CN102923696A - Method for preparing graphene through photocatalysis - Google Patents

Method for preparing graphene through photocatalysis Download PDF

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CN102923696A
CN102923696A CN2011102284589A CN201110228458A CN102923696A CN 102923696 A CN102923696 A CN 102923696A CN 2011102284589 A CN2011102284589 A CN 2011102284589A CN 201110228458 A CN201110228458 A CN 201110228458A CN 102923696 A CN102923696 A CN 102923696A
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CN102923696B (en
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吴骊珠
张慧慧
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a method for preparing graphene by photocatalysis, belongs to the technical field of materials, and relates to a method for synthesizing graphene by photocatalytic reduction in a solution by taking an organic dye or a metal complex dye as a photocatalyst and taking an organic negative hydrogen donor, an ascorbic acid derivative, an amine derivative, an alcohol derivative or an inorganic negative hydrogen donor, which comprises the following steps: pretreating graphite; oxidizing graphite; stripping the graphite oxide into graphene oxide; the graphene oxide is subjected to photocatalytic reduction under the condition of illumination, particularly visible light illumination. The photocatalytic system constructed by the invention adopts illumination, especially visible illumination, without adding any stabilizer, and a large amount of single-layer graphene with higher reduction degree is obtained through shorter reaction time.

Description

A kind of photochemical catalysis prepares the method for Graphene
Technical field
The present invention relates to a kind of method for preparing Graphene, especially relate to the method that a kind of photochemical catalysis prepares Graphene.
Background technology
Graphene is by sp 2The two-dimensional network structure that carbon consists of has excellent electricity, machinery and thermal property.Since finding first in 2004, the structure of Graphene uniqueness, very high surface-area and excellent electronic transmission performance have attracted scientist's extensive concern, at nano electron device, matrix material, solar cell, super capacitor, there is very widely application prospect the aspects such as hydrogen storage material, become one of at present the most popular material.
In order to bring into play the excellent properties of Graphene, the method that the development high yield prepares Graphene is most important, and this is because the hydrophobicity of Graphene and easy character of assembling in solution become the major obstacle of preparation Graphene.In order to overcome these difficulties, the strategy of chemical oxidation-dispersion-reduction is able to widespread use (S.Stankovich, D.A.Dikin, R.D.Piner, K.A.Kohlhaas, A.Kleinhammes, Y.Jia, Y.Wu, S.T.Nguyen and R.S.Ruoff, Carbon, 2007,45,1558).The principle of this method be first with oxygenant with graphite oxidation, then the ultra-sonic dispersion graphene oxide reduces with chemical reducing agent at last.This tactful advantage is that graphene oxide not only can prepare in a large number by chemical process, and its surperficial oxygen-containing functional group has increased the interlamellar spacing of Graphene, the dispersiveness of therefore doing well in water be a large amount of preparation Graphenes, and further functionalization is laid a good foundation.But the method for chemical reduction is used poisonous or dangerous reagent usually, the condition of high temperature, and extra tensio-active agent is to prevent the gathering of Graphene, these not enough electron-transportings that can affect Graphene bring many difficulties for the device fabrication of Graphene.
The method of the chemical reduction of using the earliest all is based on the reaction of thermal initiation, and the people such as Laura J.Cote had been developed photo-thermal method of deoxidation (L.J.Cote, R.Cruz-Silva and J.-X.Huang afterwards, J.Am.Chem.Soc., 2009,131,11027), the people such as Kamat have been developed the method (G.Williams of conductor photocatalysis reduction, B.Seger and P.V.Kamat, ACS Nano, 2008,2,1487).These methods all are to come initiating chamical reaction by light.As the reaction reagent of cleaning, " light " not only makes graphene device developed aspect lithography process, and makes Graphene-semiconductor photovoltaic material preparation become possibility.But these two kinds of methods have its limitation, although the method for photo-thermal deoxidation without any need for chemical reducing agent, can prepare pure Graphene, often need strong laser, strong photo-thermal effect is so that the graphene film of preparation easily breaks, and reducing degree is wayward.The method of photo catalytic reduction is relatively gentle, but the semiconductor catalyst such as the TiO that adopt at present 2, ZnO, H 3PW 12O 40All adopt ultraviolet excitation, and reducing degree is not high in the short period of time.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of photochemical catalysis to prepare the method for Graphene.The method adopts photochemical catalysis in the situation that do not add any stablizer, has just obtained the higher single-layer graphene of a large amount of reducing degrees through the shorter reaction times.
For solving the problems of the technologies described above, a kind of photochemical catalysis of the present invention prepares the method for Graphene, comprises the steps:
1) expansion process of graphite
9～15mL vitriol oil is heated to 75～85 ℃, adds 1.6g Potassium Persulfate and 1.6g Vanadium Pentoxide in FLAKES until solid all dissolves; Then add 1.8～2.2g graphite, under 75～85 ℃ of temperature, reacted 4～5 hours, filter, wash, obtain expanded graphite;
2) oxidation of expanded graphite
With step 1) expanded graphite that obtains joins in 75～85mL vitriol oil of ice bath cooling, slowly adds 8～12g potassium permanganate under magnetic agitation in this mixture, then 30～40 ℃ of lower reactions 3～5 hours, reacted again under the room temperature 1.5～2.5 hours; The deionized water that slowly adds 150～170mL keeps temperature to be no more than 50 ℃, continues to stir 1.5～2.5 hours; The water and the 30wt% hydrogen peroxide 8～12mL that add again 450～490mL, produce jonquilleous solution, this solution was placed after 24 hours, outwell supernatant liquor, then with remaining liquid first with the solution washing that contains 3wt% sulfuric acid, 1wt% hydrogen peroxide, and then with the 10wt%HCl washing, at last dialysis 6～8 days in water, the solid that obtains makes graphite oxide 45～55 ℃ of lower dryings;
3) graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
With step 2) graphite oxide that makes places deionized water, and through ul-trasonic irradiation 10～30 minutes, ultrasonic power was 150～250W, the graphene oxide solution that dissociates and obtain individual layer; Described graphite oxide: deionized water is 0.3mg～0.6mg: 1mL;
4) photo catalytic reduction graphene oxide
Getting step 3) the graphene oxide solution 10mL and the 20mL that obtain contain 10 -4Mol/L is to the N of saturated organic negative hydrogen donor, ascorbic acid derivates, sulfonamide derivatives, alcohol derivate or inorganic negative hydrogen donor, dinethylformamide or acetonitrile solution mix, stirred 5～10 minutes, then extremely limpid with ultrasonication, directly illumination or adding 1mL contain 1.5 * 10 -3Mol/L～1.5 * 10 -2The acetonitrile solution of the aqueous solution of mol/L organic dye or acetonitrile solution or metal complex dye, logical argon gas deoxygenation, reduced graphene oxide serving under illumination is removed organism in the system with organic solvent extraction after the reaction, the solid that obtains is washed first, then washing with acetone.
Further, described graphite is 325 purpose flaky graphites.
Further, direct illumination step 4) refers to carry out illumination with the 500W high voltage mercury lamp wavelength 900nm＞λ＞400nm.
Further, step 4) in, the photoreduction graphene oxide refers to that visible light shines or the near infrared light photograph wavelength 900nm＞λ＞400nm or 900nm＞λ＞450nm after adding dyestuff.
Further, step 4) organic negative hydrogen donor is 1 described in, 4-dihydrogen pyridine derivative, 1,2-dihydrogen pyridine derivative, 2,3-dihydro-benzimidizole derivatives, 2,3-dihydro-benzothiazole derivant, 2,3-dihydro-benzoxazole derivatives, 9,10-acridan, 1-phenylpyrrazolin.
Further, described Isosorbide-5-Nitrae-dihydrogen pyridine derivative is the compound with following structure:
Figure BDA0000082348430000021
R wherein 1=H, R 2=R 3=COOEt, R 4=H; R 1=H, R 2=R 3=COOEt, R 4=Me; R 1=H, R 2=R 3=COOEt, R 4=Et; R 1=H, R 2=R 3=COOEt, R 4=Ph; R 1=Ph, R 2=H, R 3=CONH 2, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CONH 2, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COCH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COOCH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COOH, R 4=H; R 1=CH 2Ph, R 2=H, R 3=H, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CN, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CHO, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CONHEt, R 4=H; R 1=CH 2Ph, R 2=CH 3, R 3=CONH 2, R 4=H; R 1=β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H; R 1=2,3,4,6-O-ethanoyl-β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H.
Further, described 1, the 2-dihydrogen pyridine derivative is the compound with following structure:
R 1=H, methyl (Me) or phenyl (Ph);
R 1=H, methyl (Me) or phenyl (Ph).
Further, described 2,3-dihydro-benzimidizole derivatives is the compound with following structure:
Figure BDA0000082348430000031
X=N, R 1=R 2=Me, R 3=H; X=N, R 1=R 2=Me, R 3=Ph; X=N, R 1=R 2=Me, R 3=β-D-Glucose-phenyl; X=N, R 1=R 2=Me, R 3=3 ', 4 ', 5 '-Ph.
Further, described 2,3-dihydro-benzoxazole derivatives are the compounds with following structure:
Figure BDA0000082348430000032
X=O, R 1=Me, R2=β-D-Glucose-phenyl.
Further, described 2,3-dihydro-benzothiazole derivant is the compound with following structure:
Figure BDA0000082348430000033
X=S, R 1=Me, R2=β-D-Glucose-phenyl.
Further, described 9, the 10-acridan has following structure:
Figure BDA0000082348430000034
R 1＝H，R 2＝H；R 1＝H，R 2＝Me；R 1＝H，R 2＝Ph；R 1＝Me，R 2＝H；R 1＝Me，R 2＝Me；R 1＝Me，R 2＝Ph。
Further, described 1-phenylpyrrazolin is the compound with following structure:
Figure BDA0000082348430000035
R 1＝Me，R 2＝Ph；R 1＝Ph，R 2＝Ph；R 1＝Ph，R 2＝p-MeO-C 6H 4；R 1＝Ph，R 2＝p-ClC 6H 4；R 1＝Ph，R 2＝p-NO 2C 6H 4。
Further, described ascorbic acid derivates is the compound with following structure:
Figure BDA0000082348430000036
R:C (CH 3) or Phenyl.
Further, described sulfonamide derivatives comprises trolamine, triethylamine, disodium EDTA.
Further, described alcohol derivate comprises methyl alcohol, ethylene glycol and the compound with following structure:
Figure BDA0000082348430000037
Further, described inorganic negative hydrogen donor comprises following compound: NaBH 4, NaB (OAc) 3H, NaBH 3CN or HSnPh 3
Further, step 4) organic dye described in is eosin W or W S, uranine yellow salt, 2,7-dichlorofluorescein, rhodamine B, Nile red, alizarin red S, safranine T, acridine orange, Hypocrellin A, Hypocrellin B, perylene diimide class dyestuff, porphyrin dyestuff, thiazin dyes, polyenoid class dyestuff, coumarins dyestuff, carbazoles dyestuff, the glimmering class dyestuff of fluorine boron, fullerene derivate.
Further, the selected representative molecular structures of Suo Shu perylene diimide class dyestuff, porphyrin dyestuff, thiazin dyes, polyenoid class dyestuff, coumarins dyestuff, carbazoles dyestuff, the glimmering class dyestuff of fluorine boron, fullerene derivate is as follows successively:
Wherein: R 1=R 1'=CH 3, R 2=R 2'=H, R 3=R 3'=CH 3R 1=R 1'=CH 3, R 2=R 2'=CH 3, R 3=R 3'=CH 3R 1=CH 3, R 2=H, R 3=CH 3, R 1'=phenyl (phenyl), R 2'=H, R 3'=phenyl (phenyl);
Figure BDA0000082348430000051
Further, described metal complex dye comprises the dipyridyl title complex, platinum, the phenanthroline title complex of rhenium, second bipyridine-phenanthroline or 2-phenyl-pyridine-phenanthroline title complex and the Coordination Reaction of Zinc Porphyrin Complexes of iridium of platinum, ruthenium, rhenium, osmium.
Further, the dipyridyl title complex of described platinum be terpyridyl divalence platinum complex, second bipyridine divalence platinum complex, 6-phenyl-2,2 '-second bipyridine divalence platinum complex; The dipyridyl title complex of described ruthenium is second bipyridine ruthenium complexe, terpyridyl ruthenium complexe; The dipyridyl title complex of described rhenium is the second bipyridine rhenium compound; The dipyridyl title complex second bipyridine osmium title complex of described osmium; The phenanthroline title complex of described platinum is phenanthroline divalence platinum complex; The phenanthroline title complex of described rhenium is the phenanthroline rhenium compound;
Described terpyridyl divalence platinum complex has following structure:
Figure BDA0000082348430000052
R in the formula 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CCH 2OH, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CCH 2CH 2CH 3, R 3, R 4Independently be H; Or R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C (CH 3) 3, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCOCH 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CCH 2OCOCH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer, R 3, R 4Independently be H; Or R 1Be H, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be Cl; Or R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be C ≡ CC 6H 5R in the formula 5Be Cl -, ClO 4 -Or PF 6
Described second bipyridine divalence platinum complex has following structure:
R in the formula 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, R 2Be Cl, C ≡ CC 6H 4CH 3-4, C ≡ CC 6H 4C ≡ CC 6H 5-4, C ≡ CCH 2OH, C ≡ CC 6H 5, C ≡ CC 6H 4OCH 3-4, C ≡ CC 6H 4OCOCH 3, C ≡ CSi (CH 3) 3Or C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer;
Described 6-phenyl-2,2 '-second bipyridine divalence platinum complex has following structure:
Figure BDA0000082348430000062
R in the formula 1Be H, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 5, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently be H;
Described second bipyridine ruthenium complexe has following structure:
Figure BDA0000082348430000063
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3
Described terpyridyl ruthenium complexe has following structure:
R in the formula 1Be C 6H 4OCH 3-4, R 2, R 3Independently be H; Or R 1Be C 6H 4CH 3-4, R 2, R 3Independently be H; Or R 1Be C (CH 3) 3, R 2, R 3Independently be H; Or R 1, R 2, R 3Independently be H; Or R 1, R 2, R 3Independently be C (CH 3) 3
Described second bipyridine-phenanthroline (X=N) or 2-phenyl-pyridine-phenanthroline (X=C) complex of iridium have following structure:
Figure BDA0000082348430000071
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, R 2Be H, CH 3Or p-SO 3-phenyl, X=N or C;
Described second bipyridine rhenium compound has following structure:
Figure BDA0000082348430000072
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, X=Cl or Br;
Described second bipyridine osmium title complex has following structure:
Described phenanthroline divalence platinum complex has following structure:
Figure BDA0000082348430000074
R in the formula 1Be H or CH 3R 2Be Cl, C ≡ CC 6H 4CH 3-4, C ≡ CC 6H 4C ≡ CC 6H 5-4, C ≡ CCH 2OH, C ≡ CC 6H 5, C ≡ CC 6H 4OCH 3-4, C ≡ CC 6H 4OCOCH 3, C ≡ CSi (CH 3) 3Or C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer;
Described phenanthroline rhenium compound has following structure:
Figure BDA0000082348430000075
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, X=Cl or Br;
Described Coordination Reaction of Zinc Porphyrin Complexes has following structure:
Figure BDA0000082348430000081
The present invention has following beneficial effect:
1, reaction conditions is gentle, and illumination can cause the photo catalytic reduction reaction under any stablizer room temperature condition in the situation that do not add, and some organic dye is natural dyestuff, is dirt cheap.
2, the dyestuff of anionic and negative hydrogen donor are adsorbed on the Graphene surface, can avoid the gathering of Graphene, and the Graphene that obtains is dispersed better, can effectively improve the processibility of Graphene.
3, experiment integrated operation step is simple, photochemical reaction prepares the higher Graphene of reducing degree at short notice, and simultaneous reactions is in illumination, and particularly visible light carries out under shining, save energy not only, and remarkable based on application prospect aspect the electron device of Graphene in photoetching, the preparation of light decorations.
Description of drawings
Figure 1 shows that among the embodiment 1 visible light according to or near infrared light according to (take Isosorbide-5-Nitrae-dihydropyridine (R=H) as the photoreduction agent, eosin W or W S is the atomic force microscope figure that photocatalyst prepares Graphene under the condition of 900nm＞λ＞450nm);
Figure 2 shows that among the embodiment 1 visible light according to or near infrared light according to (take Isosorbide-5-Nitrae-dihydropyridine (R=H) as the photoreduction agent, eosin W or W S is the transmission electron microscope picture that photocatalyst prepares Graphene under the condition of 900nm＞λ＞450nm);
Figure 3 shows that among the embodiment 1 visible light according to or near infrared light according to (take Isosorbide-5-Nitrae-dihydropyridine (R=H) as the photoreduction agent, eosin W or W S is the infrared spectrogram that photocatalyst prepares Graphene under the condition of 900nm＞λ＞450nm).
Embodiment
Below in conjunction with specific embodiment the present invention is for further processing, but the present invention is not limited to following examples.
Embodiment 1:
A kind of photochemical catalysis prepares the method for Graphene, comprises the steps:
1) expansion process of graphite:
The vitriol oil of 9mL is heated to 80 ℃, adds 1.6g Potassium Persulfate and 1.6g Vanadium Pentoxide in FLAKES, stirring makes solid entirely molten under this temperature, then slowly adds 2g 325 purpose crystalline flake graphites, adds in 5 minutes; This mixed solution was 80 ℃ of lower reactions 4.5 hours, and reaction finishes cool to room temperature, then adds the 350mL deionized water, places after 12 hours, with the membrane filtration of this mixture through 0.2 μ m, goes residual acid with a large amount of washings; Solid was at room temperature placed 12 hours;
2) oxidation of expanded graphite:
The vitriol oil of getting 80mL places 0 ℃ ice bath, with step 1) expanded graphite that obtains joins in the sulphuric acid soln, then the potassium permanganate that under agitation slowly adds 10g, guarantee in the process that adds that temperature is no more than 10 ℃, 35 ℃ of lower reactions 4 hours, then reacted under the room temperature 2 hours after adding, reaction adds the 160mL deionized water after finishing in batches again, originally can under ice bath, carry out, guarantee that temperature is no more than 50 ℃; At room temperature reacted after water injection 2 hours, and then the water of adding 470mL, the superoxol that adds again 10mL 30wt% after adding, produce jonquilleous solution, this solution was placed after 24 hours, outwell supernatant liquor, then with remaining centrifugal, the solution that contains 3wt% sulfuric acid, 1wt% hydrogen peroxide with 200mL is first washed twice, and then with twice of the 10wt%HCl of 200mL washing, each washing all will be first with the solids mixing stirring of washings and graphite oxide 30 minutes, and then the centrifugal washings that removes; Last obtain gel during again with the washing of 200mL, in the dialysis tubing of at this moment coagulant liquid being packed into, one week of dialysis in deionized water.Then the coagulant liquid after the dialysis is poured in the culture dish, and drying is 48 hours in 50 ℃ baking oven, obtains graphite oxide;
3) graphite oxide is peeled off and is the mono-layer graphite olefinic oxide:
Graphite oxide is dispersed in water, and ultrasonic power is 150W, through ul-trasonic irradiation 20 minutes, forms the graphene oxide solution of 0.3mg/mL;
4) photo catalytic reduction graphene oxide
Get 10mL graphene oxide solution, join and contain 25mg Isosorbide-5-Nitrae-dihydropyridine (R 1=H, R 2=R 3=COOEt, R 4In=H) the 20mL DMF solution, stirred after 5 minutes ultrasonication 1 minute, add 1mL and contain 1.5 * 10 -2The aqueous solution of mol/L eosin W or W S, logical argon gas deoxygenation 20 minutes added 900nm＞λ under the spectral filter＞450nm illumination 4 hours at the 500W high voltage mercury lamp, removed organism in the system with organic solvent extraction after the reaction, the solid that obtains washing 10 times, acetone is washed 20 times.
Embodiment 2:
Repeat embodiment 1, its difference only is: in step 4) in, described Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=H, R 2=R 3=COOEt, R 4=H) be 35mg.
Embodiment 3
Repeat embodiment 1, its difference only is: in step 3) in, the concentration of the aqueous solution of described eosin W or W S is 1.5 * 10 -3Mol/L.
Embodiment 4
Repeat embodiment 1, its difference only is: in step 4) described in 25mg1,4-dihydrogen pyridine derivative (R 1=H, R 2=R 3=COOEt, R 4=Me) 20mL acetonitrile solution.
Embodiment 5
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=H, R 2=R 3=COOEt, R 4=Et) 20mL acetonitrile solution.
Embodiment 6
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=H, R 2=R 3=COOEt, R 4=Ph) 20mL acetonitrile solution.
Embodiment 7
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=Ph, R 2=H, R 3=CONH 2, R 4=H) 20mL acetonitrile solution.
Embodiment 8
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=CONH 2, R 4=H) 20mL acetonitrile solution.
Embodiment 9
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=COCH 3, R 4=H) 20mL acetonitrile solution.
Embodiment 10
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=COOCH 3, R 4=H) 20mL acetonitrile solution.
Embodiment 11
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=COOH, R 4=H) 20mL acetonitrile solution.
Embodiment 12
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=H, R 4=H) 20mL acetonitrile solution.
Embodiment 13
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=CH 3, R 4=H) 20mL acetonitrile solution.
Embodiment 14
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=CN, R 4=H) 20mL acetonitrile solution.
Embodiment 15
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=CHO, R 4=H) 20mL acetonitrile solution.
Embodiment 16
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=H, R 3=CONHEt, R 4=H) 20mL acetonitrile solution.
Embodiment 17
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=CH 2Ph, R 2=CH 3, R 3=CONH 2, R 4=H) 20mL acetonitrile solution.
Embodiment 18
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H) 20mL acetonitrile solution.
Embodiment 19
Repeat embodiment 1, its difference only is: in step 4) described in 25mg Isosorbide-5-Nitrae-dihydrogen pyridine derivative (R 1=2,3,4,6-O-ethanoyl-β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H) 20mL acetonitrile solution.
Embodiment 20
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
Figure BDA0000082348430000101
R 1＝H。
Embodiment 21
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
Figure BDA0000082348430000102
R 1＝Me。
Embodiment 22
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
R 1＝Ph。
Embodiment 23
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
R 1＝H。
Embodiment 24
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
Figure BDA0000082348430000113
R 1＝Me。
Embodiment 25
Repeat embodiment 1, its difference only is: in step 4) in adding contain 25mg1, the 20mL acetonitrile solution of 2-dihydrogen pyridine derivative, structure is as follows:
Figure BDA0000082348430000114
R 1＝Ph。
Embodiment 26
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzimidizole derivatives (X=N, R 1=R 2=Me, R 3=H) be 25mg.
Embodiment 27
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzimidizole derivatives (X=N, R 1=R 2=Me, R 3=Ph) be 25mg.
Embodiment 28
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzimidizole derivatives (X=N, R 1=R 2=Me, R 3=β-D-Glucose-phenyl) is 25mg.
Embodiment 29
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzimidizole derivatives (X=N, R 1=R 2=Me, R 3=3 ', 4 ', 5 '-Ph) be 25mg.
Embodiment 30
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzoxazole derivatives (X=O, R 1=Me, R 2=β-D-Glucose-phenyl) is 25mg.
Embodiment 31
Repeat embodiment 1, its difference only is: in step 4) described in 2,3-dihydro-benzothiazole derivant (X=S, R 1=Me, R 2=β-D-Glucose-phenyl) is 25mg.
Embodiment 32
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=H, R 2=H) be 25mg.
Embodiment 33
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=H, R 2=Me) be 25mg.
Embodiment 34
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=H, R 2=Ph) be 25mg.
Embodiment 35
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=Me, R 2=H) be 25mg.
Embodiment 36
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=Me, R 2=Me) be 25mg.
Embodiment 37
Repeat embodiment 1, its difference only is: in step 4) described in 9,10-acridan (R 1=Me, R 2=Ph) be 25mg.
Embodiment 38
Repeat embodiment 1, its difference only is: in step 4) described in 1-phenylpyrrazolin (R 1=Me, R 2=Ph) be 25mg.
Embodiment 39
Repeat embodiment 1, its difference only is: in step 4) described in 1-phenylpyrrazolin (R 1=Ph, R 2=Ph) be 25mg.
Embodiment 40
Repeat embodiment 1, its difference only is: in step 4) described in 1-phenylpyrrazolin (R 1=Ph, R 2=p-MeO-C 6H 4) be 25mg.
Embodiment 41
Repeat embodiment 1, its difference only is: in step 4) described in 1-phenylpyrrazolin (R 1=Ph, R 2=p-ClC 6H 4) be 25mg.
Embodiment 42
Repeat embodiment 1, its difference only is: in step 4) described in 1-phenylpyrrazolin (R 1=Ph, R 2=p-NO 2C 6H 4) be 25mg.
Embodiment 43
Repeat embodiment 1, its difference only is: in step 4) described in ascorbic acid derivates be 37.5mg, structure is as follows:
Figure BDA0000082348430000121
R＝C(CH 3) 3。
Embodiment 44
Repeat embodiment 1, its difference only is: in step 4) described in ascorbic acid derivates be 37.5mg, structure is as follows:
Figure BDA0000082348430000131
R＝Phenyl。
Embodiment 45
Repeat embodiment 1, its difference only is: in step 4) described in ascorbic acid derivates be 37.5mg, structure is as follows:
Figure BDA0000082348430000132
Embodiment 46
Repeat embodiment 1, its difference only is: in step 4) described in ascorbic acid derivates be 37.5mg, structure is as follows:
Figure BDA0000082348430000133
Embodiment 47
Repeat embodiment 1, its difference only is: in step 4) described in ascorbic acid derivates be 37.5mg, structure is as follows:
Figure BDA0000082348430000134
Embodiment 48
Repeat embodiment 1, its difference only is: in step 4) described in trolamine be 15mg.
Embodiment 49
Repeat embodiment 1, its difference only is: in step 4) described in triethylamine be 15mg.
Embodiment 50
Repeat embodiment 1, its difference only is: in step 4) described in disodium EDTA be 15mg.
Embodiment 51
Repeat embodiment 1, its difference only is: in step 4) described in methyl alcohol be 1mL.
Embodiment 52
Repeat embodiment 1, its difference only is: in step 4) described in ethylene glycol be 1mL.
Embodiment 53
Repeat embodiment 1, its difference only is: in step 4) described in alcohol be 20mg, structure is as follows:
Figure BDA0000082348430000135
Embodiment 54
Repeat embodiment 1, its difference only is: in step 4) described in alcohol be 20mg, structure is as follows:
Figure BDA0000082348430000136
Embodiment 55
Repeat embodiment 1, its difference only is: in step 4) described in alcohol be 20mg, structure is as follows:
Figure BDA0000082348430000141
Embodiment 56
Repeat embodiment 1, its difference only is: in step 4) described in alcohol be 20mg, structure is as follows:
Figure BDA0000082348430000142
Embodiment 57
Repeat embodiment 1, its difference only is: in step 4) described in NaBH 4Be 10mg.
Embodiment 58
Repeat embodiment 1, its difference only is: in step 4) described in NaB (OAc) 3H is 10mg.
Embodiment 59
Repeat embodiment 1, its difference only is: in step 4) described in NaBH 3CN is 10mg.
Embodiment 60
Repeat embodiment 1, its difference only is: in step 4) described in HSnPh 3Be 10mg.
Embodiment 61
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described uranine yellow salt brine solution is 1.5 * 10 -2Mol/L, visible light shines or near infrared illumination wavelength 900nm＞λ＞400nm.
Embodiment 62
Repeat embodiment 1, its difference only is: in step 4) in, described 2, the concentration of the 7-dichlorofluorescein aqueous solution is 1.5 * 10 -2Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 63
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the described safranine T aqueous solution is 7.5 * 10 -3Mol/L.
Embodiment 64
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the described acridine orange aqueous solution is 7.5 * 10 -3Mol/L.
Embodiment 65
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described porphyrin aqueous dye solutions is 7.5 * 10 -3Mol/L.
Embodiment 66
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the described rhodamine B aqueous solution is 7.5 * 10 -3Mol/L.
Embodiment 67
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described Nile red acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 68
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described alizarin red S acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 69
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described Hypocrellin A acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 70
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of Suo Shu perylene diimide class dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 71
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described thiazin dyes acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 72
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described polyenoid class dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 73
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described coumarins dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 74
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described carbazoles dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 75
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described Hypocrellin B dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 76
Repeat embodiment 1, its difference only is: in step 4) in, the glimmering class dyestuff of described fluorine boron (R 1=R 1'=CH 3, R 2=R 2'=H, R 3=R 3'=CH 3), the concentration of its acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 77
Repeat embodiment 1, its difference only is: in step 4) in, the glimmering class dyestuff of described fluorine boron (R 1=R 1'=CH 3, R 2=R 2'=CH 3, R 3=R 3'=CH 3), the concentration of its acetonitrile solution is 7.5 * 10 -3Mol/L.
Embodiment 78
Repeat embodiment 1, its difference only is: in step 4) in, the glimmering class dyestuff of described fluorine boron (R 1=CH 3, R 2=H, R 3=CH 3, R 1'=phenyl, R 2'=H, R 3'=phenyl), the concentration of its acetonitrile solution are 7.5 * 10 -3Mol/L.
Embodiment 79
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described fullerene derivate class dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.Wherein the structure iron of fullerene derivate is:
Embodiment 80
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of described fullerene derivate class dyestuff acetonitrile solution is 7.5 * 10 -3Mol/L.Wherein the structure iron of fullerene derivate is:
Figure BDA0000082348430000161
Embodiment 81
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 82
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently be H, R 5Be ClO 4) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 83
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H.R 5Be PF 6 -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 84
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 85
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 86
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CCH 2OH, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 87
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ CCH 2CH 2CH 3, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 88
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 89
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C (CH 3) 3, R 2Be Cl, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 90
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 91
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCH 3-4, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 92
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 93
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCOCH 3, R 3, R 3Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 94
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 95
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 96
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 7, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 97
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 16, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 98
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ CCH 2OCOCH 3, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 99
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be Cl, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 100
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 101
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 102
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 7, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 103
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 16, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 104
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1Be H, R 2Be C 6H 5, R 3, R 4Independently be H, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 105
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be Cl, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 106
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl divalence platinum complex (R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be C ≡ CC 6H 5, R 5Be Cl -) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 107
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be H, R 2Be Cl, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 108
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 5, R 2Be Cl, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 109
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 110
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 111
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 112
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 113
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 114
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 115
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 116
Repeat embodiment 1, its difference only is: in step 4) in, described 6-phenyl-2,2 '-second bipyridine divalence platinum complex (R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 117
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be H, R 2Be Cl) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 118
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be CH 3, R 2Be C ≡ CC 6H 4CH 3The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 119
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be Cl, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 120
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be OCH 3, R 2Be C ≡ CCH 2The concentration of acetonitrile solution OH) is 7.5 * 10 -3Mol/L.
Embodiment 121
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 5) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 122
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 4OCH 3The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 123
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 4OCOCH 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 124
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, R 2Be C ≡ CSi (CH 3) 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 125
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, C ≡ C (CH 2) nCH 3, wherein n is 1) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 126
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, C ≡ C (CH 2) nCH 3, wherein n is 7) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 127
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine divalence platinum complex (R 1Be C (CH 3) 3, C ≡ C (CH 2) nCH 3, wherein n is 16) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 128
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine ruthenium complexe (R 1Be H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 129
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine ruthenium complexe (R 1Be CH 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 130
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine ruthenium complexe (R 1Be Cl) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 131
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine ruthenium complexe (R 1Be OCH 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 132
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine ruthenium complexe (R 1Be C (CH 3) 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 133
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl ruthenium complexe (R 1Be C 6H 4OCH 3-4, R 2, R 3Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 134
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl ruthenium complexe (R 1Be C 6H 4CH 3-4, R 2, R 3Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 135
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl ruthenium complexe (R 1, R 2, R 3Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 136
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl ruthenium complexe (R 1Be C (CH 3) 3, R 2, R 3Independently for H) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 137
Repeat embodiment 1, its difference only is: in step 4) in, described terpyridyl ruthenium complexe (R 1, R 2, R 3Independently be C (CH 3) 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 138
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine-phenanthroline complex of iridium (R 1Be H, R 2Be H, X is N) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 139
Repeat embodiment 1, its difference only is: in step 4) in, described 2-phenyl-pyridine-phenanthroline complex of iridium (R 1Be CH 3, R 2Be CH 3, X is C) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 140
Repeat embodiment 1, its difference only is: in step 4) in, described 2-phenyl-pyridine-phenanthroline complex of iridium (R 1Be Cl, R 2Be p-SO 3-phenyl, X are C) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 141
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine-phenanthroline complex of iridium (R 1Be OCH 3, R 2Be H, X is N) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 142
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine-phenanthroline complex of iridium (R 1Be C (CH 3) 3, R 2Be H, X is N) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 143
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine rhenium compound (R 1Be H, X is Cl) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 144
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine rhenium compound (R 1Be CH 3, X is Br) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 145
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine rhenium compound (R 1Be Cl, X is Br) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 146
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine rhenium compound (R 1Be OCH 3, X is Br) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 147
Repeat embodiment 1, its difference only is: in step 4) in, described second bipyridine rhenium compound (R 1Be C (CH 3) 3, X is Br) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 148
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described second bipyridine osmium title complex is 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 149
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be Cl) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 150
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be CH 3, R 2Be C ≡ CC 6H 4CH 3The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 151
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 152
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CCH 2The concentration of acetonitrile solution OH) is 7.5 * 10 -3Mol/L.
Embodiment 153
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CC 6H 5) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 154
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CC 6H 4OCH 3The concentration of acetonitrile solution-4) is 7.5 * 10 -3Mol/L.
Embodiment 155
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CC 6H 4OCOCH 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 156
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ CSi (CH 3) 3) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 157
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 158
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 7) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 159
Repeat embodiment 1, its difference only is: in step 4) in, described phenanthroline divalence platinum complex (R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 16) the concentration of acetonitrile solution be 7.5 * 10 -3Mol/L.
Embodiment 160
Repeat embodiment 1, its difference only is: in step 4) in, the acetonitrile solution (R of described phenanthroline rhenium compound 1Be H, X is Cl) concentration be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 161
Repeat embodiment 1, its difference only is: in step 4) in, the acetonitrile solution (R of described phenanthroline rhenium compound 1Be CH 3, X is Br) concentration be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 162
Repeat embodiment 1, its difference only is: in step 4) in, the acetonitrile solution (R of described phenanthroline rhenium compound 1Be Cl, X is Br) concentration be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 163
Repeat embodiment 1, its difference only is: in step 4) in, the acetonitrile solution (R of described phenanthroline rhenium compound 1Be OCH 3, X is Br) concentration be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 164
Repeat embodiment 1, its difference only is: in step 4) in, the acetonitrile solution (R of described phenanthroline rhenium compound 1Be C (CH 3) 3, X is Br) concentration be 7.5 * 10 -3Mol/L, illumination wavelength 900nm＞λ＞400nm.
Embodiment 165
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described Coordination Reaction of Zinc Porphyrin Complexes is 7.5 * 10 -3Mol/L.The structure of Coordination Reaction of Zinc Porphyrin Complexes is as follows:
Figure BDA0000082348430000221
R 1Be H.
Embodiment 166
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described Coordination Reaction of Zinc Porphyrin Complexes is 7.5 * 10 -3Mol/L.The structure of Coordination Reaction of Zinc Porphyrin Complexes is as follows:
Figure BDA0000082348430000222
R 1Be SO 3Na.
Embodiment 167
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described Coordination Reaction of Zinc Porphyrin Complexes is 7.5 * 10 -3Mol/L.The structure of Coordination Reaction of Zinc Porphyrin Complexes is as follows:
Figure BDA0000082348430000231
Embodiment 168
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described Coordination Reaction of Zinc Porphyrin Complexes is 7.5 * 10 -3Mol/L.The structure of Coordination Reaction of Zinc Porphyrin Complexes is as follows:
Figure BDA0000082348430000232
Embodiment 169
Repeat embodiment 1, its difference only is: in step 4) in, the concentration of the acetonitrile solution of described Coordination Reaction of Zinc Porphyrin Complexes is 7.5 * 10 -3Mol/L.The structure of Coordination Reaction of Zinc Porphyrin Complexes is as follows:
Figure BDA0000082348430000233
Embodiment 170
Repeat embodiment 1, its difference only is: in step 4) in, direct photoreduction graphene oxide.
Embodiment 171
A kind of photochemical catalysis prepares the method for Graphene, comprises the steps:
1) expansion process of graphite:
The vitriol oil of 15mL is heated to 85 ℃, adds 1.6g Potassium Persulfate and 1.6g Vanadium Pentoxide in FLAKES, stirring makes solid entirely molten under this temperature, then slowly adds 1.8g 325 purpose crystalline flake graphites, adds in 5 minutes; This mixed solution was 85 ℃ of lower reactions 4 hours, and reaction finishes cool to room temperature, then adds the 350mL deionized water, places after 12 hours, with the membrane filtration of this mixture through 02 μ m, goes residual acid with a large amount of washings; Solid was at room temperature placed 12 hours;
2) oxidation of expanded graphite:
The vitriol oil of getting 75mL places 0 ℃ ice bath, with step 1) expanded graphite that obtains joins in the sulphuric acid soln, then the potassium permanganate that under agitation slowly adds 8g, guarantee in the process that adds that temperature is no more than 10 ℃, 40 ℃ of lower reactions 3 hours, then reacted under the room temperature 1.5 hours after adding, reaction adds the 150mL deionized water after finishing in batches again, originally can under ice bath, carry out, guarantee that temperature is no more than 50 ℃; At room temperature reacted after water injection 1.5 hours, and then the water of adding 450mL, the superoxol that adds again 8mL 30wt% after adding, produce jonquilleous solution, this solution was placed after 24 hours, outwell supernatant liquor, then with remaining centrifugal, the solution that contains 3wt% sulfuric acid, 1wt% hydrogen peroxide with 200mL is first washed twice, and then with twice of the 10wt%HCl of 200mL washing, each washing all will be first with the solids mixing stirring of washings and graphite oxide 30 minutes, and then the centrifugal washings that removes; Last obtain gel during again with the washing of 200mL, at this moment coagulant liquid is packed in the dialysis tubing, dialysis is 6 days in deionized water.Then the coagulant liquid after the dialysis is poured in the culture dish, and drying is 48 hours in 55 ℃ baking oven, obtains graphite oxide;
3) graphite oxide is peeled off and is the mono-layer graphite olefinic oxide:
Graphite oxide is dispersed in water, and ultrasonic power is 200W, through ul-trasonic irradiation 10 minutes, forms the graphene oxide solution of 0.6mg/mL;
4) photo catalytic reduction graphene oxide
Get 10mL graphene oxide solution, join in the 20mL DMF solution that contains 25mg Isosorbide-5-Nitrae-dihydropyridine, the R of this Isosorbide-5-Nitrae-dihydropyridine is ethyl, stirs after 10 minutes ultrasonication 1 minute, adds 1mL and contains 1.5 * 10 -2The aqueous solution of mol/L eosin W or W S, logical argon gas deoxygenation 20 minutes added 900nm＞λ under the spectral filter＞450nm illumination 4 hours at the 500W high voltage mercury lamp, removed organism in the system with organic solvent extraction after the reaction, the solid that obtains washing 10 times, acetone is washed 20 times.
Embodiment 172
A kind of photochemical catalysis prepares the method for Graphene, comprises the steps:
1) expansion process of graphite:
The vitriol oil of 15mL is heated to 75 ℃, adds 1.6g Potassium Persulfate and 1.6g Vanadium Pentoxide in FLAKES, stirring makes solid entirely molten under this temperature, then slowly adds 22g 325 purpose crystalline flake graphites, adds in 5 minutes; This mixed solution was 75 ℃ of lower reactions 5 hours, and reaction finishes cool to room temperature, then adds the 350mL deionized water, places after 12 hours, with the membrane filtration of this mixture through 02 μ m, goes residual acid with a large amount of washings; Solid was at room temperature placed 12 hours;
2) oxidation of expanded graphite:
The vitriol oil of getting 85mL places 0 ℃ ice bath, with step 1) expanded graphite that obtains joins in the sulphuric acid soln, then the potassium permanganate that under agitation slowly adds 12g, guarantee in the process that adds that temperature is no more than 10 ℃, 30 ℃ of lower reactions 5 hours, then reacted under the room temperature 2.5 hours after adding, reaction adds the 170mL deionized water after finishing in batches again, originally can under ice bath, carry out, guarantee that temperature is no more than 50 ℃; At room temperature reacted after water injection 2.5 hours, and then the water of adding 490mL, the superoxol that adds again 12mL 30wt% after adding, produce jonquilleous solution, this solution was placed after 24 hours, outwell supernatant liquor, then with remaining centrifugal, the solution that contains 3wt% sulfuric acid, 1wt% hydrogen peroxide with 200mL is first washed twice, and then with twice of the 10wt%HCl of 200mL washing, each washing all will be first with the solids mixing stirring of washings and graphite oxide 30 minutes, and then the centrifugal washings that removes; Last obtain gel during again with the washing of 200mL, at this moment coagulant liquid is packed in the dialysis tubing, dialysis is 8 days in deionized water.Then the coagulant liquid after the dialysis is poured in the culture dish, and drying is 48 hours in 45 ℃ baking oven, obtains graphite oxide;
3) graphite oxide is peeled off and is the mono-layer graphite olefinic oxide:
Graphite oxide is dispersed in water, and ultrasonic power is 250W, through ul-trasonic irradiation 30 minutes, forms the graphene oxide solution of 0.45mg/mL;
4) photo catalytic reduction graphene oxide
Get 10mL graphene oxide solution, join in the 20mL DMF solution that contains 25mg Isosorbide-5-Nitrae-dihydropyridine, the R in this Isosorbide-5-Nitrae-dihydropyridine is 4-methoxyl group-phenyl, stirs after 10 minutes ultrasonication 1 minute, adds 1mL and contains 1.5 * 10 -2The aqueous solution of mol/L eosin W or W S, logical argon gas deoxygenation 20 minutes added 900nm＞λ under the spectral filter＞450nm illumination 4 hours at the 500W high voltage mercury lamp, removed organism in the system with organic solvent extraction after the reaction, the solid that obtains washing 10 times, acetone is washed 20 times.
By the synthetic Graphene of above-described embodiment, can regulate and control the degree that graphene oxide is reduced by changing photosensitive molecular and the type of photoreduction agent, the amount of photoreduction agent and the amount of catalyzer, the Graphene that embodiment 1 is obtained characterizes through atomic force microscope and transmission electron microscope.Can find out from the atomic force microscope picture of Fig. 1, the Graphene surface that obtains is substantially smooth, and thickness is 0.8nm, the consistency of thickness of the Graphene that obtains with general chemical reduction method.Simultaneously, can observe the intrinsic fold of Graphene and laminate structure at transmission electron microscope (Fig. 2), further confirm to obtain single-layer graphene by diffraction pattern, not have the structure of similar graphite.Further compare the infrared spectrogram of photo catalytic reduction graphene oxide, the graphene oxide after can finding to reduce is at 1715cm -1Corresponding carbonylic stretching vibration absorption peak, 3100～3600cm -1Corresponding hydroxyl vibration peak and 970～1050cm -1The stretching vibration absorption peak of corresponding C-O singly-bound all obviously disappears or weakens, and illustrates that this method can make the oxygen-containing functional group in the graphene oxide effectively, comprises that carbonyl, epoxy, hydroxyl are reduced largely.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Everyly belong to the row that apparent variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.

Claims (20)

1. a photochemical catalysis prepares the method for Graphene, it is characterized in that, comprises following concrete steps:
1) expansion process of graphite
9～15mL vitriol oil is heated to 75～85 ℃, adds 1.6g Potassium Persulfate and 1.6g Vanadium Pentoxide in FLAKES until solid all dissolves; Then add 1.8～22g graphite, under 75～85 ℃ of temperature, reacted 4～5 hours, filter, wash, obtain expanded graphite;
2) oxidation of expanded graphite
With step 1) expanded graphite that obtains joins in 75～85mL vitriol oil of ice bath cooling, slowly adds 8～12g potassium permanganate under magnetic agitation in this mixture, then 30～40 ℃ of lower reactions 3～5 hours, reacted again under the room temperature 1.5～2.5 hours; The deionized water that slowly adds 150～170mL keeps temperature to be no more than 50 ℃, continues to stir 1.5～2.5 hours; The water and the 30wt% hydrogen peroxide 8～12mL that add again 450～490mL, produce jonquilleous solution, this solution was placed after 24 hours, outwell supernatant liquor, then with remaining liquid first with the solution washing that contains 3wt% sulfuric acid, 1wt% hydrogen peroxide, and then with the 10wt%HCl washing, at last dialysis 6～8 days in water, the solid that obtains makes graphite oxide 45～55 ℃ of lower dryings;
3) graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
With step 2) graphite oxide that makes places deionized water, and through ul-trasonic irradiation 10～30 minutes, ultrasonic power was 150～250W, the graphene oxide solution that dissociates and obtain individual layer; Described graphite oxide: deionized water is 0.3mg～0.6mg: 1mL;
4) photo catalytic reduction graphene oxide
Getting step 3) the graphene oxide solution 10mL and the 20mL that obtain contain 10 -4Mol/L is to the N of saturated organic negative hydrogen donor, ascorbic acid derivates, sulfonamide derivatives, alcohol derivate or inorganic negative hydrogen donor, dinethylformamide or acetonitrile solution mix, stirred 5～10 minutes, then extremely limpid with ultrasonication, directly illumination or adding 1mL contain 1.5 * 10 -3Mol/L～1.5 * 10 -2The acetonitrile solution of the aqueous solution of mol/L organic dye or acetonitrile solution or metal complex dye, logical argon gas deoxygenation, reduced graphene oxide serving under illumination is removed organism in the system with organic solvent extraction after the reaction, the solid that obtains is washed first, then washing with acetone.
2. method according to claim 1 is characterized in that, described graphite is 325 purpose flaky graphites.
3. method according to claim 1 is characterized in that step 4) in, described direct illumination refers to carry out illumination with the 500W high voltage mercury lamp, wavelength 900nm＞λ＞400nm.
4. method according to claim 1 is characterized in that step 4) in, the photoreduction graphene oxide refers to that visible light shines or the near infrared light photograph wavelength 900nm＞λ＞400nm or 900nm＞λ＞450nm after adding dyestuff.
5. method according to claim 1, it is characterized in that, step 4) in, described organic negative hydrogen donor is Isosorbide-5-Nitrae-dihydrogen pyridine derivative, 1,2-dihydrogen pyridine derivative, 2,3-dihydro-benzimidizole derivatives, 2,3-dihydro-benzothiazole derivant, 2,3-dihydro-benzoxazole derivatives, 9,10-acridan, 1-phenylpyrrazolin.
6. method according to claim 5 is characterized in that, described Isosorbide-5-Nitrae-dihydrogen pyridine derivative is the compound with following structure:
Figure FDA0000082348420000011
R wherein 1=H, R 2=R 3=COOEt, R 4=H; R 1=H, R 2=R 3=COOEt, R 4=Me; R 1=H, R 2=R 3=COOEt, R 4=Et; R 1=H, R 2=R 3=COOEt, R 4=Ph; R 1=Ph, R 2=H, R 3=CONH 2, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CONH 2, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COCH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COOCH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=COOH, R 4=H; R 1=CH 2Ph, R 2=H, R 3=H, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CH 3, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CN, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CHO, R 4=H; R 1=CH 2Ph, R 2=H, R 3=CONHEt, R 4=H; R 1=CH 2Ph, R 2=CH 3, R 3=CONH 2, R 4=H; R 1=β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H; R 1=2,3,4,6-O-ethanoyl-β-D-Glucose, R 2=H, R 3=CONH 2, R 4=H.
7. method according to claim 5 is characterized in that, and is described 1, and the 2-dihydrogen pyridine derivative is the compound with following structure:
R 1=H, Me or Ph;
Figure FDA0000082348420000022
R 1=H, Me or Ph.
8. method according to claim 5 is characterized in that, and is described 2, and 3-dihydro-benzimidizole derivatives is the compound with following structure:
Figure FDA0000082348420000023
X=N, R 1=R 2=Me, R 3=H; X=N, R 1=R 2=Me, R 3=Ph; X=N, R 1=R 2=Me, R 3=β-D-Glucose-phenyl; X=N, R 1=R 2=Me, R 3=3 ', 4 ', 5 '-Ph.
9. method according to claim 5 is characterized in that, and is described 2, and 3-dihydro-benzoxazole derivatives are the compounds with following structure:
Figure FDA0000082348420000024
X=O, R 1=Me, R 2=β-D-Glucose-phenyl.
10. method according to claim 5 is characterized in that, and is described 2, and 3-dihydro-benzothiazole derivant is the compound with following structure:
Figure FDA0000082348420000025
X=S, R 1=Me, R 2=β-D-Glucose-phenyl.
11. method according to claim 5 is characterized in that, and is described 9, the 10-acridan has following structure:
Figure FDA0000082348420000026
R 1＝H，R 2＝H；R 1＝H，R 2＝Me；R 1＝H，R 2＝Ph；R 1＝Me，R 2＝H；R 1＝Me，R 2＝Me；R 1＝Me，R 2＝Ph。
12. method according to claim 5 is characterized in that, described 1-phenylpyrrazolin is the compound with following structure:
Figure FDA0000082348420000031
R 1＝Me，R 2＝Ph；R 1＝Ph，R 2＝Ph；R 1＝Ph，R 2＝p-MeO-C 6H 4；R 1＝Ph，R 2＝p-ClC 6H 4；R 1＝Ph，R 2＝p-NO 2C 6H 4。
13. method according to claim 1 is characterized in that, described ascorbic acid derivates is the compound with following structure:
R:C (CH 3) or Phenyl.
14. method according to claim 1 is characterized in that, described sulfonamide derivatives comprises trolamine, triethylamine, disodium EDTA.
15. method according to claim 1 is characterized in that, described alcohol derivate comprises methyl alcohol, ethylene glycol and the compound with following structure:
Figure FDA0000082348420000033
16. method according to claim 1 is characterized in that, described inorganic negative hydrogen donor comprises following compound: NaBH 4, NaB (OAc) 3H, NaBH 3CN or HSnPh 3
17. method according to claim 1, it is characterized in that, step 4) in, described organic dye is eosin W or W S, uranine yellow salt, 2,7-dichlorofluorescein, rhodamine B, Nile red, alizarin red S, safranine T, acridine orange, Hypocrellin A, Hypocrellin B, perylene diimide class dyestuff, porphyrin dyestuff, thiazin dyes, polyenoid class dyestuff, coumarins dyestuff, carbazoles dyestuff, the glimmering class dyestuff of fluorine boron, fullerene derivate.
18. method according to claim 7, it is characterized in that, the selected representative molecular structures of Suo Shu perylene diimide class dyestuff, porphyrin dyestuff, thiazin dyes, polyenoid class dyestuff, coumarins dyestuff, carbazoles dyestuff, the glimmering class dyestuff of fluorine boron, fullerene derivate is as follows successively:
Figure FDA0000082348420000034
Figure FDA0000082348420000041
Wherein: R 1=R 1'=CH 3, R 2=R 2'=H, R 3=R 3'=CH 3R 1=R 1'=CH 3, R 2=R 2'=CH 3, R 3=R 3'=CH 3R 1=CH 3, R 2=H, R 3=CH 3, R 1'=phenyl, R 2'=H, R 3'=phenyl;
Figure FDA0000082348420000042
19. method according to claim 1, it is characterized in that, step 4) in, described metal complex dye comprises the dipyridyl title complex, platinum, the phenanthroline title complex of rhenium, second bipyridine-phenanthroline or 2-phenyl-pyridine-phenanthroline title complex and the Coordination Reaction of Zinc Porphyrin Complexes of iridium of platinum, ruthenium, rhenium, osmium.
20. method according to claim 9 is characterized in that, the dipyridyl title complex of described platinum be terpyridyl divalence platinum complex, second bipyridine divalence platinum complex, 6-phenyl-2,2 '-second bipyridine divalence platinum complex; The dipyridyl title complex of described ruthenium is second bipyridine ruthenium complexe, terpyridyl ruthenium complexe; The dipyridyl title complex of described rhenium is the second bipyridine rhenium compound; The dipyridyl title complex second bipyridine osmium title complex of described osmium; The phenanthroline title complex of described platinum is phenanthroline divalence platinum complex; The phenanthroline title complex of described rhenium is the phenanthroline rhenium compound;
Described terpyridyl divalence platinum complex has following structure:
Figure FDA0000082348420000051
R in the formula 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CCH 2OH, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CCH 2CH 2CH 3, R 3, R 4Independently be H; Or R 1Be C (CH 3) 3, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C (CH 3) 3, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4OCOCH 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CCH 2OCOCH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ CSi (CH 3) 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer, R 3, R 4Independently be H; Or R 1Be H, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be Cl; Or R 1, R 3, R 4Independently be C (CH 3) 3, R 2Be C ≡ CC 6H 5R in the formula 5Be Cl -, ClO 4 -Or PF 6
Described second bipyridine divalence platinum complex has following structure:
R in the formula 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, R 2Be Cl, C ≡ CC 6H 4CH 3-4, C ≡ CC 6H 4C ≡ CC 6H 5-4, C ≡ CCH 2OH, C ≡ CC 6H 5, C ≡ CC 6H 4OCH 3-4, C ≡ CC 6H 4OCOCH 3, C ≡ CSi (CH 3) 3Or C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer;
Described 6-phenyl-2,2 '-second bipyridine divalence platinum complex has following structure:
Figure FDA0000082348420000061
R in the formula 1Be H, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 5, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be Cl, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C ≡ CC 6H 4Cl-4, R 3, R 4Independently be H;
Described second bipyridine ruthenium complexe has following structure:
Figure FDA0000082348420000062
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3
Described terpyridyl ruthenium complexe has following structure:
Figure FDA0000082348420000063
R in the formula 1Be C 6H 4OCH 3-4, R 2, R 3Independently be H; Or R 1Be C 6H 4CH 3-4, R 2, R 3Independently be H; Or R 1Be C (CH 3) 3, R 2, R 3Independently be H; Or R 1, R 2, R 3Independently be H; Or R 1, R 2, R 3Independently be C (CH 3) 3
Described second bipyridine-phenanthroline (X=N) or 2-phenyl-pyridine-phenanthroline (X=C) complex of iridium have following structure:
Figure FDA0000082348420000071
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, R 2Be H, CH 3Or p-SO 3-phenyl, X=N or C;
Described second bipyridine rhenium compound has following structure:
Figure FDA0000082348420000072
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, X=Cl or Br;
Described second bipyridine osmium title complex has following structure:
Figure FDA0000082348420000073
Described phenanthroline divalence platinum complex has following structure:
R in the formula 1Be H or CH 3R 2Be Cl, C ≡ CC 6H 4CH 3-4, C ≡ CC 6H 4C ≡ CC 6H 5-4, C ≡ CCH 2OH, C ≡ CC 6H 5, C ≡ CC 6H 4OCH 3-4, C ≡ CC 6H 4OCOCH 3, C ≡ CSi (CH 3) 3Or C ≡ C (CH 2) nCH 3, wherein n is 1～16 positive integer;
Described phenanthroline rhenium compound has following structure:
Figure FDA0000082348420000075
R 1Be H, CH 3, Cl, OCH 3Or C (CH 3) 3, X=Cl or Br;
Described Coordination Reaction of Zinc Porphyrin Complexes has following structure:
Figure FDA0000082348420000081
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