阅读说明：本技术 一种微波快速制备酞菁分子及其衍生物/碳复合催化剂的方法及其应用 (Method for rapidly preparing phthalocyanine molecule and derivative thereof/carbon composite catalyst by microwave and application thereof ) 是由 于畅 李文斌 邱介山 谭新义 于 2021-10-21 设计创作，主要内容包括：本发明属于碳基材料制备技术领域,一种微波快速制备酞菁分子及其衍生物/碳复合催化剂的方法及其应用,其中制备方法包括以下步骤：(1)将酞菁分子及其衍生物和碳源加入到盛有丙三醇的石英微波管中,再将石英微波管置于微波反应器中,在Ar气保护下,进行微波反应；(2)微波反应结束后,取出混合物,用去离子水和无水乙醇反复冲洗,然后放入到真空干燥箱中干燥,制得目标材料酞菁分子及其衍生物/碳复合催化剂。本发明方法工艺简单、制备时间短、成本低、绿色环保、具有普适性。利用该方法制备的酞菁分子及其衍生物/碳复合催化剂具有催化活性高、活性物质稳定、可以高效抑制析氢副反应等优点,在催化领域具有较大的应用潜力。(The invention belongs to the technical field of carbon-based material preparation, and relates to a method for quickly preparing phthalocyanine molecules and derivatives thereof/carbon composite catalysts by microwaves and application thereof, wherein the preparation method comprises the following steps: (1) adding phthalocyanine molecules and derivatives thereof and a carbon source into a quartz microwave tube containing glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction under the protection of Ar gas; (2) and after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture by using deionized water and absolute ethyl alcohol, and then putting the mixture into a vacuum drying oven for drying to obtain the target material phthalocyanine molecule and the derivative thereof/carbon composite catalyst. The method has the advantages of simple process, short preparation time, low cost, environmental protection and universality. The phthalocyanine molecule and the derivative/carbon composite catalyst thereof prepared by the method have the advantages of high catalytic activity, stable active substances, capability of efficiently inhibiting hydrogen evolution side reaction and the like, and have great application potential in the field of catalysis.)

1. A method for rapidly preparing phthalocyanine molecules and derivatives thereof/carbon composite catalysts by microwaves is characterized by comprising the following steps:

step 1, adding 2-10mg of phthalocyanine molecules and derivatives thereof and 50-100mg of carbon source into a quartz microwave tube containing 5-10mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction under the protection of Ar gas, wherein the microwave reaction power is set to 800W, and the microwave reaction time is controlled to be 5-20 min;

and 2, after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3-5 times by using deionized water and absolute ethyl alcohol, then putting the mixture into a vacuum drying oven to be dried for 8-12h, controlling the drying temperature to be 60-80 ℃, and preparing the target material phthalocyanine molecule and derivative/carbon composite catalyst thereof, wherein the phthalocyanine molecule and derivative thereof are selected from one of phthalocyanine, cobalt phthalocyanine, iron phthalocyanine, nickel phthalocyanine or copper phthalocyanine, and the carbon source is selected from one of carbon nano tubes, graphite oxide or carbon black.

2. The phthalocyanine molecule and the derivative thereof/carbon composite catalyst prepared by the method of claim 1 are used as electrode materials in the carbon dioxide electroreduction reaction.

Technical Field

The invention relates to a method for rapidly preparing phthalocyanine molecules and a phthalocyanine molecule derivative/carbon composite catalyst by microwave and application thereof, belonging to the technical field of carbon-based material preparation.

Background

Carbon dioxide is taken as a linear symmetric molecule, two sp hybridized orbitals of carbon atoms respectively form two sigma bonds with 2p orbitals of two oxygen atoms, two p orbitals of carbon atoms respectively form pi bonds with p orbitals of two oxygen atoms, and electrons on the delocalized pi orbitals of carbon dioxide form two stable large pi bonds (namely pi bonds) with three central four electrons⁴ ₃Bonds) and thus the carbon dioxide molecule has excellent chemical stability, resulting in high energy consumption for catalytic conversion of carbon dioxide. Among a plurality of technical means for converting and utilizing carbon dioxide, the electrochemical catalytic carbon dioxide conversion technology driven by renewable wind energy, solar energy and the like becomes a very promising technology due to the advantages of low energy consumption, environmental protection and the like. The electrochemical carbon dioxide conversion process is a multi-electron transfer process, involves a plurality of reaction intermediates, and is relatively complex; and thermodynamically requires a large amount of energy for carbon dioxide activation (C-O bond energy 803kJ mol)^-1) The kinetics are competitive with the hydrogen evolution reaction. Therefore, the development of an efficient and high-activity electrocatalyst is a key means for realizing electrochemical carbon dioxide catalytic conversion.

The phthalocyanine is a compound with a large conjugated system of 18 electrons, has the characteristics of low cost, easy acquisition, good chemical stability, clear active site and adjustable structure, has an easily-tailored molecular structure, and can be used for designing and assembling materials according to a target. And the phthalocyanine molecule has stronger coordination ability and can be coordinated with almost all metal elements to form a complex. Due to the unique characteristics, the phthalocyanine molecules and the derivatives thereof become an effective catalyst for carbon dioxide electroreduction. However, there are several problems as follows: (1) the catalyst has low conductivity, poor cycle stability and short service life; (2) the preparation process of the catalyst is complicated. Carbon materials are an excellent matrix or support material due to their excellent electrical conductivity. If the phthalocyanine and the derivative thereof are immobilized on the carbon matrix, the electrical conductivity of the phthalocyanine and the derivative thereof is expected to be improved, the service life of the phthalocyanine molecules and the derivative thereof is prolonged, and the overall catalytic performance of the phthalocyanine molecules and the derivative thereof is favorably improved. However, the existing method for preparing the composite catalyst has the problems of complex preparation process, long preparation time, high energy consumption and the like.

The microwave treatment is a new chemical treatment strategy, compared with the traditional method, the microwave method can greatly shorten the chemical synthesis time, has low energy consumption, reduces the waste in the chemical synthesis and conversion processes, and leads the treatment process to be more green. The phthalocyanine molecule and the derivative thereof and the carbon material are processed by a microwave method, so that the two materials can be uniformly and efficiently compounded in a very short time, and the ideal phthalocyanine molecule and the derivative thereof/carbon composite catalytic material can be prepared.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a method for quickly preparing phthalocyanine molecules and derivatives thereof/carbon composite catalysts by microwaves and application thereof. The prepared composite catalyst has the advantages of high catalytic activity, stable active substances, capability of efficiently inhibiting hydrogen evolution side reaction and the like when being used for carbon dioxide electroreduction reaction, and has great application potential in the field of catalysis.

In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a method for rapidly preparing phthalocyanine molecules and derivatives thereof/carbon composite catalysts by microwaves comprises the following steps:

step 1, adding 2-10mg of phthalocyanine molecules and derivatives thereof and 50-100mg of carbon source into a quartz microwave tube containing 5-10mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction under the protection of Ar gas, wherein the microwave reaction power is set to 800W, and the microwave reaction time is controlled to be 5-20 min;

and 2, after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3-5 times by using deionized water and absolute ethyl alcohol, then putting the mixture into a vacuum drying oven to be dried for 8-12h, controlling the drying temperature to be 60-80 ℃, and preparing the target material phthalocyanine molecule and derivative/carbon composite catalyst thereof, wherein the phthalocyanine molecule and derivative thereof are selected from one of phthalocyanine, cobalt phthalocyanine, iron phthalocyanine, nickel phthalocyanine or copper phthalocyanine, and the carbon source is selected from one of carbon nano tubes, graphite oxide or carbon black.

The phthalocyanine molecule and the derivative thereof/carbon composite catalyst prepared by the method are used as electrode materials in the carbon dioxide electroreduction reaction.

The invention has the beneficial effects that: a method for rapidly preparing phthalocyanine molecules and derivatives thereof/carbon composite catalysts by microwaves and application thereof are disclosed, wherein the preparation method comprises the following steps: (1) adding phthalocyanine molecules and derivatives thereof and a carbon source into a quartz microwave tube containing glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction under the protection of Ar gas; (2) and after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture by using deionized water and absolute ethyl alcohol, and then putting the mixture into a vacuum drying oven for drying to obtain the target material phthalocyanine molecule and the derivative thereof/carbon composite catalyst. The method has the advantages of simple process, short preparation time, low cost, environmental protection and universality. The phthalocyanine molecule and the derivative/carbon composite catalyst thereof prepared by the method have the advantages of high catalytic activity, stable active substances, capability of efficiently inhibiting hydrogen evolution side reaction and the like, and have great application potential in the field of catalysis.

Drawings

Fig. 1 is a scanning electron micrograph of the phthalocyanine/carbon nanotube composite catalyst prepared in example 1.

Fig. 2 is a high power transmission electron micrograph of the phthalocyanine/carbon nanotube composite catalyst prepared in example 2.

Fig. 3 is a graph of the carbon dioxide electroreduction polarization curve LSV of the phthalocyanine/carbon black composite catalyst prepared in example 5.

Fig. 4 is a graph of faradaic efficiency of carbon dioxide reduction of the cobalt phthalocyanine/carbon nanotube composite catalyst prepared in example 6.

Fig. 5 is a graph of faradaic efficiency of carbon dioxide reduction of the iron phthalocyanine/carbon nanotube composite catalyst prepared in example 7.

Fig. 6 is a carbon dioxide reduction stability test chart of the phthalocyanine/carbon nanotube composite catalyst prepared in example 8.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

Weighing 3mg of phthalocyanine and 100mg of carbon nano tube, placing the phthalocyanine and the carbon nano tube in a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube in a microwave reactor, and carrying out microwave reaction for 5min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 8 hours, and controlling the drying temperature to be 80 ℃ to obtain the phthalocyanine/carbon nano tube composite catalyst. As shown in fig. 1, it can be clearly seen from the scanning electron micrograph of the material that the prepared phthalocyanine/carbon nanotube composite catalyst maintains a one-dimensional morphology structure.

Example 2

Weighing 4mg of phthalocyanine and 100mg of carbon nano tubes, placing the phthalocyanine and the carbon nano tubes in a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube in a microwave reactor, and carrying out microwave reaction for 10min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 5 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 12 hours, and controlling the drying temperature to be 80 ℃ to prepare the phthalocyanine/carbon nano tube composite catalyst. As shown in fig. 2, it can be clearly observed from the high power transmission electron micrograph thereof that the prepared phthalocyanine/carbon nanotube composite catalyst is a structure of phthalocyanine coated carbon nanotubes, which proves the successful preparation of the composite catalyst.

Example 3

Weighing 10mg of nickel phthalocyanine and 100mg of graphite oxide, placing the nickel phthalocyanine and the graphite oxide into a quartz microwave tube containing 10mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction for 20min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 5 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 12 hours, and controlling the drying temperature to be 60 ℃ to obtain the nickel phthalocyanine/graphite oxide composite catalyst.

Example 4

Weighing 5mg of copper phthalocyanine and 100mg of carbon nano tubes, placing the copper phthalocyanine and the carbon nano tubes into a quartz microwave tube containing 8mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction for 5min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 8 hours, and controlling the drying temperature to be 60 ℃ to obtain the copper phthalocyanine/carbon nano tube composite catalyst.

Example 5

Weighing 4mg of phthalocyanine and 100mg of carbon black, placing the phthalocyanine and the carbon black into a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction for 10min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 12 hours, and controlling the drying temperature to be 80 ℃ to obtain the phthalocyanine/carbon black composite catalyst. Dissolving 5mg of prepared phthalocyanine/carbon black composite catalyst in 1mL of ethanol, adding 30 mu L of Nafion binder, performing ultrasonic treatment for 30min, and coating 100 mu L of the mixture on 1cm^-2Drying at room temperature on the glassy carbon electrode. Taking a glassy carbon electrode coated with phthalocyanine/carbon black composite catalyst as a working electrode, taking a silver/silver chloride electrode as a reference electrode and taking a platinum sheet as a counter electrode to form a three-electrode system, carrying out electrochemical carbon dioxide reduction performance test on the prepared phthalocyanine/carbon black composite catalyst, wherein the electrochemical workstation is Shanghai Chenghua CHI760E, the electrolytic cell is an H-type electrolytic cell, and the electrolyte is 0.1M KHCO₃And (3) solution. As can be seen from the LSV curve in FIG. 3, 1mA cm was reached^-2The current density is-0.75V.

Example 6

Weighing 4mg of cobalt phthalocyanine and 100mg of carbon nano tubes, placing the cobalt phthalocyanine and the carbon nano tubes into a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction for 10min under the protection of Ar gas and the power of 800W. After the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, and placing the mixtureDrying in a vacuum drying oven for 12h, and controlling the drying temperature at 80 ℃ to obtain the cobalt phthalocyanine/carbon nano tube composite catalyst. Dissolving 5mg of prepared cobalt phthalocyanine/carbon nano tube composite catalyst in 1mL of ethanol, adding 30 mu L of Nafion binder, performing ultrasonic treatment for 30min, and coating 100 mu L of the mixture on 1cm^-2Drying at room temperature on the glassy carbon electrode. Taking a glassy carbon electrode coated with a cobalt phthalocyanine/carbon nano tube composite catalyst as a working electrode, a silver/silver chloride electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and carrying out an electrochemical carbon dioxide reduction performance test on the prepared cobalt phthalocyanine/carbon nano tube composite catalyst, wherein the electrochemical workstation is Shanghai Chenghua CHI760E, the electrolytic cell is an H-type electrolytic cell, and the electrolyte is 0.1M KHCO₃And (3) solution. As can be seen from the faraday efficiency graph in fig. 4, the faraday efficiency of carbon monoxide is as high as 98% at-0.76V.

Example 7

Weighing 4mg of iron phthalocyanine and 100mg of carbon nano tubes, placing the iron phthalocyanine and the carbon nano tubes into a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube into a microwave reactor, and carrying out microwave reaction for 10min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 12 hours, and controlling the drying temperature to be 80 ℃ to obtain the iron phthalocyanine/carbon nano tube composite catalyst. Dissolving 5mg of prepared iron phthalocyanine/carbon nano tube composite catalyst in 1mL of ethanol, adding 30 mu L of Nafion binder, performing ultrasonic treatment for 30min, and coating 100 mu L of the mixture on 1cm^-2Drying at room temperature on the glassy carbon electrode. The prepared iron phthalocyanine/carbon nano tube composite catalyst is subjected to electrochemical carbon dioxide reduction performance test by taking a glassy carbon electrode coated with the iron phthalocyanine/carbon nano tube composite catalyst as a working electrode, a silver/silver chloride electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, wherein the electrochemical workstation is Shanghai Chenghua CHI760E, the electrolytic cell is an H-type electrolytic cell, and the electrolyte is 0.1M KHCO₃And (3) solution. As can be seen from the faraday efficiency graph in fig. 5, the faraday efficiency of carbon monoxide is as high as 86% at-0.66V.

Example 8

Weighing 4mg of phthalocyanine and 100mg of carbon nano tubes, placing the phthalocyanine and the carbon nano tubes in a quartz microwave tube containing 5mL of glycerol, placing the quartz microwave tube in a microwave reactor, and carrying out microwave reaction for 10min under the protection of Ar gas and the power of 800W. And after the microwave reaction is finished, taking out the mixture, repeatedly washing the mixture for 3 times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven to dry for 12 hours, and controlling the drying temperature to be 80 ℃ to prepare the phthalocyanine/carbon nano tube composite catalyst. Dissolving 5mg of prepared phthalocyanine/carbon nano tube composite catalyst in 1mL of ethanol, adding 30 mu L of Nafion binder, performing ultrasonic treatment for 30min, and coating 100 mu L of the mixture on 1cm^-2Drying at room temperature on the glassy carbon electrode. A glassy carbon electrode coated with phthalocyanine/carbon nano tube composite catalyst is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, a platinum sheet is used as a counter electrode to form a three-electrode system, the prepared phthalocyanine/carbon nano tube composite catalyst is subjected to electrochemical carbon dioxide reduction performance test, an electrochemical workstation is Shanghai Chenghua CHI760E, an electrolytic cell is an H-type electrolytic cell, and electrolyte is 0.1M KHCO₃And (3) solution. The phthalocyanine/carbon nano tube composite catalyst shows excellent performance, and as shown in figure 6, under the voltage of-0.76V, the current density reaches 6.5mA cm^-2The Faraday efficiency of the carbon monoxide is as high as 98 percent, and the carbon monoxide can stably run for 10 hours, which shows that the phthalocyanine/carbon nano tube composite catalyst is a stable carbon dioxide reduction electrocatalyst.