Carboxylated phthalocyanine MOF composite photocatalytic material

Abstract

The invention relates to the technical field of photocatalysis, and discloses a carboxylated phthalocyanine MOF composite photocatalytic material. The invention relates to a preparation method of a carboxylated phthalocyanine MOF composite photocatalytic material, which comprises the following steps: 1) dissolving cobalt tetracarboxyl phthalocyanine and iron nitrate nonahydrate in water, then adding glass fiber ball bundles, and carrying out hydrothermal reaction; 2) after the hydrothermal reaction in the step 1) is finished, filtering and recycling the glass fiber ball bundle composite material, and then purifying to obtain the glass fiber ball bundle loaded phthalocyanine MOF composite catalyst; and 3) carrying out vacuum activation treatment on the glass fiber ball bundle loaded phthalocyanine MOF composite catalyst obtained in the step 2) to obtain the carboxylated phthalocyanine MOF composite photocatalytic material. The carboxylated phthalocyanine MOF composite photocatalytic material provided by the invention has excellent adsorption performance and photocatalytic activity.

Description

Technical Field

[0001] The present invention relates to the field of photocatalysis technology, and in particular to a carboxylated phthalocyanine MOF composite photocatalytic material. Background Art

[0002] Printed circuit boards (PCBs) are the core basic components of modern electronic devices. Improper recycling methods will pose a serious threat to the environment and human health. Therefore, appropriate recycling methods must be adopted to recycle printed circuit boards. For example, patent CN107399928B discloses a method for preparing glass fiber pellets using waste printed circuit boards as raw materials. This method not only effectively realizes the recycling of printed circuit boards, but also the prepared glass fiber pellets have huge space and specific surface area. Therefore, the glass fiber pellets can be used as carriers of catalysts or adsorbents and applied to the field of photocatalysis or adsorption.

[0003] Phthalocyanine MOF composite catalyst is a metal-organic framework material with a three-dimensional open skeleton and high porosity. These pores not only provide a large surface area, but also provide active sites for gas adsorption, catalytic reactions, etc.

[0004] Phthalocyanine molecules have a two-dimensional conjugated π-electron structure, and their molecular structures are diverse and easy to tailor. Moreover, phthalocyanine molecules can derive a variety of substituted ligands, which can be designed, tailored and assembled according to the synthesis target. In addition, phthalocyanine molecules have strong coordination ability and can form stable complexes with almost all metal elements in the periodic table. Based on this, there are many types of phthalocyanine compounds, each with its own characteristics and wide application. Tetracarboxyl cobalt phthalocyanine (CoTCPc or CoPc(COOH)4) is a phthalocyanine compound containing cobalt ions, which introduces four carboxyl functional groups at specific positions of the phthalocyanine ring. At the same time, the center of the phthalocyanine ring is coordinated with the cobalt ion to form a stable metal phthalocyanine complex. This unique structure makes tetracarboxyl cobalt phthalocyanine show good catalytic activity as a catalyst in organic synthesis reactions.

[0005] Based on this, providing a composite photocatalytic material with glass fiber ball bundles as carriers and loaded with phthalocyanine MOF composite catalysts has become a technical problem that needs to be urgently solved by those skilled in the art. Summary of the invention

[0006] The purpose of the present invention is to provide a carboxylated phthalocyanine MOF composite photocatalytic material, which has excellent adsorption performance and photocatalytic activity.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] One of the technical solutions of the present invention:

[0009] A preparation method of a carboxylated phthalocyanine-based MOF composite photocatalytic material, comprising the following steps:

[0010] 1) Dissolve cobalt tetracarboxyl phthalocyanine and ferric nitrate nonahydrate in water, then add a bundle of glass fiber balls and carry out a hydrothermal reaction;

[0011] 2) After the hydrothermal reaction in step 1) is completed, filter to recover the composite material of the bundle of glass fiber balls, and then carry out a purification treatment to obtain a phthalocyanine-based MOF composite catalyst supported on the bundle of glass fiber balls;

[0012] 3) Carry out a vacuum activation treatment on the phthalocyanine-based MOF composite catalyst supported on the bundle of glass fiber balls obtained in step 2) to obtain the carboxylated phthalocyanine-based MOF composite photocatalytic material.

[0013] Further, in step 1), the molar ratio of the cobalt tetracarboxyl phthalocyanine to the ferric nitrate nonahydrate is 1∶(1 - 10).

[0014] Further, in step 1), the addition amount of the bundle of glass fiber balls is 0.2 - 0.8 g.

[0015] Further, in step 1), the volume of the water is 50 - 100 mL.

[0016] Further, in step 1), the hydrothermal reaction is specifically: carry out a hydrothermal reaction at 120 - 150 °C for 20 - 24 h.

[0017] Further, in step 2), the purification treatment is specifically: reflux in 95% ethanol for 8 h.

[0018] Further, in step 3), the temperature of the vacuum activation treatment is 120 - 180 °C and the time is 20 - 24 h.

[0019] The second technical solution of the present invention:

[0020] The carboxylated phthalocyanine-based MOF composite photocatalytic material prepared by the above preparation method of a carboxylated phthalocyanine-based MOF composite photocatalytic material.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The carboxylated phthalocyanine-based MOF composite photocatalytic material provided by the present invention has excellent adsorption performance and photocatalytic activity;

[0023] A carboxylated phthalocyanine-based MOF composite photocatalytic material provided by the present invention uses cobalt tetracarboxyl phthalocyanine and iron(III) nitrate nonahydrate to react to synthesize a porous metal-organic framework material, effectively improving the porosity and specific surface area of the carboxylated phthalocyanine-based MOF composite photocatalytic material, thereby effectively improving the adsorption performance and photocatalytic activity of the carboxylated phthalocyanine-based MOF composite photocatalytic material;

[0024] A carboxylated phthalocyanine-based MOF composite photocatalytic material provided by the present invention uses a glass fiber ball bundle as a carrier and loads a phthalocyanine-based MOF composite catalyst, which not only effectively realizes the recycling of printed circuit boards, but also the prepared carboxylated phthalocyanine-based MOF composite photocatalytic material has excellent adsorption performance and photocatalytic activity, expanding the scope of use of phthalocyanine materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] By reading the following detailed description of the preferred embodiments, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present invention. Moreover, throughout the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0026] Figure 1 is a physical diagram of the carboxylated phthalocyanine-based MOF composite photocatalytic material prepared in Example 2 of the present invention;

[0027] Figure 2 is an SEM diagram of the carboxylated phthalocyanine-based MOF composite photocatalytic material prepared in Example 2 of the present invention, where A is a low-magnification SEM diagram and B is a high-magnification SEM diagram;

[0028] Figure 3 is the detection result of photocatalytic performance. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0030] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0031] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0032] Without departing from the scope or spirit of the present invention, various modifications and variations can be made to the specific embodiments of the specification of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0033] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0034] In the following examples and comparative examples, the preparation method of the glass fiber ball bundle was carried out according to the preparation method described in Patent CN107399928B, specifically as follows:

[0035] 1) The waste printed circuit boards were crushed and sorted, and the non-metallic powder was collected;

[0036] 2) 100 g of the non-metallic powder obtained in step 1) was added to 300 mL of 6 mol / L nitric acid solution, heated at 85 °C for 20 h, filtered, the filtrate was extracted with ethylene glycol monoethyl ether, and the solid was washed with ethylene glycol monoethyl ether to obtain glass fiber powder; the ethylene glycol monoethyl ether extraction solution and washing solution were combined, and ethylene glycol monoethyl ether was evaporated off with a rotary evaporator to obtain recycled epoxy resin;

[0037] 3) 50 g of the glass fiber powder obtained in step 2) and 1 g of the recycled epoxy resin obtained in step 2) were added to 200 mL of a 6% ethanol solution of diethylenetriamine, heated at 50 °C for 7 h, filtered to obtain a crude glass fiber ball bundle, and then the crude glass fiber ball bundle was added to 150 mL of ethanol, heated at 40 °C for 5 h, filtered, and dried to obtain the glass fiber ball bundle.

[0038] In the following examples, a preparation method of a carboxylated phthalocyanine-based MOF composite photocatalytic material includes the following steps:

[0039] 1) Dissolve cobalt tetracarboxyl phthalocyanine and ferric nitrate nonahydrate in 50 - 100 mL of distilled water according to the molar ratio of cobalt tetracarboxyl phthalocyanine to ferric nitrate nonahydrate of 1∶(1 - 10). Then add 0.2 - 0.8 g of glass fiber ball bundles, mix well, and carry out hydrothermal reaction at 120 - 150 °C for 20 - 24 h;

[0040] 2) After the hydrothermal reaction in step 1) is completed, cool it, filter, and recover the glass fiber ball bundle composite material. Then place it in 95% ethanol and reflux for 8 h, wash, and dry to obtain the glass fiber ball bundle supported phthalocyanine - based MOF composite catalyst;

[0041] 3) Carry out vacuum activation treatment on the glass fiber ball bundle supported phthalocyanine - based MOF composite catalyst obtained in step 2) to obtain the carboxylated phthalocyanine - based MOF composite photocatalytic material;

[0042] Among them, the temperature of the vacuum activation treatment is 120 - 180 °C, and the time is 20 - 24 h.

[0043] Example 1

[0044] A carboxylated phthalocyanine - based MOF composite photocatalytic material

[0045] 1) Add 0.249 g of cobalt tetracarboxyl phthalocyanine and 0.404 g of ferric nitrate nonahydrate to 50 mL of distilled water, stir for 3 h, then add 0.2 g of glass fiber ball bundles, mix well, and carry out hydrothermal reaction at 150 °C for 20 h;

[0046] 2) After the hydrothermal reaction in step 1) is completed, cool it, filter with a 20 - mesh sieve, and recover the glass fiber ball bundle composite material. Then place the glass fiber ball bundle composite material in 95% ethanol and reflux for 8 h, wash successively with distilled water and ethanol, and dry to obtain the glass fiber ball bundle supported phthalocyanine - based MOF composite catalyst;

[0047] 3) Carry out vacuum activation treatment on the glass fiber ball bundle supported phthalocyanine - based MOF composite catalyst obtained in step 2) to obtain the carboxylated phthalocyanine - based MOF composite photocatalytic material;

[0048] Among them, the temperature of the vacuum activation treatment is 150 °C, and the time is 24 h.

[0049] Example 2

[0050] A carboxylated phthalocyanine - based MOF composite photocatalytic material

[0051] 1) Add 0.747 g of cobalt tetracarboxyl phthalocyanine and 2.02 g of ferric nitrate nonahydrate to 50 mL of distilled water, stir for 3 h, then add 0.2 g of glass fiber ball bundles, mix well, and carry out hydrothermal reaction at 130 °C for 23 h;

[0052] 2) After the hydrothermal reaction in step 1) is completed, cool it, filter it using a 20-mesh sieve, recover the glass fiber ball bundle composite material, and then place the glass fiber ball bundle composite material in 95% ethanol and reflux for 8 h. Wash it successively with distilled water and ethanol, and dry it to obtain a glass fiber ball bundle supported phthalocyanine-based MOF composite catalyst;

[0053] 3) Perform vacuum activation treatment on the glass fiber ball bundle supported phthalocyanine-based MOF composite catalyst obtained in step 2) to obtain the carboxylated phthalocyanine-based MOF composite photocatalytic material;

[0054] Among them, the temperature of the vacuum activation treatment is 160 °C and the time is 22 h.

[0055] Example 3

[0056] A carboxylated phthalocyanine-based MOF composite photocatalytic material

[0057] 1) Add 0.373 g of cobalt tetracarboxyl phthalocyanine and 2.02 g of iron(III) nitrate nonahydrate to 50 mL of distilled water, stir for 3 h, then add 0.2 g of glass fiber ball bundle, mix well, and carry out hydrothermal reaction at 120 °C for 24 h;

[0058] 2) After the hydrothermal reaction in step 1) is completed, cool it, filter it using a 20-mesh sieve, recover the glass fiber ball bundle composite material, and then place the glass fiber ball bundle composite material in 95% ethanol and reflux for 8 h. Wash it successively with distilled water and ethanol, and dry it to obtain a glass fiber ball bundle supported phthalocyanine-based MOF composite catalyst;

[0059] 3) Perform vacuum activation treatment on the glass fiber ball bundle supported phthalocyanine-based MOF composite catalyst obtained in step 2) to obtain the carboxylated phthalocyanine-based MOF composite photocatalytic material;

[0060] Among them, the temperature of the vacuum activation treatment is 180 °C and the time is 20 h.

[0061] Effect verification

[0062] The physical picture of the carboxylated phthalocyanine-based MOF composite photocatalytic material prepared in Example 2 is as Figure 1 shown;

[0063] As can be seen from Figure 1 the carboxylated phthalocyanine-based MOF composite photocatalytic material prepared in the present invention is an orange spherical solid.

[0064] The SEM image of the carboxylated phthalocyanine-based MOF composite photocatalytic material prepared in Example 2 is as Figure 2 shown, where A is a low-magnification SEM image and B is a high-magnification SEM image;

[0065] As can be seen from Figure 2It can be seen that the prepared carboxylated phthalocyanine-based MOF composite photocatalytic material shows closely arranged particles, forming a structure similar to a layered structure.

[0066] The photocatalytic performance of the composite photocatalytic materials prepared in Examples 1 to 3 was detected. The photocatalytic performance detection method was as follows:

[0067] Prepare methylene blue of 10 mg / mL. Take 50 mL of the dye and 0.1 g of the composite photocatalytic material and put them into a glass conical flask. Place it in an air bath constant temperature oscillator and shake it in the dark at 180 r / min for 30 min for adsorption and degradation. Then turn on the light source for irradiation. During this period, collect 3 mL of the suspension with a syringe every 30 min; filter it with a 0.22-um needle filter and place it in a quartz cuvette, and use a UV-visible spectrophotometer to measure the absorbance of the organic dye at its characteristic absorption peak to determine the degradation effect of the composite photocatalytic material on methylene blue;

[0068] The photocatalytic performance detection results are as Figure 3 shown;

[0069] It can be Figure 3 seen that Example 2 has the best degradation effect on methylene blue. The adsorption rate can reach 61.3% in 30 min, and the degradation effect can reach 98.6% in three hours.

[0070] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above examples, those of ordinary skill in the art should understand that: still can modify the specific implementation manners of the present invention or make equivalent substitutions, and any modification or equivalent substitution without departing from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material, characterized in that: The following steps are involved: 1) dissolving tetracarboxylphthalocyanine cobalt and ferric nitrate nonahydrate in water, and then adding glass fiber ball bundles for hydrothermal reaction; 2) After the hydrothermal reaction in step 1) is completed, filtering and recovering the glass fiber ball bundle composite material, and then purifying it to obtain a glass fiber ball bundle-loaded phthalocyanine MOF composite catalyst; 3) vacuum activation treatment is performed on the glass fiber ball bundle loaded with phthalocyanine MOF composite catalyst obtained in step 2) to obtain the carboxylated phthalocyanine MOF composite photocatalytic material.

2. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 1), the molar ratio of tetracarboxyphthalocyanine cobalt to ferric nitrate nonahydrate is 1:(1-10).

3. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 1), the amount of glass fiber ball bundle added is 0.2 to 0.8 g.

4. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 1), the volume of water is 50-100 mL.

5. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 1), the hydrothermal reaction is specifically: hydrothermal reaction at 120-150° C. for 20-24 hours.

6. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 2), the purification treatment is specifically: reflux in 95% ethanol for 8 hours.

7. The method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material according to claim 1, characterized in that: In step 3), the temperature of the vacuum activation treatment is 120-180° C. and the time is 20-24 hours.

8. A carboxylated phthalocyanine MOF composite photocatalytic material prepared by the method for preparing a carboxylated phthalocyanine MOF composite photocatalytic material as claimed in any one of claims 1 to 7.

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