CN108232216A - A kind of ordered mesopore carbon loads ceria and binuclear phthalocyanine cobalt material and preparation method thereof altogether - Google Patents

Abstract

The invention discloses an ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material and a preparation method thereof. The preparation method comprises steps: (1) adding ordered mesoporous carbon material into deionized water, cerium nitrate solution and sodium hydroxide solution, mixing and stirring for 3-4 hours, filtering, washing, and drying at 100-120°C After 1 to 3 hours, roast to obtain a ceria-doped ordered mesoporous carbon material; (2) mix the ceria-doped ordered mesoporous carbon material, deionized water and cobalt dinuclear phthalocyanine, and ultrasonically After 4 to 6 hours, drying at 60 to 80° C. for 10 to 15 hours to obtain ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine materials. The preparation method of the invention has low cost, and the adopted raw materials have no obvious toxicity to the human body, and can minimize the influence on the mesoporous structure of the material during the synthesis process, so that the cerium dioxide can be doped on the ordered mesoporous carbon material.

Description

An ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material and its preparation method

technical field

The invention belongs to the field of mesoporous materials, and in particular relates to an ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material and a preparation method thereof.

Background technique

There are 17 rare earth elements in the periodic table, including 15 elements of the lanthanide series plus the closely related elements scandium and yttrium. Cerium (Ce) is the most abundant rare earth element, and it is widely used in solid oxide fuel cells, catalysts, ceramics, and ultraviolet absorption. A prominent feature of cerium is that it can form CeO _2-x oxides by releasing and capturing oxygen in an oxygen atmosphere, so that the valence state of cerium can be converted between Ce ³⁺ and Ce ⁴⁺ , resulting in the compound surface Vacancies are formed, called "oxygen-deficient sites". It is precisely because of these defect sites that ceria (CeO ₂ ) materials have excellent redox properties. And some studies have found that if it is combined with some carbon supports, better electrochemical performance can be obtained. As an important member of the carbon material family, ordered mesoporous carbon (OMC) has attracted much attention because of its high specific surface area, orderly pore structure, large pore volume, and good electrical and thermal conductivity. It has a good promotion effect on oxygen reduction activity in fuel cells.

Phthalocyanine is a macrocyclic compound with a hole in the ring that can accommodate metal elements such as iron, copper, cobalt, nickel or zinc. The metal atom replaces the two hydrogen atoms located in the center of the planar molecule, and due to the conjugation of multiple electrons in the molecule, the distribution of its electron density is quite uniform. The dinuclear cobalt phthalocyanine is a benzene ring shared by two phthalocyanine molecules, forming a highly conjugated planar structure. Phthalocyanines have become very important catalysts in many fields such as chemical engineering because of their unique high catalytic activity and selectivity.

Ordered mesoporous carbons are mostly synthesized by soft template method. However, the raw materials used in the soft template method are mainly formaldehyde and resorcinol, which have great harm to the human body, and it is easy to cause a large amount of loss during the synthesis process, and the operation process is cumbersome. Therefore, it has become a research hotspot in this field to seek a simple, non-toxic and inexpensive process for synthesizing mesoporous carbon carrier-supported ceria and binuclear cobalt phthalocyanine materials for fuel cells.

Contents of the invention

The purpose of the present invention is to provide a method for preparing ordered mesoporous carbon co-supported cerium oxide and dinuclear cobalt phthalocyanine material in view of the deficiencies in the prior art. The preparation method selects raw materials that are harmless to the human body, avoids the harm of the raw materials to the human body, and at the same time has a simple operation process, and can effectively reduce the loss of materials in the synthesis process so as to save costs.

The purpose of the present invention is also to provide an ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material prepared by the above preparation method. The ordered mesoporous carbon co-supports ceria and the binuclear cobalt phthalocyanine material is loaded with ceria, has high electrocatalytic activity, and has broad application prospects in the field of fuel cell cathode catalysts.

The purpose of the present invention is achieved through the following technical solutions.

A method for preparing ordered mesoporous carbon co-supported ceria and cobalt phthalocyanine materials, comprising the following steps:

(1) Add the ordered mesoporous carbon material to deionized water, cerium nitrate solution and sodium hydroxide solution, mix and stir for 3-4 hours, filter, wash, and dry at 100-120°C for 1-3 hours, Roasting to obtain a ceria-doped ordered mesoporous carbon material, denoted as y%CeO ₂ /OMC, wherein y% is the mass fraction of OMC occupied by cerium;

(2) Mix ceria-doped ordered mesoporous carbon material (y%CeO ₂ /OMC), deionized water and binuclear cobalt phthalocyanine, after ultrasonication for 4-6 hours, dry at 60-80°C for 10- After 15 hours, the ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material was obtained, denoted as Bi-CoPc/y%CeO ₂ /OMC.

Further, in step (1), the ordered mesoporous carbon material is prepared through the following steps:

(1-1) Mix polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water and hydrochloric acid solution, stir at 40-60°C for 4-5 hours, then add ethyl orthosilicate The ester continued to stir for 18-22 hours to obtain a white suspension;

(1-2) Add the white suspension into a polypropylene bottle, crystallize at 80-100°C for 48-60 hours, filter and wash, then dry at 60-90°C for 10-14 hours, and dry the dried solid at 400-100°C Calcined at 600°C for 5-7 hours to obtain a white solid;

(1-3) Add sucrose, deionized water and concentrated sulfuric acid to the white solid, mix evenly, dry at 80-100°C for 6-8 hours, then heat up to 150-160°C and carbonize for 5-6 hours to obtain a brown solid;

(1-4) Grind the brown solid thoroughly, add sucrose, deionized water and concentrated sulfuric acid again and mix evenly, dry again at 80-100°C for 6-8 hours, and heat up to 150-160°C for carbonization for 5-6 hours, Then calcined at 800-1000°C for 3-4 hours to obtain a black solid;

(1-5) Heat and reflux the black solid in a sodium hydroxide solution at 90-100°C for 6-8 hours to remove the template, and then dry the product at 90-100°C for 6-8 hours after washing to obtain ordered mesoporous carbon Material.

Further, in step (1-1), the mass ratio of the polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water, hydrochloric acid solution and tetraethyl orthosilicate is 3.5-4.0 :30:110～130:8.5.

Even more preferably, in step (1-1), the concentration of the hydrochloric acid solution is 1-2 mol/L.

Furthermore, in step (1-3), the mass ratio of the white solid, sucrose, deionized water and concentrated sulfuric acid is 1:1.25-1.5:4-5:0.14.

More preferably, in step (1-3), the concentration of the concentrated sulfuric acid is 16mol/L.

Furthermore, in step (1-4), the mass ratio of the brown solid, sucrose, deionized water and concentrated sulfuric acid is 0.3-0.5:0.8:5:0.09.

More preferably, in step (1-4), the concentration of the concentrated sulfuric acid is 16mol/L.

Furthermore, in step (1-5), the solvent of the sodium hydroxide solution is a mixed solvent of equal volumes of ethanol and water, and the concentration of the sodium hydroxide solution is 1-2 mol/L.

Further, in step (1), the mass ratio of the ordered mesoporous carbon material, deionized water, cerium nitrate solution and sodium hydroxide solution is 0.5:150:1.9-7.6:16-20.

Furthermore, in step (1), the concentration of the cerium nitrate solution is 0.046mol/L.

Furthermore, in step (1), the concentration of the sodium hydroxide solution is 1-2 mol/L.

Further, in step (1), the calcination is performed under nitrogen atmosphere at 300-450° C. for 2-4 hours.

Further, in step (2), the mass ratio of the ceria-doped ordered mesoporous carbon material, deionized water and dinuclear cobalt phthalocyanine is 0.5:90-110:0.25.

An ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material prepared by any one of the above preparation methods.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The ordered mesoporous carbon material used in the preparation method of the present invention is self-synthesized, and highly ordered mesoporous carbon materials can be synthesized;

(2) The present invention mainly adopts raw materials such as dinuclear cobalt phthalocyanine and cerium nitrate, which are cheap, convenient and easy to obtain, and have no obvious toxicity to the human body;

(3) The preparation process of the present invention is simple and clear, and will not cause the loss of raw materials in the intermediate preparation process;

(4) The loading method of the dinuclear cobalt phthalocyanine of the present invention is a direct ultrasonic impregnation method, which can avoid the loss of active components to the greatest extent;

(5) In the preparation process of the present invention, the calcination of the ordered mesoporous carbon material y%CeO ₂ /OMC doped with ceria is carried out at a non-high temperature, and the two Cerium oxide can be doped onto ordered mesoporous carbon materials, making the materials have higher electrocatalytic activity.

Description of drawings

Fig. 1 a is the transmission electron microscope (TEM) spectrogram of the ordered mesoporous carbon material OMC prepared in embodiment 1;

Figure 1b is a transmission electron microscope (TEM) spectrum of the ordered mesoporous carbon material 6%CeO ₂ /OMC prepared in Example 3;

Figure 1c is a transmission electron microscope (TEM) spectrum of ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material Bi-CoPc/3%CeO ₂ /OMC prepared in Example 5;

Figure 1d is a transmission electron microscope (TEM) spectrum of ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material Bi-CoPc/6%CeO ₂ /OMC prepared in Example 6;

Figure 1e is a transmission electron microscope (TEM) spectrum of ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material Bi-CoPc/12%CeO ₂ /OMC prepared in Example 7;

Fig. 2 is the small-angle X-ray diffraction pattern of the materials prepared in Example 1, Example 3 and Examples 5-7.

Detailed ways

The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments and accompanying drawings, but the protection scope and implementation methods of the present invention are not limited thereto.

Example 1

The preparation of the ordered mesoporous carbon material OMC specifically includes the following steps:

OMC was prepared by using polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (referred to as P123) as a template and tetraethyl orthosilicate (TEOS) as a silicon source.

Weigh 4g of P123, 30g of deionized water and 120g of hydrochloric acid (2mol/L) in a beaker and mix them in a beaker, stir for 4 hours under heating in an oil bath at 40°C to make them fully mixed, then add 8.5g of orthosilicic acid dropwise to the mixed solution Ethyl ester, keep the temperature constant and continue to stir for 20 hours; pour the resulting white emulsion into a polypropylene bottle, put it in an oven at 80°C for crystallization for 48 hours; filter the precipitate, wash it with deionized water, and place the solid in Dry in an oven at 60°C for 10 hours; finally put the dried solid into a box-type resistance furnace to raise the temperature to 400°C, and bake for 5 hours to obtain the SBA-15 template.

Weigh 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), mix evenly, so that the solid particles are completely dissolved to obtain a white viscous liquid, which is placed in an oven, Dry at 80°C for 6 hours first, then adjust the temperature to 150°C and continue drying and carbonization for 5 hours to obtain a brown solid.

Grind 0.3g of the brown solid into a powder, mix and dissolve it thoroughly with 0.8g of sucrose, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain a brown liquid, dry it at 80°C for 6 hours, and then adjust the temperature to 150°C Continue to dry and carbonize for 5 hours; put the obtained brown solid into a tube furnace after being ground, and roast at 800° C. for 3 hours in a nitrogen atmosphere; put the gained solid into 90 _{° C.} : 1) was refluxed for 6 hours to remove the silicon template; filtered, washed with water and ethanol in turn, and the resulting solid was placed in an oven at 90° C. and dried for 6 hours to obtain an ordered mesoporous carbon material OMC.

Example 2

The preparation of ceria-doped ordered mesoporous carbon material 3%CeO ₂ /OMC (3% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

OMC was prepared by using polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (referred to as P123) as a template and tetraethyl orthosilicate (TEOS) as a silicon source.

Mix 4g of P123, 30g of deionized water and 120g of hydrochloric acid (2mol/L) in a beaker, stir for 5 hours under heating in an oil bath at 50°C to make it fully mixed, and then add 8.5g of ethyl orthosilicate dropwise to the mixed solution ester, keep the temperature constant and continue to stir for 18 hours; pour the obtained white emulsion into a polypropylene bottle, put it in an oven at 90°C for crystallization for 50 hours; filter the precipitate, wash it with deionized water, and place the obtained solid in an oven Dry at 70°C for 11 hours; finally put the dried solid into a box-type resistance furnace to raise the temperature to 500°C, and bake it for 6 hours to obtain the SBA-15 template.

Weigh 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), mix evenly, so that the solid particles are completely dissolved to obtain a white viscous liquid, which is placed in an oven, Dry at 90°C for 7 hours first, then adjust the temperature to 160°C and continue drying and carbonization for 6 hours to obtain a brown solid.

Grind 0.32g of the brown solid into powder, mix and dissolve it thoroughly with 0.8g of sucrose, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain a brown liquid, dry it at 90°C for 7 hours, and then adjust the temperature to 160°C Continue to dry and carbonize for 6 hours; put the obtained brown solid into a tube furnace after being ground, and roast it at 900° C. for 4 hours in a nitrogen atmosphere; put the gained solid into 90 _{° C.} : 1) was refluxed for 7 hours to remove the silicon template; filtered, washed with water and ethanol in turn, and the resulting solid was placed in an oven and dried at 90° C. for 7 hours to obtain the ordered mesoporous carbon material OMC.

2g of cerium nitrate hexahydrate (Ce(NO ₃ ) ₃ 6H ₂ O) solid was prepared into 100mL of cerium nitrate solution; weighed 1.9g of cerium nitrate solution and 0.5g of OMC and mixed evenly, then added 150mL of deionized water and 18mL of 2mol/ L NaOH solution, stirred at room temperature for 3 hours, washed, then dried in a blast oven at 100°C for 1 hour, and finally put the obtained black solid in a box-type resistance furnace, and roasted at 300°C for 2 hours under a nitrogen atmosphere to obtain Cerium-doped ordered mesoporous carbon material 3%CeO ₂ /OMC.

Example 3

The preparation of ceria-doped ordered mesoporous carbon material 6%CeO ₂ /OMC (6% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

OMC was prepared by using polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (referred to as P123) as a template and tetraethyl orthosilicate (TEOS) as a silicon source.

Mix 4g of P123, 30g of deionized water and 120g of hydrochloric acid (1mol/L) in a beaker, stir for 5 hours under heating in an oil bath at 60°C to make it fully mixed, and then add 8.5g of ethyl orthosilicate dropwise to the mixed solution ester, keep the temperature constant and continue to stir for 22 hours; pour the obtained white emulsion into a polypropylene bottle, put it in an oven at 100°C for crystallization for 54 hours; filter the precipitate, wash it with deionized water, and place the obtained solid in an oven Dry at 80°C for 12 hours; finally put the dried solid into a box-type resistance furnace to raise the temperature to 600°C, and bake it for 7 hours to obtain the SBA-15 template.

Weigh 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), mix evenly, so that the solid particles are completely dissolved to obtain a white viscous liquid, which is placed in an oven, Dry at 100°C for 8 hours first, then adjust the temperature to 150°C and continue drying and carbonization for 5 hours to obtain a brown solid.

Grind 0.35g of the brown solid into powder, mix and dissolve it thoroughly with 0.8g of sucrose, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain a brown liquid, dry it at 100°C for 8 hours, and then adjust the temperature to 150°C Continue to dry and carbonize for 5 hours; Put the obtained brown solid into a tube furnace after being ground, and roast it at 1000° C. for 4 hours in a nitrogen atmosphere; Put the 1mol/L NaOH aqueous ethanol solution (V _ethanol : V _water = 1:1) for 8 hours to remove the silicon template; filtered, washed with water and ethanol in sequence, and the resulting solid was dried in an oven at 90°C for 8 hours to obtain the ordered mesoporous carbon material OMC.

2g of cerium nitrate hexahydrate (Ce(NO ₃ ) ₃ 6H ₂ O) solid was prepared into 100mL of cerium nitrate solution; weighed 3.8g of cerium nitrate solution and 0.5g of OMC and mixed evenly, then added 150mL of deionized water and 18mL of 1mol/ L NaOH solution, stirred at room temperature for 4 hours, washed, then dried in a blast oven at 110°C for 2 hours, and finally put the obtained black solid in a box-type resistance furnace, and roasted at 450°C for 4 hours under a nitrogen atmosphere to obtain ceria Doped ordered mesoporous carbon material 6%CeO ₂ /OMC.

Example 4

The preparation of ceria-doped ordered mesoporous carbon material 12%CeO ₂ /OMC (12% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

OMC was prepared by using polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (referred to as P123) as a template and tetraethyl orthosilicate (TEOS) as a silicon source.

Mix 4g of P123, 30g of deionized water and 120g of hydrochloric acid (1mol/L) in a beaker, stir for 4 hours under heating in an oil bath at 40°C to make it fully mixed, and then add 8.5g of ethyl orthosilicate dropwise to the mixed solution , keep the temperature constant and continue to stir for 20 hours; pour the obtained white emulsion into a polypropylene bottle, put it in an oven at 100°C for crystallization for 58 hours; filter the precipitate, wash it with deionized water, and place the obtained solid in an oven Dry at 90°C for 13 hours; finally put the dried solid into a box-type resistance furnace to raise the temperature to 500°C, and bake for 5 hours to obtain the SBA-15 template.

Weigh 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), mix evenly, so that the solid particles are completely dissolved to obtain a white viscous liquid, which is placed in an oven, Dry at 80°C for 6 hours first, then adjust the temperature to 160°C and continue drying and carbonization for 6 hours to obtain a brown solid.

Grind 0.34g of the brown solid into powder, mix and dissolve it thoroughly with 0.8g of sucrose, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain a brown liquid, dry it at 80°C for 6 hours, and then adjust the temperature to 160°C Continue to dry and carbonize for 6 hours; Put the obtained brown solid into a tube furnace after being ground, and roast it at 800° C. for 3 hours in a nitrogen atmosphere; Put the 1mol/L NaOH aqueous ethanol solution (V _ethanol : V _water = 1:1) for 6 hours to remove the silicon template; filtered, washed with water and ethanol in sequence, and the resulting solid was dried in an oven at 100°C for 6 hours to obtain the ordered mesoporous carbon material OMC.

2g of cerium nitrate hexahydrate (Ce(NO ₃ ) ₃ 6H ₂ O) solid was prepared into 100mL of cerium nitrate solution; weighed 7.6g of cerium nitrate solution and 0.5g of OMC and mixed evenly, then added 150mL of deionized water and 18mL of 2mol/ L NaOH solution, stirred at room temperature for 3 hours, washed, then dried in a blast oven at 120°C for 3 hours, and finally put the obtained black solid in a box-type resistance furnace, and roasted at 400°C for 3 hours under a nitrogen atmosphere to obtain ceria Doped ordered mesoporous carbon material 12%CeO ₂ /OMC.

Example 5

The preparation of ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/3%CeO ₂ /OMC (3% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

Weigh 0.5g of 3% CeO ₂ /OMC and 0.25g of dinuclear cobalt phthalocyanine in Example 2 and dissolve them in 100mL of deionized water. After ultrasonicating the mixed solution for 4 hours, the solution is directly placed in an oven at 60°C and dried for 15 hours to obtain Ordered mesoporous carbon co-supported ceria and cobalt phthalocyanine material Bi-CoPc/3%CeO ₂ /OMC.

Example 6

The preparation of ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/6%CeO ₂ /OMC (6% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

Weigh 0.5g of 6% CeO ₂ /OMC and 0.25g of dinuclear cobalt phthalocyanine in Example 3 and dissolve them in 100mL of deionized water. After ultrasonicating the mixed solution for 5 hours, the solution is directly placed in an oven and dried at 70°C for 12 hours to obtain Ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/6%CeO ₂ /OMC.

Example 7

The preparation of ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/12%CeO ₂ /OMC (12% is the mass fraction of OMC occupied by cerium element), specifically includes the following steps:

Weigh 0.5g of 12% CeO ₂ /OMC and 0.25g of dinuclear cobalt phthalocyanine in Example 4 and dissolve them in 100mL of deionized water. After ultrasonicating the mixed solution for 6 hours, the solution is directly placed in an oven and dried at 80°C for 10 hours to obtain Ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/12%CeO ₂ /OMC.

Microscopic morphology test and analysis

Carry out transmission electron microscope (TEM) characterization to the material obtained in embodiment 1, embodiment 3 and embodiment 5～7: take appropriate amount of product and dissolve in ethanol solvent, sonicate for 2 hours, the solution after sonication is dropped on copper net, adopts The morphology of the materials was characterized by a transmission electron microscope (JEM-2100F, JEOL Ltd.). The TEM images of the materials obtained in Example 1, Example 3 and Examples 5-7 are shown in Figures 1a-1e.

From Figures 1a to 1e, it can be seen that the carrier OMC has a well-ordered hexagonal pore structure, indicating that although NaOH solution was used to remove the silica template during the synthesis process, its ordered pore structure has not been changed. And from the TEM images of 6%CeO ₂ /OMC, Bi-CoPc/3%CeO ₂ /OMC, Bi-CoPc/6%CeO ₂ /OMC and Bi-CoPc/12%CeO ₂ /OMC (Figure 1b, Figure 1c , Figure 1d and Figure 1e), it can be clearly seen that there are dark black spots gathered on the surface of the catalyst, indicating that ceria has been successfully loaded on the OMC. In addition, it can be seen from Figure 1c to Figure 1e that there are layered substances on the edge of the material, which is because Bi-CoPc molecules are relatively large and wrapped around the carrier OMC, which also proves that Bi-CoPc has been loaded on the catalyst; However, it can be seen from Figure 1e that the pore structure of the carrier is no longer obvious, because the doping amount of cerium nitrate is too large and the carrier is completely wrapped.

Small-angle X-ray diffraction analysis was carried out on the materials obtained in Example 1, Example 3, and Examples 5-7, and the analysis was performed using a Smartlab X-ray diffractometer from Rigaku Corporation. The small-angle X-ray diffraction patterns of the materials obtained in Example 1, Example 3, and Examples 5-7 are shown in FIG. 2 .

As can be seen from Figure 2, the OMC carrier (curve a) has a strong and obvious diffraction peak, and the calcined 6%CeO ₂ /OMC (curve b), Bi-CoPc/3%CeO ₂ /OMC (curve c ) and Bi-CoPc/6%CeO ₂ /OMC (curve d) catalysts also have significantly reduced diffraction peaks, indicating that the mesoporous structure has become less obvious after heating and with the increase of doping amount, but it still shows that the catalyst There are still exposed mesoporous structures on the surface. However, the intensity of the diffraction peak of Bi-CoPc/12%CeO ₂ /OMC (curve e) becomes particularly weak, which is because the ordered mesoporous carbon has been completely encapsulated due to the excessive doping amount of cerium nitrate, which is different from that of this catalyst The transmission electron microscope images are also consistent.

The Ce and Co elements in the materials obtained in Example 3 and Examples 5-7 were subjected to elemental analysis, and the instrument used was an atomic absorption spectrophotometer (Hitachi Z-2000 type). Table 1 shows the analysis results of Co and Ce elements in the materials obtained in Example 3 and Examples 5-7.

Co and Ce elemental analysis results in the material obtained in Table 1 Example 3 and Examples 5-7

As can be seen from Table 1, in the material obtained in Example 3 and Examples 5 to 7, the content of cobalt is substantially constant in the range of 1.0 to 1.1%. However, the actual measurement of cerium showed a doubling trend with the increase of the amount of cerium nitrate added, indicating that there was basically no loss of cerium nitrate during the synthesis process.

The above embodiments are all preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and any other changes, modifications, substitutions, combinations and modifications made without departing from the spirit and principles of the present invention Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

1. A preparation method of ordered mesoporous carbon co-supported ceria and cobalt phthalocyanine material, is characterized in that, comprises the steps: (1) Add the ordered mesoporous carbon material to deionized water, cerium nitrate solution and sodium hydroxide solution, mix and stir for 3-4 hours, filter, wash, and dry at 100-120°C for 1-3 hours, Roasting to obtain a ceria-doped ordered mesoporous carbon material; (2) Mix the ordered mesoporous carbon material doped with ceria, deionized water and dinuclear cobalt phthalocyanine, after ultrasonication for 4-6 hours, dry at 60-80°C for 10-15 hours to obtain ordered mesoporous Carbon co-supported ceria and binuclear cobalt phthalocyanine materials. 2. preparation method according to claim 1, is characterized in that, in step (1), described ordered mesoporous carbon material is made through the following steps: (1-1) Mix polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water and hydrochloric acid solution, stir at 40-60°C for 4-5 hours, then add ethyl orthosilicate The ester continued to stir for 18-22 hours to obtain a white suspension; (1-2) Add the white suspension into a polypropylene bottle, crystallize at 80-100°C for 48-60 hours, filter and wash, then dry at 60-90°C for 10-14 hours, and dry the dried solid at 400-100°C Calcined at 600°C for 5-7 hours to obtain a white solid; (1-3) Add sucrose, deionized water and concentrated sulfuric acid to the white solid, mix evenly, dry at 80-100°C for 6-8 hours, then heat up to 150-160°C and carbonize for 5-6 hours to obtain a brown solid; (1-4) Grind the brown solid thoroughly, add sucrose, deionized water and concentrated sulfuric acid again and mix evenly, dry again at 80-100°C for 6-8 hours, and heat up to 150-160°C for carbonization for 5-6 hours, Then calcined at 800-1000°C for 3-4 hours to obtain a black solid; (1-5) Heat and reflux the black solid in a sodium hydroxide solution at 90-100°C for 6-8 hours to remove the template, and then dry the product at 90-100°C for 6-8 hours after washing to obtain ordered mesoporous carbon Material. 3. preparation method according to claim 2, is characterized in that, in step (1-1), described polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water, hydrochloric acid solution The mass ratio to ethyl orthosilicate is 3.5-4.0:30:110-130:8.5; the concentration of the hydrochloric acid solution is 1-2 mol/L. 4. the preparation method according to claim 2 is characterized in that, in step (1-3), the mass ratio of described white solid, sucrose, deionized water and concentrated sulfuric acid is 1: 1.25～1.5: 4～5 : 0.14; the concentration of the concentrated sulfuric acid is 16mol/L. 5. The preparation method according to claim 2, characterized in that, in step (1-4), the mass ratio of the brown solid, sucrose, deionized water and concentrated sulfuric acid is 0.3～0.5:0.8:5:0.09 ; The concentration of the concentrated sulfuric acid is 16mol/L. 6. preparation method according to claim 2, is characterized in that, in step (1-5), the solvent of described sodium hydroxide solution is the mixed solvent of ethanol and water equivolume, and the concentration of sodium hydroxide solution is 1 ~2mol/L. 7. The preparation method according to claim 1, characterized in that, in step (1), the mass ratio of the ordered mesoporous carbon material, deionized water, cerium nitrate solution and sodium hydroxide solution is 0.5: 150 : 1.9～7.6: 16～20; the concentration of the cerium nitrate solution is 0.046mol/L; the concentration of the sodium hydroxide solution is 1～2mol/L. 8 . The preparation method according to claim 1 , characterized in that, in step (1), the calcination is under a nitrogen atmosphere at 300-450° C. for 2-4 hours. 9. preparation method according to claim 1, is characterized in that, in step (2), the mass ratio of the ordered mesoporous carbon material, deionized water and binuclear phthalocyanine cobalt of described ceria doping is 0.5 :90～110:0.25. 10. An ordered mesoporous carbon co-supported ceria and dinuclear cobalt phthalocyanine material prepared by the preparation method according to any one of claims 1-9.