CN113200539B - Porphyrin edge covalent fused graphene nonlinear nano hybrid material and preparation method thereof - Google Patents
Porphyrin edge covalent fused graphene nonlinear nano hybrid material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin edge covalent fused graphene nonlinear nano hybrid material and a preparation method thereof. According to the invention, the porphyrin ring is formed by condensation reaction of the amino porphyrin and the ortho-position diketone at the edge of GO, so that the novel organic-inorganic covalent functionalized nano hybrid material with fused edges is successfully prepared, and the conjugation degree, electronic coupling and transmission between porphyrin graphene are enhanced by the pyrazine ring, so that the prepared material has more enhanced nonlinear optical performance in the nanosecond visible light field compared with the traditional material, and has very strong reference significance.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic functional composite materials, and relates to a porphyrin edge covalent fused graphene nonlinear nano hybrid material and a preparation method thereof.
Background
In the existing graphene porphyrin nanometer hybrid material system, due to third-order nonlinear scattering of graphene caused by laser thermal effect, reverse saturated absorption of porphyrin monomers and electron/energy transfer from the porphyrin monomers as electron donors to graphene, more and more work is carried out around changing the connection mode of porphyrin and graphene. By changing the connection mode of graphene and porphyrin, the process of electron/energy transfer can be changed, so that the third-order nonlinear optical performance of the porphyrin monomer graphene nano hybrid material is caused. At present, there are many reports on changing the connection mode between porphyrin monomer and graphene, and the summary is mainly divided into the following connection modes:
1. esterification reaction: the esterification reaction is mainly characterized in that hydroxyl on the surface of graphene oxide is connected with carboxyl porphyrin monomer to form the nano hybrid material.
2. Acylation reaction: the acylation reaction is to modify amino functional groups relatively easily by using porphyrin monomers, and further react with carboxyl on the surface of graphene oxide. In order to improve the reaction yield, generally, carboxyl is subjected to acyl chlorination reaction in advance, and then is further connected with porphyrin, which is one of the most common methods for constructing porphyrin monomer covalent connection graphene hybrid materials.
3. Free radical addition reaction: the free radical addition reaction occurs on the surface of the graphene more, one molecule of nitrogen is removed through amino azotization, and the formed free radical attacks sp on the surface of the graphene 2 Hybridized carbon atom to form the hybridized material system with graphene and porphyrin monoThe body is in a vertical state, the porphyrin monomer is planted on the graphene soil like a tree seedling, the graphene is low in requirement in the direction, oxygen-containing groups are not needed, and therefore the method is suitable for pure graphene and reduced graphene oxide systems and has the defect that the loading yield is low. The previous section addresses this problem by a combinatorial approach.
4. 1, 3-dipolar cycloaddition reaction: the 1, 3-dipolar cycloaddition reaction is similar to the Diels-Alder reaction, and generally, a stable five-membered ring structure is formed by the ring-opening reaction of N-methylglycine and porphyrin monomer containing aldehyde group on the surface of graphene. Because the related groups are flexible and variable, the requirement on reaction conditions is not high, and the loading rate is high, the 1, 3-dipolar cycloaddition reaction is one of the most common means for graphene surface functionalization.
5. Click chemistry: click chemistry is a two-step reaction, firstly, alkynyl protected trimethylsilylacetylene is loaded on the surface of graphene through azote addition reaction, then tetramethylsilicon on the surface of alkynyl is rapidly removed, and click reaction is rapidly carried out on the tetramethylsilicon and azide of porphyrin under the catalysis condition of copper ions to form a five-membered nitrogen heterocycle, so that porphyrin monomers and graphene bonds are connected together.
In addition to the above five methods, the preparation of porphyrin monomers also includes electrostatic reaction, binell reaction, substitution reaction, and certainly, a novel porphyrin monomer and graphene nano hybrid material prepared by combining different methods with each other.
Observation and summary can find that the configurations of the components of the porphyrin monomer and the graphene nano hybrid material prepared by the method are relatively uniform, one is that the porphyrin monomer and the graphene nano hybrid material are connected at the edge of graphene oxide through esterification reaction and acylation reaction, the graphene main body and the porphyrin monomer are connected through a single line, especially the nano hybrid material further combined with substitution reaction through the reactions is long in bridge connection and belongs to a flexible bridge connection group, so that the porphyrin monomer is similar to a 'balloon' bound on the porphyrin edge, the position of the porphyrin monomer is not fixed very much, therefore, the porphyrin monomer partially transfers electrons/energy of graphene through the bridge connection group single line transmission, and on the other hand, through the curling of a flexible chain, a part of the porphyrin monomer is likely to generate pi-stacking effect with the graphene plane again, whereby an electron/charge transfer occurs that resembles a supramolecular structure, and the efficiency of this electron/energy transfer has been shown to be inferior to the transfer effect of covalent attachment. The second type is that ring opening reaction is carried out above the plane of graphene by taking free radical addition reaction, 1, 3-dipolar cycloaddition reaction and click chemistry reaction as main bodies, and the reaction has better electron/energy transfer efficiency compared with esterification reaction and acylation reaction, but the current research on the materials is stopped in the two reaction systems, and the single-line bridging mode cannot improve the efficiency of electron transfer in the materials, so that the three-order nonlinear performance of the materials is further optimized.
The present invention has been made in view of the above background.
Disclosure of Invention
The invention aims to provide a porphyrin edge covalent fused graphene nonlinear nano hybrid material and a preparation method thereof.
The invention aims to develop a novel porphyrin covalent functionalized graphene nonlinear absorption material with a stronger third-order nonlinear absorption coefficient aiming at the application limitation of the traditional material and the application requirement of the current strong laser protection material. According to the invention, the diaminoporphyrin is parallelly bonded at the GO edge through a condensation reaction, and the three-order nonlinear coefficient of the organic-inorganic hybrid material is enhanced through the enhanced electronic coupling and transmission effect between the diaminoporphyrin and the GO. According to the invention, the diaminoporphyrin and the ortho-diketone at the edge of GO form a pyrazine ring through a condensation reaction, so that the novel organic-inorganic covalent functionalized nano hybrid material with fused edges is successfully prepared, and the conjugation degree, electronic coupling and transmission between porphyrin graphene are enhanced by the pyrazine ring, so that the prepared material has more enhanced nonlinear optical performance in the nanosecond visible light field compared with the traditional material, and has very strong reference significance.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a porphyrin edge covalent fused graphene nonlinear nano hybrid material,
in order to prepare the porphyrin edge covalent fused graphene nonlinear nano hybrid material GO-Pr, beta-ortho-diaminoporphyrin is prepared firstly. In the first step, the propionic acid is used for catalyzing pyrrole condensation reaction to prepare tetraphenylporphyrin in a large quantity. In order to introduce an amino group at the beta-position of porphyrin, a nitro group needs to be introduced at the beta-position of porphyrin. And the introduction of the nitro group at the beta position has extremely strong selectivity, and the open-shell metal copper ion needs to be introduced in advance at the central position of the tetraphenylporphyrin obtained in the first step, so that a nitro group can be selectively introduced at one beta position. Further reacting with 4-amino-1, 2, 4-triazole, introducing an amino group at the adjacent beta position of the nitro group, then removing copper ions by strong acid, and reducing the nitro group by palladium carbon and sodium borohydride to successfully obtain beta-o-diaminoporphyrin. Due to the instability of the diaminoporphyrin, the target hybrid material GO-Pr is successfully prepared by directly carrying out condensation reaction with the graphene oxide prepared by the improved Hummers method without further purification.
Specifically, the preparation method comprises the following steps:
(1) oxidizing flake graphite sequentially in a concentrated sulfuric acid, sodium nitrate and potassium permanganate system, adding hydrogen peroxide after the reaction is finished, filtering, washing and drying to obtain graphene oxide fluffy solid;
(2) dissolving tetraphenylporphyrin in a trichloromethane solution, adding copper acetate dissolved in a methanol solution in advance, and stirring for reaction to obtain copper tetraphenylporphyrin;
(3) reacting tetraphenylporphyrin copper with excessive lithium nitrate under the catalysis of acetic acid and acetic anhydride to obtain 2-nitro-tetraphenylporphyrin copper;
(4) reacting 2-nitro-copper tetraphenylporphyrin with 4-amino-1, 2, 4-triazole and excessive KOH in a mixed solution of toluene and ethanol, and separating by column chromatography to obtain 2-nitro-3-amino-copper tetraphenylporphyrin;
(5) dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in a chloroform solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, reacting quickly, stirring and pouring deionized water, and separating to obtain 2-nitro-3-amino-tetraphenylporphyrin without copper ions;
(6) dissolving 2-nitro-3-amino-tetraphenylporphyrin in dichloromethane and methanol solution, adding 10% (by weight of palladium) palladium carbon, stirring uniformly, continuing adding sodium borohydride, reacting under the monitoring of thin-layer chromatography, and separating to obtain 2, 3-diaminoporphyrin;
(7) and dispersing the graphene oxide fluffy solid in anhydrous DMF, carrying out nitrogen bubbling treatment, adding 2, 3-diaminoporphyrin dissolved in anhydrous dichloromethane, continuing to bubble, carrying out a dark reaction, and washing to obtain the target product, namely the porphyrin edge covalent fused graphene nonlinear nano hybrid material.
Further, in the step (1), the adding amount ratio of the crystalline flake graphite, the concentrated sulfuric acid, the sodium nitrate and the potassium permanganate is 500 mg: (22-28) mL: (400- & lt600- & gt) mg: (2-4) g. Here, by reducing the amount and time of the oxidant, the prepared GO can have a more diketone structure, so as to further prepare the edge-melted hybrid material.
Further, in the step (1), the whole oxidation process specifically comprises: under the ice-bath condition, the crystalline flake graphite is firstly stirred in concentrated sulfuric acid for 15-25min, and then in NaNO 3 Stirring the mixture in the system for reaction for 0.5-1.5h, then removing the ice bath after the potassium permanganate is added, and continuing the reaction for 0.5-1.5h after the reaction system is restored to the normal temperature.
Further, in the step (1), after the reaction is finished, deionized water is added into the reaction system, and then hydrogen peroxide is dropwise added until the reaction system is brownish yellow.
Furthermore, in the step (2), the molar ratio of tetraphenylporphyrin to copper acetate is 1: 3-5. Here, by introducing an open-shell metal ion into the ring first, the subsequent selective introduction of a nitro group at the β position is facilitated, instead of introducing a nitro group on the benzene ring at the meso position.
Further, in the step (2), the reaction is carried out at room temperature with stirring.
Further, in the step (3), the volume ratio of acetic acid to acetic anhydride is 1: 6-10.
Further, in the step (3), the reaction is carried out at room temperature for 3-5 h.
Further, in the step (4), the molar ratio of the copper 2-nitro-tetraphenylporphyrin to the 4-amino-1, 2, 4-triazole is 1.5: 30-60.
Further, in the step (4), the volume ratio of the toluene to the ethanol is 220-280: 20.
Further, in the step (5), the adding amount ratio of the 2-nitro-3-amino-tetraphenylporphyrin copper, the concentrated sulfuric acid and the trifluoroacetic acid is (1.0-1.2) mmol: (30-50) ml:10 mL.
Further, in the step (5), the rapid reaction is carried out in an ice bath for 10-15 min. The demetallization reaction here can guarantee the subsequent precise structural characterization, simultaneously remove other influencing factors on the performance, and in addition, the demetallization must be carried out before the reduction of the nitro group, because the bisaminoporphyrin is difficult to keep stable under the strong oxidation acid condition. The reaction time must be controlled during the demetallization process, otherwise the reaction such as carbonization decomposition of porphyrin can occur, and other side products of porphyrin can be generated.
Further, in the step (6), the adding amount ratio of the 2-nitro-3-amino-tetraphenylporphyrin to the palladium carbon to the sodium borohydride is 0.7 mmol: (400-600) mg: (8-12) mmol. The reaction is carried out under the condition of keeping out light, and the cyclization reaction of the diamino under the condition of illumination is reduced. Therefore, the reaction can not stay in the chromatographic column for a long time for slow purification after the reaction is finished, and the reaction is directly put into the next reaction. In the reduction reaction process, a small amount of sodium borohydride must be added for many times, so that the reaction danger is avoided.
Further, in the step (7), the reaction is carried out under the protection of inert gas, and the reaction time is 36-60 h.
Further, in the step (7), the correspondingly added 2, 3-diaminoporphyrin is prepared from 0.6-0.8 mmol of 2-nitro-3-amino-tetraphenylporphyrin in terms of 10mg of graphene oxide fluffy solid. The solvent for the reaction here must be an anhydrous solvent, including DMF and dichloromethane. The metered condensation reaction must be carried out under protection from light and nitrogen, and it is necessary to remove the dissolved oxygen from the solvent by bubbling. The reaction is controlled at normal temperature or low temperature, and the self-cyclization reaction of the diaminoporphyrin can be reduced.
The second technical scheme of the invention provides a porphyrin edge covalent fused graphene nonlinear nano hybrid material, the nano hybrid material is obtained by connecting diaminoporphyrin at the GO edge in parallel through condensation reaction, and the three-order nonlinear coefficient of the organic-inorganic hybrid material is enhanced through enhanced electronic coupling and transmission effect between the two materials. In the nano hybrid material, the diamino porphyrin and ortho-position diketone at the edge of GO form a pyrazine ring through a condensation reaction.
The pyrazine ring enhances the conjugation degree, electronic coupling and transmission among porphyrin graphene, so that the prepared material has more enhanced nonlinear optical performance in the nanosecond visible light field compared with the traditional material, and has very strong reference significance.
Furthermore, the nanometer hybrid material has broadband linear absorption at 375-800nm, and the fluorescence quenching efficiency reaches 90%.
Compared with the prior art, the invention has the following advantages:
first, the hybrid material has strong broadband linear absorption at 375-800nm, spans the entire visible light field, rather than showing significant absorption at the characteristic soret and Q band positions of porphyrin.
And secondly, the fluorescence quenching efficiency of GO-Pr reaches 90 percent and is far higher than that of the traditional single-wire connection material, and the more efficient electron transfer and transmission efficiency between GO-Pr connected through pyrazine rings is proved.
And under the irradiation of 532nm nanosecond laser, the hybrid material GO-Pr has enhanced nonlinear absorption compared with the parent materials GO and Pr, and has better nonlinear performance compared with the traditional amidated porphyrin covalent functionalized graphene oxide hybrid material (GO-Pr1, the synthesis is shown in the following examples).
And fourthly, the hybrid material GO-Pr is characterized in that the third-order nonlinear absorption coefficient at 532nm is twice that of the traditional amidated porphyrin covalent functionalized graphene oxide hybrid material GO-Pr 1.
Drawings
FIG. 1 is a preparation route of GO-Pr nano hybrid materials prepared by the invention.
FIG. 2 shows the preparation of reference organic porphyrin 7.
FIG. 3 is a route for the preparation of the reference hybrid material GO-Pr1 linked by amidation.
FIG. 4 is the Raman spectrum of GO-Pr nano hybrid material prepared by the invention and the reference material GO-Pr1 thereof.
FIG. 5 is an X-ray photoelectron spectrum of GO-Pr nano hybrid materials prepared by the present invention;
FIG. 6 is a transmission electron microscope image (from left to right GO-Pr, GO-Pr1) of GO-Pr nano hybrid materials and reference materials GO-Pr1 prepared by the invention.
FIG. 7 is atomic force microscope atlas and height file of GO-Pr nano hybrid material prepared by the invention.
FIG. 8 is a thermogravimetric analysis spectrum of GO-Pr nano hybrid materials and precursor materials GO and Pr thereof prepared by the invention.
FIG. 9 shows the linear absorption spectrum and fluorescence emission spectrum of GO-Pr nano-hybrid materials and precursor materials prepared by the present invention and reference hybrid materials.
FIG. 10 is the nonlinear optical absorption spectra of the GO-Pr nano hybrid material and precursor material prepared by the present invention and the reference material under 532nm,4ns laser.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting materials are from research platform, Annaige, Bailingwei, etc., wherein the synthetic method of tetraphenylporphyrin is referred to in the literature (Ostrowski, S., Grzyb, S. (2012), Direct β -amino reaction in porous systems-a simple route to compounds control two amino reagents bottom β -positions of the sample propyl unit tetrahedron Letters,53 (6347), 55-
The rest of the raw materials or processing techniques are conventional commercial products or conventional techniques in the field if not specifically mentioned.
Example 1:
referring to fig. 1, this example provides a preparation method of a porphyrin edge covalent fused graphene-based nonlinear nano hybrid material:
the first step is as follows:
graphene oxide GO containing a diketone structure is synthesized by an improved Hummers method, and the use amount and the oxidation time length of an oxidant are reduced, so that the surface of the obtained GO is mainly provided with epoxy groups, ketone groups, carboxyl groups and a small amount of even no hydroxyl groups.
Specifically, 500mg of crystalline flake graphite is added into 25ml of concentrated sulfuric acid, the reaction system is transferred into an ice bath at 0 ℃, the mixture is stirred and dispersed, and after the temperature of the system is stabilized to 0 ℃ for about 20min, 500mg of NaNO is slowly added into the mixture five times 3 The reaction was stirred at 0 ℃ for 1 h. Followed by a slower and multiple addition of 3g of KMnO to the reaction system 4 ，KMnO 4 After the addition, the ice bath was removed, and the reaction was continued for 1h after the reaction system was returned to normal temperature. After the reaction is finished, slowly dropwise adding deionized water into a vigorously stirred reaction system to ensure that the temperature of the reaction system rises to be close to boiling, keeping for 30min, continuously adding 100ml of deionized water after 30min, and then slowly dropwise adding 10ml of aqueous hydrogen peroxide. After the dropwise addition is finished, the reaction system is brownish yellow, and the reaction system is repeatedly washed and filtered, so that the pH value approaches to neutrality as much as possible (the difficulty of filtering is increased when the pH value is increased to approach to neutrality, the subsequent high-speed centrifugation at 3000rpm of a centrifugal machine is carried out, bottom sediments are removed, the supernatant is transferred together, the high-speed centrifugation at 12000rpm of the supernatant is carried out sequentially to obtain brownish black adherends at the bottom, the brownish black adherends are collected together and ultrasonically dispersed in 300ml of deionized water, and after the bottom layer of a refrigerator is frozen overnight, the loose and loose glue is obtained by freeze dryingGO 108mg)
The second step:
tetraphenylporphyrin 1(1228mg,2.0mmol, synthesized according to literature methods, (Ostrowski, S., Grzyb, S. (2012). Direct. beta. -amino reaction in porphyrin systems-a simple route to a complex contacting of two nitro porphyrin substituents. beta. -positions of the same solvent unit, tetrahedron Letters,53(47),6355-6357.) was dissolved in 100ml of dichloromethane solution, sonicated to complete dissolution 2 ·H 2 O (1601mg,8.0mmol) was sonicated in 20ml of methanol to dissolve as much as possible, and the Cu (OAc) solution was added 2 ·H 2 Pouring the O solution into dichloromethane solution of tetraphenylporphyrin, stirring the reaction at room temperature for 2h, monitoring the reaction by TLC until the relatively low polarity tetraphenylporphyrin is nearly disappeared, pouring the reaction mixture into water and extracting with dichloromethane for several times, collecting the organic layer, and Na 2 SO 4 The organic layer was dried, the organic solvent was distilled off under reduced pressure, and column chromatography (dichloromethane/petroleum ether: 1:2) gave copper tetraphenylporphyrin 2(1284mg, 95%) as a purple solid. Because copper porphyrin has magnetism and cannot be characterized by nuclear magnetic resonance, the following copper porphyrin is characterized by adopting matrix-assisted time-of-flight mass spectrometry (Maldi-TOF) in combination with electron absorption spectroscopy, and copper ions of the final compound are removed by concentrated sulfuric acid and then the final compound is subjected to nuclear magnetic characterization.
UV-Vis(CH 2 Cl 2 )λ max ,nm；log(ε):414(2.78),539(1.46).MS(MALDI-TOF):m/zcalcd for C 44 H 28 CuN 4 676.16,found 676.26[M] + .
The third step:
copper porphyrin 2(1217mg,1.8mmol) was dissolved in 1000ml of chloroform solution, LiNO 3 (1248mg,1.8mmol) was dissolved in a mixed solution of acetic acid and acetic anhydride by acidification (acetic acid: acetic anhydride 20ml:160ml), and then added to a trichloromethane solution of copper porphyrin 2, stirred at room temperature for 4 hours, the reaction was checked by TLC, after the reaction was completed, the mixed system was washed and extracted with deionized water and saturated sodium bicarbonate solution several times, the organic phase was separated and then anhydrous sulfur was usedSodium acid was dried, the organic solvent was distilled off under reduced pressure, and column chromatography (dichloromethane/petroleum ether ═ 1:1) was performed to give copper 2-nitro-tetraphenylporphyrin 3(1168mg, 90%).
UV-Vis(CH 2 Cl 2 )λ max ,nm；log(ε):423(1.97),548(0.83),592(0.65).MS(MALDI-TOF):m/z calcd for C 44 H 27 CuN 5 O 2 721.25,found 721.26[M] +
The fourth step:
β -nitroporphyrin 3(1080mg,1.5mmol), 4-amino-1, 2, 4-triazole (3780mg,45.0mmol), potassium hydroxide (8.40g,150.0mmol) in a mixed solution of toluene and ethanol (toluene: ethanol 250ml:20ml) was heated to reflux and monitored by TLC until the starting material reaction was complete. After the reaction was completed, the solvent was distilled off under reduced pressure, dissolved in a dichloromethane solution, washed with deionized water several times, the organic phase was collected, purified with anhydrous sodium sulfate, subjected to column chromatography (dichloromethane/petroleum ether ═ 2:3, and trace triethylamine was added to reduce tailing) and recrystallized in a dichloromethane/ethanol mixed system to give copper 2-amino-3-nitroporphyrin 4(904mg, 82%)
UV-Vis(CHCl 3 )λ max (ε х 10 -3 )nm:315(4.28),440(5.18),561(4.13),605(3.97).MS(MALDI-TOF):m/z calcd for C 44 H 28 CuN 6 O 2 735.16,found 736.29[M] +
The fifth step:
to pass nuclear magnetic resonance hydrogen spectrum 1 The porphyrin structure is accurately characterized by H NMR, and the target compound with nonmagnetic copper ions complexed in the center of a porphyrin ring is prepared by using strong acid to perform demetallization reaction on 2-nitro-3-amino-tetraphenylporphyrin copper (porphyrin 4). Porphyrin 4(808mg,1.1mmol) was dissolved in chloroform solution at 0 ℃. Adding concentrated H thereto 2 SO4 and trifluoroacetic acid (TFA) (H) 2 SO 4 40 mL/TFA: 10 mL). Stirring for 10-15min in ice bath, and quickly pouring into cold water. Extracting with chloroform and collecting organic phase, sequentially with NaHCO 3 Aqueous solution and water wash. Anhydrous Na for solution 2 SO 4 Drying and concentrating by evaporation. Eluting with petroleum ether/dichloromethane (1:2) to obtain 2-amino-3Nitroporphyrin 5, in 70% yield (519 mg).
1 H NMR(600MHz,CHCl 3 -d,TMS,δ/ppm):8.97(d,J＝7.8Hz,1H,β-H pyrrole),8.81(d,J＝7.8Hz,1H,β-H pyrrole),8.78(d,J＝7.2Hz,1H,β-H pyrrole),8.64(m,J＝4.6Hz,2H,β-H pyrrole),8.60(d,J＝4.8Hz,1H,β-H pyrrole),8.38(d,J＝7.2Hz,2H,H Ph),8.20(m,6H,H Ph),8.00(m,3H,H Ph),7.82(m,9H,H Ph),6.89(s,2H,NH 2 ),2.60and 2.41(2s,2H,2NH).MS(MALDI-TOF):m/z calcd.for C 44 H 30 N 6 O 2 :674.2403；Found:674.2489[M] + .UV-Vis(CHCl 3 )λ max (logε)nm:661(3.49),604.5(3.62),568.5(3.81),529.5(4.05),431(5.26)nm.
And a sixth step:
2-amino-3-nitroporphyrin 5(472mg,0.7mmol), 10% palladium on carbon (500mg) was charged into a 500ml two-necked flask, and the reaction system was replaced with a nitrogen atmosphere by a double-vented tube, and 200ml of freshly distilled anhydrous dichloromethane and 15ml of anhydrous methanol were added thereto and dissolved with stirring. After the reaction system is dispersed stably, adding NaBH into the mixed system which is stirred vigorously for many times 4 (378mg,10.0mmol) and the addition was completed in 1 h. After the reaction is finished, monitoring the reaction process by TLC, after all the raw materials are completely reacted, quickly washing and extracting by using deionized water and dichloromethane, drying by using anhydrous sodium sulfate, quickly passing through a flash chromatography column filled with diatomite, keeping at a lower temperature, and carrying out reduced pressure distillation, wherein the obtained ortho-position bisaminoporphyrin 6 (namely 2, 3-diaminoporphyrin) is very unstable, so that the next reaction is directly carried out without further treatment.
And (2) ultrasonically dispersing the prepared GO (10mg) in 15ml of anhydrous dry DMF for 4 hours, bubbling the mixture for 20 minutes by using nitrogen, quickly transferring the mixture into a two-opening reaction bottle protected by nitrogen, simultaneously dissolving the freshly prepared porphyrin 6 in 6ml of anhydrous dichloromethane, transferring the dichloromethane solution of the bisaminoporphyrin 6 into the two-opening reaction bottle by using an injector, continuously bubbling for 15 minutes, and reacting for 48 hours under the condition of normal temperature and nitrogen protection. After the reaction is finished, DMF, tetrahydrofuran, dichloromethane, deionized water and ethanol solution are sequentially used for repeated ultrasonic washing and filtration through a polytetrafluoroethylene film (0.22 mu m), and vacuum drying is carried out to obtain the GO-Pr (8.1mg) of the edge fused porphyrin graphene nano hybrid material.
Due to the structural characteristics of GO, the structure of the obtained nano hybrid material cannot be accurately characterized, especially by instruments which can accurately determine the structure to a great extent, such as a nuclear magnetic resonance hydrogen spectrum. To further verify that porphyrin 6 and GO are formed by formation of pyrazine ring through quantitative condensation between diamino group and diketone group, porphyrin 7, a reference compound, was synthesized by controlling reaction variables. Reacting the bisaminoporphyrin with the organic micromolecule 9, 10-phenanthrenequinone with a determined structure.
Referring to FIG. 2, the bisaminoporphyrin 6 (about 0.5mmol) freshly prepared as described above was dissolved in 6ml of dichloromethane under nitrogen protection, 9, 10-phenanthrenequinone (62mg,0.3mmol) was added to 30ml of anhydrous DMF solution, and after bubbling with nitrogen for 20min, it was transferred to a 100ml two-necked flask under nitrogen protection, and the dichloromethane solution of bisaminoporphyrin 6Pr1 was transferred thereto by syringe, and after bubbling for 15min, the reaction was continued at room temperature for 48 hours. After completion of the reaction, DMF was removed by washing with deionized water dichloromethane in a large amount, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure, and column chromatography (tetrahydrofuran/dichloromethane/petroleum ether ═ 1:20:40) gave reference porphyrin 7(122mg, 50%).
1 H NMR(600MHz,toluene-d,δ/ppm):-3.14(2H,s,-NH),7.14-7.57(8H,m,HPh),7.70(4H,d,J＝8.4Hz,H Ph),7.79-7.91(8H,m,H Ph),8.02(8H,m,H Ph),8.74(6H,m,Hβ-pyrrole).MS(MALDI-TOF):m/z calcd for C 58 H 36 N 6 816.3,found 816.97M + .
FIG. 3 shows a reference hybrid material GO-Pr1 prepared by the present invention, in which porphyrin and graphene are connected by a single line through a traditional amidation reaction, in order to compare the difference in structure and performance between the two materials, the synthesis of the reference hybrid material GO-Pr1 is as consistent as possible with the synthesis method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material GO-Pr prepared by the present invention, and a beta-substituted monoamino porphyrin is also selected, and the synthesis method is specifically implemented as follows:
the first step is as follows:
synthesis of 2-nitrotetraphenylporphyrin by demetallization of copper 2-nitroporphyrin, the procedure was as described for the demetallization of copper 2-amino-3-nitroporphyrin in example 1. Porphyrin 3(800mg,1.11mmol) was dissolved in chloroform solution at 0 ℃. Adding concentrated H thereto 2 SO 4 And trifluoroacetic acid (TFA) (H) 2 SO 4 5 mL/TFA ═ 20 mL). Stirring for 10-15min in ice bath, and quickly pouring into cold water. Extracting with chloroform and collecting organic phase, sequentially with NaHCO 3 Aqueous solution and water wash. Anhydrous Na for solution 2 SO 4 Drying and concentrating by evaporation. Elution with petroleum ether/dichloromethane (1:2) gave 527mg of 2-nitrotetraphenylporphyrin in 72% yield.
1 H NMR(600MHz,CHCl 3 -d,TMS,δ/ppm):-2.59(br s,2H,center NH),7.72-7.84(m,12H,H Ph),8.18-8.28(m,8H,H Ph),8.82-9.01(m,6H,β-H pyrrole),9.08(s,1H,β-H pyrrole).MS(MALDI-TOF):m/z calcd.for C 44 H 29 N 5 O 2 :659.2123,found:659.4754[M] + .
The second step is that:
synthesis of 2-amino tetraphenyl porphyrin referring to the synthesis method of bisamino tetraphenyl porphyrin, sodium borohydride and palladium carbon are used for reduction. 2-Nitrocentriphenylporphyrin (462mg,0.7mmol) and 10% palladium on carbon (400mg) were added to a mixed solvent of dichloromethane/methanol (200mL:15mL), stirred well and then NaBH was added slowly in portions 4 (378mg,10mmol) and the addition was completed in 1 h. After the reaction (TLC monitoring of complete consumption of raw materials), deionized water and dichloromethane are used for rapid washing and extraction, anhydrous sodium sulfate is dried, the mixture rapidly passes through a flash chromatography column filled with kieselguhr, the solvent is removed by reduced pressure distillation, and the mixed eluent of petroleum ether/dichloromethane (2:3) is used for column chromatography purification to obtain purple solid 2-amino tetraphenyl porphyrin (343mg, 79% yield).
1 H NMR(600MHz,CHCl 3 -d,TMS,δ/ppm):-2.69(br s,2H,center NH),4.45(br s,2H,NH 2 ),7.68-7.81(m,12H,H Ph),8.14(d,4H,J＝9.6Hz,H Ph),8.22(d,4H,J＝9.6Hz,H Ph),8.53(d,1H,J＝6.0Hz,β-H pyrrole),8.59(d,1H,J＝6.0Hz,β-Hpyrrole),8.75(d,4H,J＝6.4Hz,β-H pyrrole),8.80(s,1H,β-H pyrrole).MS(MALDI-TOF):m/z calcd.for C 44 H 31 N 5 629.4504,found 629.5439[M] + .
The third step:
adding 10mg GO prepared in the above step into 10ml thionyl chloride (SOCl) 2 ) Performing medium ultrasonic dispersion, adding 0.5ml of DMF into the system, heating to reflux, and reacting for 24 hours. And after the reaction is finished, carrying out reduced pressure distillation to recover thionyl chloride, adding the residual mixture into 30ml of DMF, carrying out ultrasonic dispersion, fully and ultrasonically filtering and washing the mixture sequentially through DMF, triethylamine, tetrahydrofuran, deionized water and a methanol solution to obtain GO-Cl, and continuously dispersing the GO-Cl into 15ml of DMF. To the resulting black homodisperse system was added 2-aminotetraphenylporphyrin (343mg,0.5mmol), and after bubbling with nitrogen for 20min, the reaction was continued at 80 ℃ for 48 hours under nitrogen protection. After the mixed system is cooled to room temperature, repeatedly performing ultrasonic washing and filtration through a polytetrafluoroethylene film (0.22 mu m) by sequentially using DMF (dimethyl formamide), tetrahydrofuran, dichloromethane, deionized water and ethanol solution, and checking the final filtrate by TLC (thin layer chromatography) to ensure that no porphyrin is absorbed in the final washing process, thereby finally preparing the amidated porphyrin graphene nano hybrid material GO-Pr1(8.4 mg).
FIG. 4 shows Raman spectra of porphyrin edge covalent fused graphene nonlinear nano hybrid material GO-Pr, parent material and reference material GO-Pr1 prepared by the method of the invention. The covalent functionalization process results in two main spectral bands (D band: 1330-1380 cm) of the carbon-based material -1 And G-band: 1400-1600cm -1 ) With a large difference in intensity. Extensive preliminary work has shown that D and G bands are separated from sp 3 -and sp 2 The greater the ratio of the intensities of the D and G bands, with respect to the hybridized carbon atoms, means the greater the degree of disorder of the carbon-based material and, consequently, the greater the degree of functionalization. In the present invention, the strength ratio (I) of the D band to G band areas of GO-Pr1 D /I G ) 1.23, GO-Pr D and G bands I D /I G 1.12, indicating that the functionalization degree of the amidated nano material GO-Pr1 is slightly stronger than that of the edge melting nano hybrid material GO-Pr. Interestingly, however, the porphyrin structure expands the GO structure to some extent by edge melting, and thus the vibration of electronsThe scattering reflects the GO information and the porphyrin information to a certain extent, so that rarely, a Raman signal of porphyrin appears on a GO-Pr Raman spectrum for the first time, the effective covalent functionalization is proved, the unique part of the connection mode is also proved, and the existence of pyrazine ring is suggested.
The binding of porphyrin units to the graphene edge is further demonstrated by X-ray photoelectron spectroscopy (XPS) of fig. 5. The total elemental composition of the GO and GO-Pr samples was determined by an initial broadband scan at 0-1200 eV. Both samples showed sharp carbon peaks and relatively weak oxygen peaks. The presence of porphyrin is confirmed by the appearance of the peak N1s of the GO-Pr spectrum. The peak separation is carried out on the N1s high-resolution XPS spectrum, and the area ratio of 2: 1:1, three peaks. According to literature reports, the peaks at 396.8eV and 398.4eV can be considered as porphyrin-derived pyrrolic N, while the peak at 401.8eV can be attributed to the newly formed pyrazine ring.
FIG. 6 shows transmission electron microscope images of porphyrin edge covalent fused graphene nonlinear nano hybrid material GO-Pr and reference material GO-Pr 1. As can be seen from the figure, the number of layers of GO-Pr1 is less than that of GO-Pr, and the dispersion is more uniform, because in GO-Pr1, porphyrin and graphene are connected through a flexible single bond, so that the spatial position of porphyrin is more flexible and can be twisted between graphene layers, thereby increasing the dispersibility of GO-Pr1 and preventing the accumulation of the layers. The GO-Pr is obtained by an edge melting method, the rigid structure of the pyrazine ring organizes the torsion of porphyrin molecules, and the plane of the GO is enlarged, so the dispersity is slightly poor.
FIG. 7 shows an atomic force microscope image and its height document of the GO-Pr edge fused porphyrin graphene nano hybrid material in the smart tapping mode. As can be seen from the figure, the hybrid material is distributed in irregular flakes with a size of about 1-2 μm, and the average thickness data of the hybrid material can be obtained by selecting two points outside the hybrid material flakes, and the thickness of the hybrid material is about 5 nm. The thickness of the monolayer graphene without obvious defects obtained by the CVD method is about 1 nm; after the fully oxidized graphene oxide obtained by the Hummers method is fully oxidized, a mica sheet sample is prepared by uniformly dispersing in water due to the existence of a large amount of carboxyl and hydroxyl functional groups, and the thickness measured by an atomic force microscope is about 1-2 nm; the thickness of the edge fused porphyrin graphene nano hybrid material prepared by the invention is about 5nm, and the porphyrin monomer aggravates the pi-pi stacking effect between layers to a certain extent, so that the obtained nano hybrid material has more than one layer, about 2-3 layers, and the result is consistent with that of a transmission electron microscope.
Fig. 8 shows thermogravimetric analysis of the raw material GO, porphyrin and edge fused porphyrin graphene nano hybrid material GO-Pr under nitrogen flow. Since GO contains many oxygen-containing groups, GO loses 8% of its weight at about 300 ℃ and 500 ℃. The main degradation range of porphyrin is 400-500 ℃, the quality is greatly changed, and about 30 percent of the quality is lost. There are mainly two mass reductions for the hybrid material GO-Pr, of which the fraction involved in porphyrin degradation is around 20%.
FIG. 9 shows UV-visible absorption spectra of GO, tetraphenylporphyrin Pr, edge fused porphyrin graphene nanohybrid GO-Pr, and amidated porphyrin graphene nanohybrid GO-Pr 1. As shown, GO has substantially no absorption other than the oscillation absorption peak of the benzene ring at around 270 nm. While the steady-state absorption curve of tetraphenylporphyrin shows the characteristic absorption peaks of porphyrin molecule, i.e. soret band (B band) at 419nm and Q band at 549 nm. It is worth noting that the absorption spectrum curves of the nano hybrid materials GO-Pr and GO-Pr1 are also significantly different, wherein the absorption curve of the porphyrin graphene nano hybrid material prepared by the amidation method is similar to that of other hybrid materials reported previously, the broadband absorption of GO is shown at 300-800nm, the characteristic absorption of porphyrin is also shown, the soret band absorption of porphyrin is shown at 423nm, and the red shift of 4nm is generated, which suggests the electron/energy transfer from the porphyrin monomer to the graphene oxide. In the novel porphyrin graphene nanometer hybrid material GO-Pr prepared by the edge melting method, obviously enhanced continuous absorption appears between 350-800nm, and relatively obvious absorption peak positions are about 410nm,550nm,640nm and 670 nm. In previous reports, no matter porphyrin is subjected to acylation reaction, esterification reaction, free radical addition reaction, click chemistry or even combination reaction, the main body of the porphyrin monomer and graphene are connected through a single line, so that a conjugated system is not obviously enhanced. The unexpected change side proves that the conjugation degree of the system is increased by connecting the porphyrin monomer and the graphene oxide plane through the pyrazine ring, so that the porphyrin monomer becomes a part of graphene at a certain angle and has the absorption characteristic (broadband absorption) of the graphene oxide; meanwhile, the graphene oxide also plays a role of a part of a growing porphyrin monomer conjugated system, and the result is consistent with the characteristic absorption of the fused porphyrin polymer, namely the porphyrin monomer which is subjected to the fusion process is like the cleavage of a fused porphyrin dimer soret band, and a part of blue shift and a part of red shift (419-410nm and 419-550 nm). FIG. 8 also shows fluorescence emission spectra of two nano-hybrid materials GO-Pr, GO-Pr1 and tetraphenylporphyrin Pr, as well as GO, under excitation at a wavelength of 420 nm. The fluorescence emission spectrum of Pr occurs at 662nm, GO has no fluorescence emission, while the fluorescence of GO-Pr and GO-Pr1 are quenched to different degrees, probably due to photo-induced electron/energy transfer behavior generated between the porphyrin and graphene oxide components. The difference is that the degree of quenching of GO-Pr1 is relatively low, quenching approximately 66% of the fluorescence, whereas the fluorescence quenching in GO-Pr is close to 90%. The difference of GO-Pr and GO-Pr1 in fluorescence quenching proves that more efficient electron/energy transfer exists in the molecule of the conjugated enhanced porphyrin graphene nano hybrid material formed by the edge melting method.
After the steady-state photophysical properties of the material are detected, it can be preliminarily recognized that more efficient electron/energy transfer exists between novel edge-fused porphyrin graphene nano hybrid materials, so far, some reports on graphene oxide and covalently functionalized graphene oxide (for example, covalent functionalization of GO through porphyrin, phthalocyanine and polymer molecules, amidation reaction, esterification reaction, 1, 3-dipolar cycloaddition reaction, free radical addition reaction of azoate, click chemistry and the like) have appeared, and it is proved that effective electron/energy transfer has a very obvious promotion effect on three-order nonlinear enhancement of nano hybrid materials, however, no report on porphyrin graphene nano hybrid materials with edges fused to form a larger conjugated system exists at present, so the work is performed on a precursor GO material, the three-order nonlinear energy of the tetraphenylporphyrin Pr edge fused porphyrin graphene nano hybrid material GO-Pr and the amidated porphyrin graphene nano hybrid material GO-Pr1 under 532nm nanosecond laser is researched, and the application of the carbon-based material in photoelectrons and photonic devices can be further widened through the thought.
FIG. 10 shows the open cell Z scan test results for GO, Pr, GO-Pr, and the reference material GO-Pr 1. The Nonlinear (NLO) performances of GO, Pr, GO-Pr and GO-Pr1 were explored at 532nm under a 4ns laser pulse condition. The two nano hybrid materials show better NLO response than a precursor material GO or a porphyrin monomer (Pr), which is an obvious characteristic of covalent functionalized connection, and is a result of synergistic effect of different nonlinear response mechanisms of the precursor material, mainly including nonlinear scattering and a small amount of two-photon absorption of GO, reverse saturation absorption of Pr, and electron/energy transfer from porphyrin to graphene oxide. In the GO-Pr curve, the minimum transmittance value at the focus is 42%, and the minimum transmittance value at the focus of the GO-Pr1 tested under the same condition is 55%, so that the GO-Pr shows better nonlinear response and optical amplitude limiting performance through two nano hybrid materials connected in different modes. In order to further determine the third-order nonlinear absorption coefficient of the material, fitting is carried out on multiple average data to obtain values of the third-order nonlinear absorption coefficients beta of GO, Pr, GO-Pr and GO-Pr1 which are respectively 2.1 multiplied by 10 -1 ，2.3×10 -1 ，9.8×10 -1 And 4.8X 10 -1 cm/GM, according to the results of the Z-scan test, the porphyrin graphene nano hybrid material obtained by edge melting can be judged to have better third-order nonlinear performance, and the method provides a new idea for designing and preparing more, more flexible and better nonlinear optical materials and devices in the future.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A porphyrin edge covalent fused graphene nonlinear nano hybrid material is characterized in that 2, 3-diaminoporphyrin and ortho-diketone at the edge of graphene oxide form a pyrazine ring through a condensation reaction in the nano hybrid material;
the nanometer hybrid material is prepared by the following processes:
(1) oxidizing flake graphite sequentially in a concentrated sulfuric acid, sodium nitrate and potassium permanganate system, adding hydrogen peroxide after the reaction is finished, filtering, washing and drying to obtain a graphene oxide fluffy solid;
(2) dissolving tetraphenylporphyrin in a trichloromethane solution, adding copper acetate dissolved in a methanol solution in advance, and stirring for reaction to obtain copper tetraphenylporphyrin;
(3) reacting tetraphenylporphyrin copper with excessive lithium nitrate under the catalysis of acetic acid and acetic anhydride to obtain 2-nitro-tetraphenylporphyrin copper;
(4) reacting 2-nitro-copper tetraphenylporphyrin with 4-amino-1, 2, 4-triazole and excessive KOH in a mixed solution of toluene and ethanol, and separating by column chromatography to obtain 2-nitro-3-amino-copper tetraphenylporphyrin;
(5) dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in a trichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring deionized water after rapid reaction, and separating to obtain 2-nitro-3-amino-tetraphenylporphyrin with copper ions removed;
(6) dissolving 2-nitro-3-amino-tetraphenylporphyrin in dichloromethane and methanol solution, adding 10% palladium carbon, stirring uniformly, adding sodium borohydride continuously, reacting under the monitoring of thin-layer chromatography, and separating to obtain 2, 3-diaminoporphyrin;
(7) dispersing graphene oxide fluffy solids in anhydrous DMF, carrying out nitrogen bubbling treatment, adding 2, 3-diaminoporphyrin dissolved in anhydrous dichloromethane, continuing bubbling, carrying out a dark reaction, and washing to obtain a target product, namely a porphyrin edge covalent fused graphene nonlinear nano hybrid material;
in the step (1), the adding amount ratio of the crystalline flake graphite, the concentrated sulfuric acid, the sodium nitrate and the potassium permanganate is 500 mg: (22-28) mL: (400- & gt 600) mg: (2-4) g;
the whole oxidation process specifically comprises the following steps: under the ice bath condition, the crystalline flake graphite is firstly stirred in concentrated sulfuric acid for 15-25min, and then is stirred in NaNO 3 Stirring the mixture in the system for reaction for 0.5 to 1.5 hours, then removing the ice bath after adding the potassium permanganate, and continuing the reaction for 0.5 to 1.5 hours after the reaction system is restored to the normal temperature;
after the reaction is finished, adding deionized water into the reaction system, and then dropwise adding hydrogen peroxide until the reaction system is brown yellow;
in the step (7), the reaction is carried out under the protection of inert gas, and the reaction time is 36-60 h;
the method comprises the following steps of (1) counting 10mg of graphene oxide fluffy solid, and preparing the correspondingly added 2, 3-diaminoporphyrin from 0.6-0.8 mmol of 2-nitro-3-amino-tetraphenylporphyrin;
the chemical structural formula of the 2, 3-diaminoporphyrin is as follows:
2. the method for preparing the porphyrin edge covalent fused graphene nonlinear nano hybrid material as claimed in claim 1, comprising the following steps:
(1) oxidizing flake graphite sequentially in a concentrated sulfuric acid, sodium nitrate and potassium permanganate system, adding hydrogen peroxide after the reaction is finished, filtering, washing and drying to obtain a graphene oxide fluffy solid;
(2) dissolving tetraphenylporphyrin in a trichloromethane solution, adding copper acetate dissolved in a methanol solution in advance, and stirring for reaction to obtain copper tetraphenylporphyrin;
(3) reacting tetraphenylporphyrin copper with excessive lithium nitrate under the catalysis of acetic acid and acetic anhydride to obtain 2-nitro-tetraphenylporphyrin copper;
(4) reacting 2-nitro-copper tetraphenylporphyrin with 4-amino-1, 2, 4-triazole and excessive KOH in a mixed solution of toluene and ethanol, and separating by column chromatography to obtain 2-nitro-3-amino-copper tetraphenylporphyrin;
(5) dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in a trichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring deionized water after rapid reaction, and separating to obtain 2-nitro-3-amino-tetraphenylporphyrin with copper ions removed;
(6) dissolving 2-nitro-3-amino-tetraphenylporphyrin in dichloromethane and methanol solution, adding 10% palladium carbon, stirring uniformly, adding sodium borohydride continuously, reacting under the monitoring of thin-layer chromatography, and separating to obtain 2, 3-diaminoporphyrin;
(7) dispersing graphene oxide fluffy solids in anhydrous DMF, carrying out nitrogen bubbling treatment, adding 2, 3-diaminoporphyrin dissolved in anhydrous dichloromethane, continuing bubbling, carrying out a dark reaction, and washing to obtain a target product, namely a porphyrin edge covalent fused graphene nonlinear nano hybrid material;
in the step (1), the adding amount ratio of the crystalline flake graphite, the concentrated sulfuric acid, the sodium nitrate and the potassium permanganate is 500 mg: (22-28) mL: (400- & lt600- & gt) mg: (2-4) g;
the whole oxidation process specifically comprises the following steps: under the ice-bath condition, the crystalline flake graphite is firstly stirred in concentrated sulfuric acid for 15-25min, and then in NaNO 3 Stirring the mixture in the system for reaction for 0.5 to 1.5 hours, then removing the ice bath after adding the potassium permanganate, and continuing the reaction for 0.5 to 1.5 hours after the reaction system is restored to the normal temperature;
after the reaction is finished, adding deionized water into the reaction system, and then dropwise adding hydrogen peroxide until the reaction system is brown yellow;
in the step (7), the reaction is carried out under the protection of inert gas, and the reaction time is 36-60 h;
the method comprises the following steps of (1) counting 10mg of graphene oxide fluffy solid, and preparing the correspondingly added 2, 3-diaminoporphyrin from 0.6-0.8 mmol of 2-nitro-3-amino-tetraphenylporphyrin;
the chemical structural formula of the 2, 3-diaminoporphyrin is as follows:
3. the preparation method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material according to claim 2, wherein in the step (2), the molar ratio of tetraphenylporphyrin to copper acetate is 1: 3-5;
the reaction was stirred at room temperature.
4. The preparation method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material according to claim 2, wherein in the step (3), the volume ratio of acetic acid to acetic anhydride is 1: 6-10;
the reaction is carried out at room temperature for 3-5 h.
5. The preparation method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material according to claim 2, wherein in the step (4), the molar ratio of the copper 2-nitro-tetraphenylporphyrin to the 4-amino-1, 2, 4-triazole is 1.5: 30-60 parts of;
the volume ratio of the toluene to the ethanol is 220-280: 20.
6. The preparation method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material according to claim 2, wherein in the step (5), the addition amount ratio of 2-nitro-3-amino-tetraphenylporphyrin copper, concentrated sulfuric acid and trifluoroacetic acid is (1.0-1.2) mmol: (30-50) mL:10 mL;
the rapid reaction is carried out in ice bath for 10-15 min.
7. The preparation method of the porphyrin edge covalent fused graphene nonlinear nano hybrid material according to claim 2, wherein in the step (6), the addition amount ratio of 2-nitro-3-amino-tetraphenylporphyrin, 10% palladium on carbon and sodium borohydride is 0.7 mmol: (400-600) mg: (8-12) mmol.
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