while magnetic agitation, sucking filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, that is, Obtain visible light-responded nano-photocatalyst.

Embodiment 12:

Select n, n '-pyridine radicals-p- benzyl-imidodicarbonic diamide is as pi-conjugated organic molecule, wherein pyridine radicals-p- benzyl Base is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the burning of the chloroform soln of n '-pyridine radicals-p- benzyl-imidodicarbonic diamide It is slowly injected into 500 ml methanol in cup, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, finally give stable N, the dispersion liquid of n '-pyridine radicals-p- benzyl-imidodicarbonic diamide nanofiber, chloroform wherein used and methanol are employing The anhydrous solvent that solvent distilling apparatus refine；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n of coated by titanium dioxide, n '-pyridine radicals-p- Benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n of coated by titanium dioxide, n '-pyridine radicals-p- benzyl-imidodicarbonic diamide is scattered in again containing 10% 3 ethanol In 100 ml deionized water solution of amine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, magnetic force 350 watts of high voltage mercury lamp radiations are adopted 1 hour while stirring, sucking filtration, 100 DEG C of vacuum drying ovens of temperature are dried 12 hours, that is, obtain Visible light-responded nano-photocatalyst.

Embodiment 13:

Select n, n '-piperidyl-p- benzyl-imidodicarbonic diamide is as pi-conjugated organic molecule, wherein piperidyl-p- benzyl Base is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the burning of the chloroform soln of n '-piperidyl-p- benzyl-imidodicarbonic diamide It is slowly injected into 500 ml methanol in cup, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, finally give stable N, the dispersion liquid of n '-piperidyl-p- benzyl-imidodicarbonic diamide nanofiber, chloroform wherein used and methanol are employing The anhydrous solvent that solvent distilling apparatus refine；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n of coated by titanium dioxide, n '-piperidyl-p- Benzyl-imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n of coated by titanium dioxide, n '-piperidyl-p- benzyl-imidodicarbonic diamide is scattered in again containing 10% 3 ethanol In 100 ml deionized water solution of amine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, magnetic force 350 watts of high voltage mercury lamp radiations are adopted 1 hour while stirring, sucking filtration, 100 DEG C of vacuum drying ovens of temperature are dried 12 hours, that is, obtain Visible light-responded nano-photocatalyst.

Embodiment 14:

Select n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion derivant as pi-conjugated Organic molecule, wherein imidodicarbonic diamide ring expansion derivant are the derivant of the horizontal ring expansion of ring of imidodicarbonic diamide, dimethyl amine Base-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step presses embodiment 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion It is slowly injected into 500 ml methanol, with sealing film phonograph seal and in 20 DEG C of environment of constant temperature in the beaker of the chloroform soln of derivant Middle standing 24 hours, finally gives stable n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion and derives The dispersion liquid of thing nanofiber, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion derivates nanometer fiber；

Carried metal Pt nanoparticle 3:

Again the n- dodecyl-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion is derived Thing is scattered in the 100 ml deionized water solution containing 10% triethanolamine again, under nitrogen protection, adds 3.33 milliliter 0.1 The chloroplatinic acid aqueous solution of gram per liter, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of temperature Vacuum drying oven is dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 15:

Select n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide ring expansion derivant as pi-conjugated Organic molecule, wherein imidodicarbonic diamide ring expansion derivant are the derivant of the ring longitudinal direction ring expansion of imidodicarbonic diamide, dimethyl amine Base-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step presses embodiment 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Carried metal Pt nanoparticle 3:

Embodiment 16:

Select n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivant as pi-conjugated organic Molecule, wherein imidodicarbonic diamide ring expansion derivant are the derivant of the horizontal ring expansion of ring of imidodicarbonic diamide, piperidyl-p- benzyl For electron-donating group, with chloroform as good solvent with methanol is as poor solvent, concrete operation step is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled derive containing 0.025 gram of n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion It is slowly injected into 500 ml methanol in the beaker of the chloroform soln of thing, with sealing film phonograph seal and quiet in 20 DEG C of environment of constant temperature Put 24 hours, finally give stable n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivates nanometer fine The dispersion liquid of dimension, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivates nanometer fiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivant weight Newly it is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliters 0.1 gram often The chloroplatinic acid aqueous solution rising, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum of temperature Oven drying 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 17:

Select n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivant as pi-conjugated organic Molecule, wherein imidodicarbonic diamide ring expansion derivant are the derivant of the ring longitudinal direction ring expansion of imidodicarbonic diamide, piperidyl-p- benzyl For electron-donating group, with chloroform as good solvent with methanol is as poor solvent, concrete operation step is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Carried metal Pt nanoparticle 3:

Embodiment 18:

Select n- dodecyl-n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide as pi-conjugated organic molecule, its Middle dimethyl amido-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operations walk Suddenly carry out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain the three of 0.025 gram of n- dodecyl-n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide It is slowly injected into 500 ml methanol, standing is 24 little with sealing film phonograph seal and in 20 DEG C of environment of constant temperature in the beaker of chloromethanes solution When, finally give the dispersion liquid of stable n- dodecyl-n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide nanofiber, Chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Dimethyl amido-p- benzyl-benzene-naphthalene diimide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n- dodecyl-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-benzene-naphthalene diimide is disperseed again In the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add the chlorine of 3.33 milliliter of 0.1 gram per liter Platinic acid aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum drying ovens of temperature are done Dry 12 hours, that is, 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, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the chloroform soln of n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide Beaker in be slowly injected into 500 ml methanol, with sealing film phonograph seal and in 20 DEG C of environment of constant temperature stand 24 hours, finally give The dispersion liquid of stable n, n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide nanofiber, chloroform wherein used and first Alcohol is the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n of coated by titanium dioxide, n '-dimethyl amine Base-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 10% 3 In 100 ml deionized water solution of ethanolamine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, 350 watts of high voltage mercury lamp radiations are adopted 1 hour while magnetic agitation, sucking filtration, dry 12 hours of 100 DEG C of vacuum drying ovens of temperature, that is, Obtain visible light-responded nano-photocatalyst.

Embodiment 20:

Select n- dodecyl-n '-piperidyl-p- benzyl-benzene-naphthalene diimide as pi-conjugated organic molecule, wherein piperazine Piperidinyl-p- benzyl is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is pressed and implemented Example 1 is carried out:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters of three chloromethanes containing 0.025 gram of n- dodecyl-n '-piperidyl-p- benzyl-benzene-naphthalene diimide will be filled It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, in the beaker of alkane solution Obtain the dispersion liquid of stable n- dodecyl-n '-piperidyl-p- benzyl-benzene-naphthalene diimide nanofiber eventually, wherein used three Chloromethanes and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Piperidyl-p- benzyl-benzene-naphthalene diimide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n- dodecyl-n ' of coated by titanium dioxide-piperidyl-p- benzyl-benzene-naphthalene diimide is again scattered in and contains In 100 ml deionized water solution of 10% triethanolamine, under nitrogen protection, add the chloroplatinic acid of 3.33 milliliter of 0.1 gram per liter Aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, and 100 DEG C of vacuum drying ovens of temperature are dried 12 Hour, that is, 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 Base is electron-donating group, and with chloroform as good solvent with methanol is as poor solvent, concrete operation step is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n, the burning of the chloroform soln of n '-piperidyl-p- benzyl-benzene-naphthalene diimide It is slowly injected into 500 ml methanol in cup, with sealing film phonograph seal and standing 24 hours in 20 DEG C of environment of constant temperature, finally give stable N, the dispersion liquid of n '-piperidyl-p- benzyl-benzene-naphthalene diimide nanofiber, chloroform wherein used and methanol are employing The anhydrous solvent that solvent distilling apparatus refine；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, 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 10% 3 ethanol In 100 ml deionized water solution of amine, under nitrogen protection, add the chloroplatinic acid aqueous solution of 3.33 milliliter of 0.1 gram per liter, magnetic force 350 watts of high voltage mercury lamp radiations are adopted 1 hour while stirring, sucking filtration, 100 DEG C of vacuum drying ovens of temperature are dried 12 hours, that is, 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 are electron-donating group, with chloroform as good solvent with methanol is as poor solvent, tool Body operating procedure is carried out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n- dodecyl-n '-dimethyl amido-p- benzyl-coronene two acyl Asia It is slowly injected into 500 ml methanol in the beaker of the chloroform soln of amine, with sealing film phonograph seal and quiet in 20 DEG C of environment of constant temperature Put 24 hours, finally give stable n- dodecyl-n '-dimethyl amido-p- benzyl-coronene imidodicarbonic diamide Nanowire The dispersion liquid of dimension, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Dimethyl amido-p- benzyl-coronene imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again by the n- dodecyl-n ' of coated by titanium dioxide-dimethyl amido-p- benzyl-coronene imidodicarbonic diamide weight Newly it is scattered in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliters 0.1 gram often The chloroplatinic acid aqueous solution rising, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum of temperature Oven drying 12 hours, that is, 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, with chloroform as good solvent with methanol is as poor solvent, concrete operation step Carry out by embodiment 1:

Preparing 1-dimention nano fiber 4 is skeleton:

100 milliliters will be filled and contain 0.025 gram of n- dodecyl-n '-piperidyl-p- benzyl-coronene imidodicarbonic diamide It is slowly injected into 500 ml methanol, with sealing film phonograph seal and standing 24 in 20 DEG C of environment of constant temperature in the beaker of chloroform soln Hour, finally give the dispersion of stable n- dodecyl-n '-piperidyl-p- benzyl-coronene imidodicarbonic diamide nanofiber Liquid, chloroform wherein used and methanol are the anhydrous solvent being refined using solvent distilling apparatus；

Surface coating titanium oxide inorganic semiconductor nano layer 2:

Under nitrogen protection and magnetic agitation, by Deca in the chloroform of the nanofiber obtaining/methanol dispersion 1 milliliter of anhydrous chloroform soln of 0.46 microlitre of isopropyl epoxide titanium, completion of dropping in 1 hour, and continue to stir 2 hours, It is added dropwise over 20 milliliter of 90% methanol aqueous solution again, after completion of dropping, continue stirring 12 hours, finally organic using 0.45 micron Membrane filtration, methanol washs, and 100 DEG C of vacuum drying ovens of temperature are dried 6 hours, obtain the n- dodecyl-n ' of coated by titanium dioxide- Piperidyl-p- benzyl-coronene imidodicarbonic diamide nanofiber；

Carried metal Pt nanoparticle 3:

Again the n- dodecyl-n ' of coated by titanium dioxide-piperidyl-p- benzyl-coronene imidodicarbonic diamide is divided again Dissipate in the 100 ml deionized water solution containing 10% triethanolamine, under nitrogen protection, add 3.33 milliliter of 0.1 gram per liter Chloroplatinic acid aqueous solution, adopts 350 watts of high voltage mercury lamp radiations 1 hour while magnetic agitation, sucking filtration, 100 DEG C of vacuum drying ovens of temperature It is dried 12 hours, that is, obtain visible light-responded nano-photocatalyst.

Embodiment 24

Any one visible-light response nano photocatalyst described in embodiment 1- embodiment 23 is used equally to visible ray 1 Lower hydrogen production by water decomposition, the basic embodiment of photocatalysis experiment is as follows:

The visible-light response nano obtaining photocatalyst is scattered in 100 milliliters that concentration is 10% triethanolamine or methanol In aqueous solution, it is placed in light-catalyzed reaction kettle, emptying twice, is shone using 400 watts of xenon lamps (400 nanometers of band pass filters of configuration) Penetrate, carry out the photocatalytic hydrogen production by water decomposition reaction under visible ray 1, produced gas uses online gas chromatogram test, result table Bright:

As can be seen from the table: visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst of the present invention is in visible Rhizoma Dioscoreae (peeled) Hydrogen production by water decomposition under part, the high efficiency photocatalyst for building visible light-responded provides new thinking and important reference.

Claims

1. a kind of visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst is it is characterised in that this photocatalyst is with one-dimensional organic half Conductor nanofiber (4) is skeleton, after Surface coating inorganic semiconductor nanometer layer (2), and uniform load metal nanoparticle (3) The nano-complex building, wherein one-dimensional organic semiconductor nanofiber (4) skeleton is with pi-conjugated organic molecule two acyl Imine derivative or imidodicarbonic diamide ring expansion derivant, benzene-naphthalene diimide derivative or coronene diimide derivative are former Material, anhydrous chloroform and absolute methanol, anhydrous chloroform and dehydrated alcohol, or anhydrous chloroform and anhydrous n-hexane are Solvent, using the preparation of body phase Supramolecular self assembly method；Inorganic semiconductor in inorganic semiconductor nanometer layer (2) is titanium dioxide Titanium, is coated on one-dimensional organic semiconductor nanofiber surface by organic titanium source for isopropyl epoxide titanium in-situ hydrolysis method；Gold Metal in metal nano-particle (3) is platinum, is supported on titanium dioxide surface by chloroplatinic acid photo-reduction method original position.

2. catalyst according to claim 1 it is characterised in that described diimide derivative be n- dodecyl- N '-dimethyl amido-p- phenyl-imidodicarbonic diamide, n- dodecyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide, N- dodecyl-n '-pyridine radicals-p- phenyl-imidodicarbonic diamide, n- dodecyl-n '-pyridine radicals-p- benzyl-two acyl is sub- Amine, n- dodecyl-n '-piperidyl-p- phenyl-imidodicarbonic diamide, n- dodecyl-n '-piperidyl-p- benzyl-two Acid imide, n-3- ethyl-heptyl-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide, n-3,5 ,-dioxy heptyl-n '-diformazan Base amido-p- benzyl-imidodicarbonic diamide, n- propionate-n '-dimethyl amido-p- benzyl-imidodicarbonic diamide, n, n '-diformazan Base amido-p- benzyl-imidodicarbonic diamide, n, n '-pyridine radicals-p- benzyl-imidodicarbonic diamide or n, n '-piperidyl-p- benzyl Base-imidodicarbonic diamide；Imidodicarbonic diamide ring expansion derivant is n- dodecyl-n '-dimethyl amido-p- benzyl-two acyl is sub- Amine ring expansion derivant or n- dodecyl-n '-piperidyl-p- benzyl-imidodicarbonic diamide ring expansion derivant；Benzene-naphthalene diimide spreads out Biological is n- dodecyl-n '-dimethyl amido-p- benzyl-benzene-naphthalene diimide, n, n '-dimethyl amido-p- benzyl-naphthalene Imidodicarbonic diamide, n- dodecyl-n '-piperidyl-p- benzyl-benzene-naphthalene diimide or n, n '-piperidyl-p- benzyl-naphthalene two acyl Imines；Coronene diimide derivative is n- dodecyl-n '-dimethyl amido-p- benzyl-coronene two acyl is sub- Amine or n- dodecyl-n '-piperidyl-p- benzyl-coronene imidodicarbonic diamide.

3. catalyst according to claim 1 is it is characterised in that described diimide derivative or imidodicarbonic diamide Ring expansion derivant, benzene-naphthalene diimide derivative or coronene diimide derivative have supplied for electronic electrophilic structure Molecule, 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.

4. the visible light-responded water decomposition hydrogen manufacturing nano-photocatalyst described in a kind of claim 1 is sacrificing reagent methanol or three second In the aqueous solution of hydramine it is seen that under light (1) decomposition water hydrogen making purposes.