CN104891822A - Sulfonic acid group phthalocyanine nickel-graphene oxide composite film material and preparation method thereof - Google Patents

Abstract

A sulfonic acid-based phthalocyanine nickel-graphene oxide composite thin film material and a preparation method, the invention belongs to the field of nonlinear optics, and aims to solve the problem of poor third-order nonlinear optical performance of existing nonlinear optical thin film materials. The sulfonic acid phthalocyanine nickel-graphene oxide composite thin film material is formed into a film by an electrostatic self-assembly method from an aqueous solution of a phthalocyanine compound and graphene oxide. Preparation method: 1. Quartz substrates are alternately placed in PDDA solution and PSS solution to prepare negatively charged substrates; 2. Substrates are sequentially placed in PDDA solution, α-SLPcNi aqueous solution, PDDA solution and graphene oxide aqueous solution ; 4. Step 2 is repeated several times to obtain a composite film material. The present invention selects tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine whose center metal is nickel, and the third-order nonlinear absorption coefficient β of the composite film material is 4.16×10 ^-5 m/W, which has good three-dimensional first-order nonlinear optical properties.

Description

A kind of sulfonic acid phthalocyanine nickel-graphene oxide composite film material and its preparation method

technical field

The invention belongs to the field of nonlinear optics, and in particular relates to a metal phthalocyanine-graphene oxide composite film material and a preparation method.

Background technique

Nonlinear optical materials play an important role in the design and development of optical functional devices. The assembly of nonlinear optical materials into solid thin films is a requirement for the instrumentation of functional materials. Both phthalocyanine and graphene are good nonlinear optical materials. As a classic organic nonlinear optical material, phthalocyanine ligands have a special planar conjugated π electron structure, and the conjugated macrocyclic system has a strong π-π electron interaction, so this type of compound has special optical, electrical, Special properties such as magnetism. Graphene, a rising star of nonlinear optical materials, the thinnest two-dimensional material in the world, has attracted extensive attention from researchers. The carbon atoms in graphene are connected to each other by large conjugated π bonds with very high bond energy. Due to its unique energy band structure and excellent properties, these properties make graphene have potential applications in optoelectronic devices. However, the application of graphene in the optical field is limited due to the difficulty of solubility. The graphene is oxidized to add many oxygen-containing functional groups on the surface, such as hydroxyl, carboxyl, etc., which improves the solubility of graphene and effectively changes its photoelectric properties. Both phthalocyanine and graphene oxide have a two-dimensional planar structure. Physically combining phthalocyanine and graphene can achieve π-π stacking, and they can adsorb each other through electrostatic interaction and have stable performance. At this time, the composite material is the same as Compared with a single material (phthalocyanine or graphene oxide), it has a higher nonlinear absorption coefficient, so the compounded phthalocyanine and graphene oxide are more suitable for light confinement materials.

Electrostatic self-assembled thin film technology refers to the multilayer film formed by the alternate deposition of oppositely charged ions by electrostatic interaction. Since the 1990s, this technology was proposed by Sagi et al. Due to its unique advantages over other coating technologies and the ability to control the composition and thickness of the film, it can realize the functions of light, electricity, magnetism, and release of the film. change. Therefore, it has received extensive attention in the field of self-assembly technology.

Contents of the invention

The purpose of the present invention is to solve the problem of poor third-order nonlinear optical performance of existing nonlinear optical film materials, and provide a sulfonic acid-based phthalocyanine nickel-graphene oxide composite film material and a preparation method.

The sulfonic acid-based phthalocyanine nickel-graphene oxide composite thin film material of the present invention is formed into a film by an electrostatic self-assembly method of an aqueous solution of a phthalocyanine compound and graphene oxide, wherein the phthalocyanine compound is a charged tetra-α-( 4-sulfonic acid phenoxy) nickel phthalocyanine (α-PhSPcNi), its structural formula is:

The preparation method of the sulfonic acid base phthalocyanine nickel-graphene oxide composite film material of the present invention is realized according to the following steps:

1. Soak the pretreated quartz substrate in a PDDA (polydiallyldimethylammonium chloride) solution with a mass concentration of 10% for 8 to 10 minutes, take it out, wash it with distilled water, and dry it with _N2 Then immerse in a PSS (sodium polystyrene sulfonate) solution with a mass concentration of 10% for 8 to 10 minutes, take it out, wash it with distilled water, and dry it with _N2 to complete the PDDA-PSS soaking process once, and repeat the PDDA-PSS The soaking process was performed three times to obtain a negatively charged substrate;

Two, put the negatively charged substrate obtained in step 1 into a PDDA solution with a mass concentration of 10% and soak for 8 to 10 minutes, take it out, wash it with distilled water, dry it with N ₂ and immerse it in tetra-α-(4 - sulfonic acid phenoxy) phthalocyanine nickel (α-SLPcNi) aqueous solution for 8 to 10 minutes, take it out, wash it with distilled water, blow dry with _N2 and then immerse it in a PDDA solution with a mass concentration of 10% for 8 to 10 minutes, After taking it out, wash it with distilled water, dry it with _N2 , and finally immerse it in the graphene _oxide (GO) aqueous solution for 8-10 minutes. 4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide composite film assembly;

3. Repeat the assembly process of a single pair of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite films in step 2 multiple times to obtain a composite film material of nickel phthalocyanine sulfonate-graphene oxide .

The present invention selects tetra-alpha-(4-sulfonic acid phenoxy)nickel phthalocyanine whose central metal is nickel, and the charge transfer between the central metal and the phthalocyanine ring effectively increases the electron delocalization energy of phthalocyanine, making the phthalocyanine The nonlinear susceptibility of cyanine is at least two orders of magnitude greater than that of metal-free phthalocyanine, and the third-order nonlinear susceptibility χ ⁽³⁾ of phthalocyanine solution can reach a maximum value of 10 ^-10 esu. Graphene oxide prepared by the Hummers method has good dispersion. The tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide composite thin film material was obtained by electrostatic self-assembly method, and the thickness of the thin film was determined by the number of assembled layers. The operation process of electrostatic self-assembly is simple, and the experimental conditions are relaxed. Both phthalocyanine complexes and graphene have a two-dimensional planar structure. During the film formation process, phthalocyanine and graphene can be closely packed, which is conducive to electron transfer between the two, and a larger conjugated π electron system is formed. It is beneficial to the third-order nonlinear absorption, and the third-order nonlinear absorption coefficient β of the sulfonic acid phthalocyanine nickel-graphene oxide composite film is 4.16×10 ^-5 m/W. The tetra-alpha-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide composite nonlinear thin film material has stable performance and good third-order nonlinear optical performance, and can be applied in the fields of optical limiting and laser protection.

Description of drawings

Fig. 1 is the ultraviolet-visible absorption spectrum of the 1-10 layer four-α-(4-sulfonic acid phenoxy group) nickel phthalocyanine-graphene oxide composite nonlinear film that embodiment two obtains, along the arrow direction nonlinear optics The number of layers of the film is reduced, 1-tetra-α-(4-sulfonic acid phenoxy) nickel phthalocyanine aqueous solution, 2-graphene oxide aqueous solution;

Fig. 2 is the atomic force diagram of 30 pairs of layers of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite nonlinear optical film obtained in embodiment four;

Fig. 3 is the three-dimensional perspective view of 30 pairs of layers of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite nonlinear optical film obtained in embodiment four;

Fig. 4 is the Raman spectrogram of 20 pairs of layers of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite nonlinear optical film obtained in embodiment three;

Fig. 5 is the opening Z-scan curve of 30 pairs of layers of four-α-(4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide composite nonlinear optical film obtained in Example 4.

Detailed ways

Specific Embodiment 1: In this embodiment, the sulfonic acid-based phthalocyanine nickel-graphene oxide composite film material is formed by electrostatic self-assembly of an aqueous solution of phthalocyanine compound and graphene oxide, wherein the phthalocyanine compound is charged Tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine (α-PhSPcNi), its structural formula is:

Embodiment 2: This embodiment is different from Embodiment 1 in that the graphene oxide is prepared by the Hummers method.

The graphene oxide described in this embodiment is prepared by the Hummers method, has good dispersibility, and its structural formula is

Specific embodiment three: the preparation method of sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material of this embodiment is implemented according to the following steps:

1. Soak the pretreated quartz substrate in a PDDA (polydiallyldimethylammonium chloride) solution with a mass concentration of 10% for 8 to 10 minutes, take it out, wash it with distilled water, and dry it with _N2 Then immerse in a PSS (sodium polystyrene sulfonate) solution with a mass concentration of 10% for 8 to 10 minutes, take it out, wash it with distilled water, and dry it with _N2 to complete the PDDA-PSS soaking process once, and repeat the PDDA-PSS The soaking process was performed three times to obtain a negatively charged substrate;

Two, put the negatively charged substrate obtained in step 1 into a PDDA solution with a mass concentration of 10% and soak for 8 to 10 minutes, take it out, wash it with distilled water, dry it with N ₂ and immerse it in tetra-α-(4 - sulfonic acid phenoxy) phthalocyanine nickel (α-SLPcNi) aqueous solution for 8 to 10 minutes, take it out, wash it with distilled water, blow dry with _N2 and then immerse it in a PDDA solution with a mass concentration of 10% for 8 to 10 minutes, After taking it out, wash it with distilled water, dry it with _N2 , and finally immerse it in the graphene _oxide (GO) aqueous solution for 8-10 minutes. 4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide composite film assembly;

3. Repeat the assembly process of a single pair of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite films in step 2 multiple times to obtain a composite film material of nickel phthalocyanine sulfonate-graphene oxide .

This embodiment uses the electrostatic self-assembly method to prepare a tetra-α-(4-sulfonic acid phenoxy)nickel-graphene oxide composite thin film material that tends to be used in practical applications, and can be used in nonlinear optics and laser protection. field. The whole preparation process is simple, convenient to operate, has no special requirements on equipment, and is an environment-friendly method.

Specific embodiment four: the difference between this embodiment and specific embodiment three is that the quartz substrate after the pretreatment described in step one is that the quartz substrate is first wiped clean with acetone, and then immersed in the NaOH solution of 1mol/L for 5min, After taking it out, it is washed and dried to obtain a pretreated quartz substrate. Other steps and parameters are the same as those in the third embodiment.

Embodiment 5: The difference between this embodiment and Embodiment 3 or 4 is that the concentration of tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine aqueous solution described in step 2 is 0.8-1.5 mg/ml. Other steps and parameters are the same as those in Embodiment 3 or 4.

Embodiment 6: This embodiment differs from Embodiment 5 in that the concentration of tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine aqueous solution described in step 2 is 1 mg/ml. Other steps and parameters are the same as those in Embodiment 3 or 4.

Embodiment 7: This embodiment differs from Embodiment 3 to Embodiment 6 in that the concentration of the graphene oxide aqueous solution described in step 2 is 0.08-0.15 mg/ml. Other steps and parameters are the same as one of the third to sixth specific embodiments.

Embodiment 8: This embodiment differs from Embodiment 7 in that the concentration of the graphene oxide aqueous solution described in step 2 is 0.1 mg/ml. Other steps and parameters are the same as those in Embodiment 7.

Specific embodiment nine: This embodiment is different from one of the specific embodiments three to eight in that step three is repeated 15 to 30 times and step two is a single pair of four-alpha-(4-sulfonic acid phenoxy)nickel phthalocyanine- Graphene oxide composite film assembly process. Other steps and parameters are the same as those in the third to eighth specific embodiments.

Embodiment 1: The preparation method of the sulfonic acid-based nickel phthalocyanine-graphene oxide composite film material in this embodiment is implemented according to the following steps:

1. Soak the pretreated quartz substrate in a PDDA (polydiallyldimethylammonium chloride) solution with a mass concentration of 10% for 10 minutes, take it out, wash it with secondary water, and dry it with _N2 Then immerse in the PSS (sodium polystyrene sulfonate) solution with a mass concentration of 10% for 10 minutes, take it out, wash it with secondary water, blow dry with _N2 , complete the PDDA-PSS soaking process once, and repeat the PDDA-PSS The soaking process was performed three times to obtain a negatively charged substrate;

2. Put the negatively charged substrate obtained in step 1 into a PDDA solution with a mass concentration of 10% and soak for 10 minutes, take it out, wash it with secondary water, dry it with _N2 and immerse it in a PDDA solution with a concentration of 1mg/ml. Tetra-α-(4-sulfonic acid phenoxy) nickel phthalocyanine (α-SLPcNi) aqueous solution for 10min, take it out, wash it with secondary water, dry it with _N2 and then immerse it in the PDDA solution with a mass concentration of 10%. Soak in water for 10min, take it out, wash it with secondary water, dry it with _N2 , and finally immerse it in a graphene oxide aqueous solution with a concentration of 0.1mg/ml for 10min, take it out, wash it with secondary water, and dry it with _N2 , to complete the assembly of a single pair of four-α-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide composite films.

Both PDDA and PSS used in this example were purchased from Sigma-Aldrich. Tetra-α-(4-sulfonic acid phenoxy) nickel phthalocyanine is synthesized by using α-(4-sulfonic acid phenoxy) phthalonitrile as a precursor, anhydrous zinc acetate as the metal salt, and synthesized by DBU template method , the solvent is n-amyl alcohol, the metal salt is anhydrous nickel chloride NiCl ₂ , and the reaction temperature is controlled at 140°C. The synthesis method of the precursor α-(4-sulfonic acid phenoxy)phthalonitrile is as follows: 3-nitrophthalonitrile and 4-hydroxybenzenesulfonic acid are fed at a ratio of 1:1, anhydrous potassium carbonate As a catalyst, react at room temperature for 3-4 days under the protection of nitrogen.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that step 3 is repeated 1 to 10 times respectively, and step 2 is a single pair of four-α-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide composite film During the assembly process, a sulfonic acid phthalocyanine nickel-graphene oxide composite thin film material is obtained.

The growth process of 1 to 10 pairs of α-PhSPcNi/PDDA/GO electrostatic self-assembled multilayer films was tested by ultraviolet-visible absorption spectroscopy, and the measured wavelength range was adjusted at 200-850nm. Fig. 1 is the ultraviolet-visible absorption spectrum, as can be seen from the figure, the absorption peaks of four-alpha-(4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide thin film material are around 230nm and 680nm, this shows that composite The characteristic peaks of phthalocyanine and graphene oxide are reflected in the ultraviolet-absorption spectrum of the material, and the maximum absorption peak of tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide film material and phthalocyanine aqueous solution Compared with both, a certain degree of red shift occurs, indicating that the aggregation of phthalocyanine molecules in the film is face-to-face close packing. In addition, as the number of film layers increases, the maximum absorption value of the Q-band of the film increases. It shows that the electrostatic self-assembly provides a uniform and orderly film deposition process for the phthalocyanine-graphene oxide composite.

Embodiment 3: The difference between this embodiment and Embodiment 1 is that step 3 is repeated 20 times respectively, and step 2 is a single pair of four-α-(4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide composite film assembly process , to obtain sulfonic acid phthalocyanine nickel-graphene oxide composite thin film material.

Test Example 20 Raman spectroscopy was performed on the layer tetra-α-(4-sulfonic acid phenoxy)nickel phthalocyanine-graphene oxide composite nonlinear optical thin film material, and the laser wavelength was 458nm. It can be seen from the figure that the α-SLPcNi/PDDA/GO film exhibits two main characteristic bands of graphene at 1372.7cm ^-1 (D band) and 1594.9cm ^-1 (G band), and the D peak is A _1g is related to the order degree of graphene; the G peak is the characteristic peak of graphene and is related to the E _2g Raman active mode of sp ² hybridized carbon atoms. It shows that GO molecules are deposited on the α-SLPcNi/PDDA/GO electrostatic self-assembled film.

Embodiment 4: The difference between this embodiment and Embodiment 1 is that step 3 is repeated 30 times respectively, and step 2 is a single pair of four-α-(4-sulfonic acid phenoxy) phthalocyanine nickel-graphene oxide composite film assembly process , to obtain sulfonic acid phthalocyanine nickel-graphene oxide composite thin film material.

Use an atomic force microscope to observe the surface morphology of the phthalocyanine-graphene oxide material at a scale of 20 μm, select 30 pairs of α-PhSPcNi/PDDA thin film materials for observation in a 2×2um area, and give its atomic force plan and three-dimensional images . From Fig. 2 and Fig. 3, it can be clearly seen that densely packed pointed nanoparticles are formed on the substrate, and the particle distribution is relatively uniform. Graphene has a large sheet structure and uniform and flat particle distribution, with a roughness of 13.529nm and an average diameter of 3.09um. During the deposition of electrostatic self-assembled films, metal phthalocyanine and graphene molecular aggregates are formed on the surface of the substrate.

In open Z-scan testing, a YAG laser is used as the light source. The energy is 1.16μJ, the wavelength is 532nm, and the pulse width is 4ns. The metal phthalocyanine-graphene oxide composite thin film material is fixed, and the output laser is shot on the thin film material. The computer is used to collect and process the data, and pass through the energy detector. A sent data Zolix SC300-2A motion controller. The numerical value of the Z-scan is fitted to obtain the Z-scan curve. The third-order nonlinear optical parameters of the α-SLPcNi/PDDA/GO thin film: the third-order nonlinear absorption coefficient β is 4.16×10 ^-5 m/W, and the value of the imaginary part Imχ ⁽³⁾ is 1.51×10 ^-6 esu. The α-SLPcNi/PDDA/GO film has a trough curve, and the polymer electrolytes PDDA and PSS used in the film-making have no third-order nonlinear optical properties. The third-order nonlinear optical properties of the α-SLPcNi/PDDA/GO film are α-SLPcNi and GO, indicating that the sample has good reverse saturable absorption properties.

Claims (9)

1. A sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material, the sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material is formed into a film by electrostatic self-assembly of an aqueous solution of a phthalocyanine compound and graphene oxide , wherein the phthalocyanine compound is charged four-alpha-(4-sulfonic acid phenoxy)nickel phthalocyanine, its structural formula is: 2. a kind of sulfonic acid base phthalocyanine nickel-graphene oxide composite film material according to claim 1, is characterized in that described graphene oxide adopts Hummers method to prepare. 3. a kind of preparation method of sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material is characterized in that is to realize according to the following steps: 1. Soak the pretreated quartz substrate in a PDDA solution with a mass concentration of 10% for 8-10 minutes, take it out, wash it with distilled water, dry it with _N2 , and then immerse it in a PSS solution with a mass concentration of 10% 8 to 10 minutes, take it out, wash it with distilled water, blow it dry with _N2 , complete the PDDA-PSS soaking process once, repeat the PDDA-PSS soaking process three times, and get a negatively charged substrate; Two, put the negatively charged substrate obtained in step 1 into a PDDA solution with a mass concentration of 10% and soak for 8 to 10 minutes, take it out, wash it with distilled water, dry it with N ₂ and immerse it in tetra-α-(4 - sulfonic acid phenoxy) nickel phthalocyanine aqueous solution for 8-10 minutes, take it out and wash it with distilled water, blow it dry with _N2 and then immerse it in a PDDA solution with a mass concentration of 10% for 8-10 minutes, take it out and wash it with distilled water Clean, blow dry with N ₂ and finally immerse in the graphene oxide aqueous solution for 8-10 minutes, take it out, wash it with distilled water, and blow dry with N ₂ to complete the monolayer tetra-α-(4-sulfonic acid phenoxy) Assembly of nickel phthalocyanine-graphene oxide composite thin films; 3. Repeat the assembly process of a single pair of four-alpha-(4-sulfonic acid phenoxy) nickel phthalocyanine-graphene oxide composite films in step 2 multiple times to obtain a composite film material of nickel phthalocyanine sulfonate-graphene oxide . 4. the preparation method of a kind of sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material according to claim 3 is characterized in that the quartz substrate after the pretreatment described in step one is that the quartz substrate is used first Wipe it clean with acetone, then immerse it in a 1mol/L NaOH solution for 5 minutes, take it out, wash it and dry it, and obtain a pretreated quartz substrate. 5. the preparation method of a kind of sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material according to claim 3 is characterized in that four-alpha-(4-sulfonic acid phenoxy)phthalein described in step 2 The concentration of the nickel cyanine aqueous solution is 0.8-1.5 mg/ml. 6. the preparation method of a kind of sulfonic acid base phthalocyanine nickel-graphene oxide composite film material according to claim 5 is characterized in that the four-alpha-(4-sulfonic acid phenoxy)phthalein described in step 2 The concentration of the nickel cyanine aqueous solution was 1 mg/ml. 7. The method for preparing a sulfonic acid phthalocyanine nickel-graphene oxide composite film material according to claim 3, characterized in that the concentration of the graphene oxide aqueous solution described in step 2 is 0.08-0.15 mg/ml. 8. The preparation method of a kind of sulfonic acid phthalocyanine nickel-graphene oxide composite film material according to claim 7, characterized in that the concentration of the graphene oxide aqueous solution described in step 2 is 0.1mg/ml. 9. the preparation method of a kind of sulfonic acid base phthalocyanine nickel-graphene oxide composite thin film material according to claim 3 is characterized in that the single pair of layer four-alpha-(4 -Sulphonic acid phenoxy)nickel phthalocyanine-graphene oxide composite thin film assembly process.