CN108232216B - Ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material and preparation method thereof - Google Patents
Ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material and a preparation method thereof. The preparation method comprises the following steps: (1) adding an ordered mesoporous carbon material into deionized water, a cerium nitrate solution and a sodium hydroxide solution, mixing, stirring for 3-4 hours, filtering, washing, drying at 100-120 ℃ for 1-3 hours, and roasting to obtain a cerium dioxide doped ordered mesoporous carbon material; (2) mixing the cerium dioxide-doped ordered mesoporous carbon material, deionized water and binuclear cobalt phthalocyanine, performing ultrasonic treatment for 4-6 hours, and drying at 60-80 ℃ for 10-15 hours to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material. The preparation method has low cost, the adopted raw materials have no obvious toxicity to human bodies, and the influence on the mesoporous structure of the material can be reduced to the greatest extent in the synthesis process, so that the cerium dioxide can be doped on the ordered mesoporous carbon material.
Description
Technical Field
The invention belongs to the field of mesoporous materials, and particularly relates to an ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material and a preparation method thereof.
Background
The rare earth elements in the periodic table of the elements are 17 in total, including the 15 elements of the lanthanide series plus the closely related elements scandium and yttrium. Cerium (Ce) is the most abundant rare earth element, and in the fields of solid oxide fuel cells, catalysts, ceramic industry, ultraviolet absorption and the like,all have wide application. The cerium element has the following outstanding characteristics: capable of forming CeO by releasing and capturing oxygen under oxygen atmosphere2-xOxide of cerium in the valence state of Ce3+And Ce4+Thereby causing vacancies, referred to as "oxygen defect sites," to form at the compound surface. It is due to these defect sites that the cerium oxide (CeO)2) The material has excellent oxidation-reduction performance. And some researches find that better electrochemical performance can be obtained if the carbon-based composite material is compounded with some carbon carriers. Ordered Mesoporous Carbon (OMC), an important member of a family of carbon materials, attracts attention due to its advantages of high specific surface area, Ordered pore structure, large pore volume, good electrical and thermal conductivity, etc., and has a good promoting effect on oxygen reduction activity when applied to fuel cells.
The phthalocyanine is a macrocyclic compound, and a cavity is formed in the ring and can accommodate metal elements such as iron, copper, cobalt, nickel or zinc. The metal atom replaces 2 hydrogen atoms located in the center of the planar molecule, and the electron density distribution is fairly uniform due to the conjugation of multiple electrons in the molecule. The binuclear cobalt phthalocyanine is a highly conjugated planar structure formed by two phthalocyanine molecules sharing a benzene ring. The phthalocyanine substance is an important catalyst in chemical engineering and other fields due to the unique high catalytic activity and selectivity.
At present, the ordered mesoporous carbon is mostly synthesized by adopting a soft template method. However, the raw materials used in the soft template method are mainly formaldehyde, resorcinol and other substances, which are harmful to human body, and a large amount of loss is easily caused in the synthesis process, and the operation process is complicated. Therefore, the research focus in the field is to find a process for synthesizing the mesoporous carbon carrier supported cerium dioxide and binuclear cobalt phthalocyanine material with simple operation, no toxicity and low cost to apply to the fuel cell.
Disclosure of Invention
The invention aims to provide a preparation method of an ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material aiming at the defects of the prior art. The preparation method adopts raw materials harmless to human body, avoids the damage of the raw materials to human body, has simple operation process, and can effectively reduce the loss of materials in the synthesis process so as to save cost.
The invention also aims to provide the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material prepared by the preparation method. The ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material is loaded with cerium dioxide, has high electrocatalytic activity, and has wide application prospect in the field of fuel cell cathode catalysts.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material comprises the following steps:
(1) adding the ordered mesoporous carbon material into deionized water, a cerium nitrate solution and a sodium hydroxide solution, mixing, stirring for 3-4 hours, filtering, washing, drying at 100-120 ℃ for 1-3 hours, and roasting to obtain a cerium dioxide doped ordered mesoporous carbon material, which is recorded as y% CeO2OMC, wherein y% is the mass fraction of cerium element in the OMC;
(2) cerium dioxide doped ordered mesoporous carbon material (y% CeO)2OMC), deionized water and binuclear cobalt phthalocyanine are mixed, subjected to ultrasonic treatment for 4-6 hours, and dried at 60-80 ℃ for 10-15 hours to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material, which is recorded as Bi-CoPc/y% CeO2/OMC。
Further, in the step (1), the ordered mesoporous carbon material is prepared by the following steps:
(1-1) mixing a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water and a hydrochloric acid solution, stirring for 4-5 hours at 40-60 ℃, then adding tetraethoxysilane, and continuously stirring for 18-22 hours to obtain a white suspension;
(1-2) adding the white suspension into a polypropylene bottle, crystallizing at 80-100 ℃ for 48-60 hours, filtering, washing, drying at 60-90 ℃ for 10-14 hours, and roasting the dried solid at 400-600 ℃ for 5-7 hours to obtain a white solid;
(1-3) adding sucrose, deionized water and concentrated sulfuric acid into the white solid, uniformly mixing, drying at 80-100 ℃ for 6-8 hours, and then heating to 150-160 ℃ for carbonization for 5-6 hours to obtain brown solid;
(1-4) fully grinding the brown solid, adding sucrose, deionized water and concentrated sulfuric acid again, uniformly mixing, drying at 80-100 ℃ for 6-8 hours, heating to 150-160 ℃ for carbonization for 5-6 hours, and roasting at 800-1000 ℃ for 3-4 hours to obtain a black solid;
(1-5) heating and refluxing the black solid in a sodium hydroxide solution at the temperature of 90-100 ℃ for 6-8 hours to remove the template, washing the product, and drying at the temperature of 90-100 ℃ for 6-8 hours to obtain the ordered mesoporous carbon material.
Furthermore, in the step (1-1), the mass ratio of the polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, the deionized water, the hydrochloric acid solution and the tetraethoxysilane is 3.5-4.0: 30: 110-130: 8.5.
More preferably, in the step (1-1), the concentration of the hydrochloric acid solution is 1-2 mol/L.
Furthermore, in the step (1-3), the mass ratio of the white solid, the sucrose, the deionized water and the concentrated sulfuric acid is 1: 1.25-1.5: 4-5: 0.14.
Still more preferably, in the step (1-3), the concentration of the concentrated sulfuric acid is 16 mol/L.
Furthermore, in the step (1-4), the mass ratio of the brown solid, the sucrose, the deionized water and the concentrated sulfuric acid is 0.3-0.5: 0.8:5: 0.09.
Still more preferably, in the step (1-4), the concentration of the concentrated sulfuric acid is 16 mol/L.
Furthermore, in the step (1-5), the solvent of the sodium hydroxide solution is a mixed solvent of ethanol and water with equal volume, and the concentration of the sodium hydroxide solution is 1-2 mol/L.
Further, in the step (1), the mass ratio of the ordered mesoporous carbon material, the deionized water, the cerium nitrate solution and the sodium hydroxide solution is 0.5:150: 1.9-7.6: 16-20.
Further, in the step (1), the concentration of the cerium nitrate solution is 0.046 mol/L.
Furthermore, in the step (1), the concentration of the sodium hydroxide solution is 1-2 mol/L.
Further, in the step (1), the roasting is carried out for 2-4 hours at 300-450 ℃ in a nitrogen atmosphere.
Further, in the step (2), the mass ratio of the cerium dioxide doped ordered mesoporous carbon material, the deionized water and the binuclear cobalt phthalocyanine is 0.5: 90-110: 0.25.
The ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material prepared by the preparation method is provided.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the ordered mesoporous carbon material adopted by the preparation method is self-synthesized, and the highly ordered mesoporous carbon material can be synthesized;
(2) the invention mainly adopts the raw materials of binuclear cobalt phthalocyanine, cerium nitrate and the like, has low price, is convenient and easy to obtain, and has no obvious toxicity to human bodies;
(3) the preparation process is simple and clear, and raw material loss in the intermediate preparation process can not be caused;
(4) the method for loading the binuclear cobalt phthalocyanine is a direct ultrasonic impregnation method, so that the loss of active components can be avoided to the greatest extent;
(5) in the preparation process of the invention, cerium dioxide doped ordered mesoporous carbon material y% CeO2The roasting of the/OMC is carried out at non-high temperature, and under the condition of having minimum influence on the mesoporous structure of the material, the cerium dioxide can be doped on the ordered mesoporous carbon material, so that the material has higher electrocatalytic activity.
Drawings
FIG. 1a is a Transmission Electron Microscope (TEM) spectrum of an ordered mesoporous carbon material OMC prepared in example 1;
FIG. 1b is a 6% CeO ceria doped ordered mesoporous carbon material prepared in example 32Transmission Electron Microscope (TEM) spectra of/OMC;
FIG. 1c is a drawing showing a preparation process of example 5Prepared ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/3% CeO2Transmission Electron Microscope (TEM) spectra of/OMC;
FIG. 1d shows the ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/6% CeO prepared in example 62Transmission Electron Microscope (TEM) spectra of/OMC;
FIG. 1e shows the ordered mesoporous carbon co-supported ceria and binuclear cobalt phthalocyanine material Bi-CoPc/12% CeO prepared in example 72Transmission Electron Microscope (TEM) spectra of/OMC;
FIG. 2 is a small angle X-ray diffraction pattern for the materials prepared in examples 1, 3 and 5-7.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, but the scope and implementation of the present invention are not limited thereto.
Example 1
The preparation method of the ordered mesoporous carbon material OMC specifically comprises the following steps:
the OMC is prepared by taking a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (P123 for short) as a template agent and Tetraethoxysilane (TEOS) as a silicon source.
Weighing 4g P123 g, 30g of deionized water and 120g of hydrochloric acid (2mol/L) to mix in a beaker, stirring for 4 hours under the heating of 40 ℃ oil bath to fully and uniformly mix, then dropwise adding 8.5g of tetraethoxysilane into the mixed solution, and continuously stirring for 20 hours while keeping the temperature unchanged; pouring the obtained white emulsion into a polypropylene bottle, and putting the bottle into an oven at 80 ℃ for crystallization for 48 hours; filtering the precipitate, taking out, washing with deionized water, and drying the obtained solid in an oven at 60 ℃ for 10 hours; and finally, putting the dried solid into a box-type resistance furnace, heating to 400 ℃, and roasting for 5 hours to obtain the SBA-15 template.
Weighing 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), uniformly mixing to completely dissolve solid particles to obtain white viscous liquid, placing the obtained liquid in an oven, drying at 80 ℃ for 6 hours, then adjusting the temperature to 150 ℃, and continuously drying and carbonizing for 5 hours to obtain brown solid.
Grinding 0.3g of brown solid into powder, fully mixing and dissolving the powder with 0.8g of cane sugar, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain brown liquid, drying the brown liquid at 80 ℃ for 6 hours, then adjusting the temperature to 150 ℃, and continuing drying and carbonizing the brown liquid for 5 hours; grinding the obtained brown solid, putting the ground brown solid into a tube furnace, and roasting the brown solid for 3 hours at 800 ℃ in a nitrogen atmosphere; the solid obtained is placed in a 2mol/L NaOH aqueous ethanol solution (V) at 90 DEG CEthanol∶VWater (W)1: 1) under reflux for 6 hours to remove the silicon template; filtering, washing with water and ethanol in sequence, and drying the obtained solid in an oven at 90 ℃ for 6 hours to obtain the ordered mesoporous carbon material OMC.
Example 2
Cerium dioxide doped ordered mesoporous carbon material 3% CeO2The preparation of OMC (3% is the mass fraction of cerium element in OMC), which comprises the following steps:
the OMC is prepared by taking a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (P123 for short) as a template agent and Tetraethoxysilane (TEOS) as a silicon source.
Mixing 4g P123, 30g of deionized water and 120g of hydrochloric acid (2mol/L) in a beaker, stirring for 5 hours under the heating of 50 ℃ oil bath to ensure that the materials are fully and uniformly mixed, then dropwise adding 8.5g of tetraethoxysilane into the mixed solution, and continuously stirring for 18 hours while keeping the temperature unchanged; pouring the obtained white emulsion into a polypropylene bottle, and putting the bottle into a drying oven at the temperature of 90 ℃ for crystallization for 50 hours; filtering the precipitate, taking out, washing with deionized water, and drying the obtained solid in an oven at 70 ℃ for 11 hours; and finally, putting the dried solid into a box-type resistance furnace, heating to 500 ℃, and roasting for 6 hours to obtain the SBA-15 template.
Weighing 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), uniformly mixing to completely dissolve solid particles to obtain white viscous liquid, placing the obtained liquid in an oven, drying at 90 ℃ for 7 hours, adjusting the temperature to 160 ℃, and continuously drying and carbonizing for 6 hours to obtain brown solid.
0.32g of brown solid was ground into powder and thoroughly mixed with 0.8g of sucrose, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L)Mixing and dissolving to obtain brown liquid, drying at 90 deg.C for 7 hr, adjusting temperature to 160 deg.C, and further drying and carbonizing for 6 hr; grinding the obtained brown solid, putting the ground brown solid into a tube furnace, and roasting the brown solid for 4 hours at 900 ℃ in a nitrogen atmosphere; the solid obtained is placed in a 2mol/L NaOH aqueous ethanol solution (V) at 90 DEG CEthanol∶VWater (W)1: 1) for 7 hours to remove the silicon template; filtering, washing with water and ethanol in sequence, and drying the obtained solid in an oven at 90 ℃ for 7 hours to obtain the ordered mesoporous carbon material OMC.
2g of cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) preparing a solid into 100mL of a cerium nitrate solution; weighing 1.9g of cerium nitrate solution and 0.5g of OMC, uniformly mixing, adding 150mL of deionized water and 18mL of 2mol/L NaOH solution, stirring at normal temperature for 3 hours, washing, placing in a forced air oven for drying at 100 ℃ for 1 hour, finally placing the obtained black solid in a box-type resistance furnace, and roasting at 300 ℃ for 2 hours under the nitrogen atmosphere to obtain the cerium dioxide doped ordered mesoporous carbon material 3% CeO2/OMC。
Example 3
Cerium dioxide doped ordered mesoporous carbon material 6% CeO2The preparation of OMC (6 percent is the mass fraction of cerium element in the OMC) comprises the following steps:
the OMC is prepared by taking a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (P123 for short) as a template agent and Tetraethoxysilane (TEOS) as a silicon source.
Mixing 4g P123, 30g of deionized water and 120g of hydrochloric acid (1mol/L) in a beaker, stirring for 5 hours under the heating of 60 ℃ oil bath to ensure that the mixture is fully and uniformly mixed, then dropwise adding 8.5g of tetraethoxysilane into the mixed solution, and continuously stirring for 22 hours while keeping the temperature unchanged; pouring the obtained white emulsion into a polypropylene bottle, and putting the bottle into a drying oven at 100 ℃ for crystallization for 54 hours; filtering the precipitate, taking out, washing with deionized water, and drying the obtained solid in an oven at 80 ℃ for 12 hours; and finally, putting the dried solid into a box-type resistance furnace, heating to 600 ℃, and roasting for 7 hours to obtain the SBA-15 template.
Weighing 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), uniformly mixing to completely dissolve solid particles to obtain white viscous liquid, placing the obtained liquid in an oven, drying at 100 ℃ for 8 hours, then adjusting the temperature to 150 ℃, and continuing to dry and carbonize for 5 hours to obtain brown solid.
Grinding 0.35g of brown solid into powder, fully mixing and dissolving the powder with 0.8g of cane sugar, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain brown liquid, drying the brown liquid at 100 ℃ for 8 hours, and then adjusting the temperature to 150 ℃ to continue drying and carbonizing the brown liquid for 5 hours; grinding the obtained brown solid, putting the ground brown solid into a tube furnace, and roasting the brown solid for 4 hours at 1000 ℃ in a nitrogen atmosphere; the obtained solid was placed in a 1mol/L NaOH ethanol aqueous solution (V) at 90 deg.CEthanol∶VWater (W)1: 1) for 8 hours to remove the silicon template; filtering, washing with water and ethanol in sequence, and drying the obtained solid in an oven at 90 ℃ for 8 hours to obtain the ordered mesoporous carbon material OMC.
2g of cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) preparing a solid into 100mL of a cerium nitrate solution; weighing 3.8g of cerium nitrate solution and 0.5g of OMC, uniformly mixing, adding 150mL of deionized water and 18mL of 1mol/L NaOH solution, stirring at normal temperature for 4 hours, washing, drying at 110 ℃ in a forced air oven for 2 hours, finally placing the obtained black solid in a box-type resistance furnace, roasting at 450 ℃ for 4 hours under the nitrogen atmosphere to obtain the cerium dioxide doped ordered mesoporous carbon material 6% CeO2/OMC。
Example 4
Cerium dioxide doped ordered mesoporous carbon material 12% CeO2The preparation of OMC (12% is the mass fraction of cerium element in OMC), which comprises the following steps:
the OMC is prepared by taking a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (P123 for short) as a template agent and Tetraethoxysilane (TEOS) as a silicon source.
Mixing 4g P123, 30g of deionized water and 120g of hydrochloric acid (1mol/L) in a beaker, stirring for 4 hours under the heating of 40 ℃ oil bath to fully and uniformly mix, then dropwise adding 8.5g of tetraethoxysilane into the mixed solution, and continuously stirring for 20 hours while keeping the temperature unchanged; pouring the obtained white emulsion into a polypropylene bottle, and putting the bottle into a drying oven at 100 ℃ for crystallization for 58 hours; filtering the precipitate, taking out, washing with deionized water, and drying the obtained solid in an oven at 90 ℃ for 13 hours; and finally, putting the dried solid into a box-type resistance furnace, heating to 500 ℃, and roasting for 5 hours to obtain the SBA-15 template.
Weighing 1g of SBA-15, 1.25g of sucrose, 5g of deionized water and 0.14g of concentrated sulfuric acid (16mol/L), uniformly mixing to completely dissolve solid particles to obtain white viscous liquid, placing the obtained liquid in an oven, drying at 80 ℃ for 6 hours, adjusting the temperature to 160 ℃, and continuously drying and carbonizing for 6 hours to obtain brown solid.
Grinding 0.34g of brown solid into powder, fully mixing and dissolving the powder with 0.8g of cane sugar, 5g of deionized water and 0.09g of concentrated sulfuric acid (16mol/L) to obtain brown liquid, drying the brown liquid at 80 ℃ for 6 hours, then adjusting the temperature to 160 ℃, and continuing drying and carbonizing the brown liquid for 6 hours; grinding the obtained brown solid, putting the ground brown solid into a tube furnace, and roasting the brown solid for 3 hours at 800 ℃ in a nitrogen atmosphere; the obtained solid was placed in a 1mol/L aqueous NaOH solution (V) at 100 deg.CEthanol∶VWater (W)1: 1) under reflux for 6 hours to remove the silicon template; filtering, washing with water and ethanol in sequence, and drying the obtained solid in an oven at 100 ℃ for 6 hours to obtain the ordered mesoporous carbon material OMC.
2g of cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) preparing a solid into 100mL of a cerium nitrate solution; weighing 7.6g of cerium nitrate solution and 0.5g of OMC, uniformly mixing, adding 150mL of deionized water and 18mL of 2mol/L NaOH solution, stirring at normal temperature for 3 hours, washing, drying at 120 ℃ in a forced air oven for 3 hours, finally placing the obtained black solid in a box-type resistance furnace, roasting at 400 ℃ for 3 hours in a nitrogen atmosphere to obtain the cerium dioxide doped ordered mesoporous carbon material 12% CeO2/OMC。
Example 5
Ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/3% CeO2The preparation of OMC (3% is the mass fraction of cerium element in OMC), which comprises the following steps:
0.5g of 3% CeO of example 2 was weighed2OMC and 0.25g binuclear cobalt phthalocyanine are dissolved in 100mL deionized water, and after the mixed solution is subjected to ultrasonic treatment for 4 hours, the solution is directly placed inDrying for 15 hours in an oven at 60 ℃ to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/3% CeO2/OMC。
Example 6
Ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/6% CeO2The preparation of OMC (6 percent is the mass fraction of cerium element in the OMC) comprises the following steps:
0.5g of 6% CeO of example 3 was weighed2dissolving/OMC and 0.25g of binuclear cobalt phthalocyanine in 100mL of deionized water, ultrasonically treating the mixed solution for 5 hours, directly drying the solution in an oven at 70 ℃ for 12 hours to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/6% CeO2/OMC。
Example 7
Ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/12% CeO2The preparation of OMC (12% is the mass fraction of cerium element in OMC), which comprises the following steps:
0.5g of 12% CeO of example 4 was weighed2dissolving/OMC and 0.25g of binuclear cobalt phthalocyanine in 100mL of deionized water, ultrasonically treating the mixed solution for 6 hours, directly drying the solution in an oven at 80 ℃ for 10 hours to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material Bi-CoPc/12% CeO2/OMC。
Micro-topography testing and analysis
The materials obtained in examples 1, 3 and 5 to 7 were characterized by Transmission Electron Microscopy (TEM): dissolving a proper amount of the product in an ethanol solvent, carrying out ultrasonic treatment for 2 hours, dripping the ultrasonic solution on a copper net, and carrying out shape characterization on the material by adopting a transmission electron microscope of JEM-2100F, Japan Electron Co. TEM images of the materials obtained in examples 1 and 3 and examples 5 to 7 are shown in FIGS. 1a to 1 e.
As can be seen from fig. 1a to 1e, the support OMC has a well-ordered hexagonal pore structure, which indicates that although the silica template is removed using NaOH solution during the synthesis process, the ordered pore structure is not changed. And from 6% CeO2/OMC、Bi-CoPc/3％CeO2/OMC、Bi-CoPc/6％CeO2OMC and Bi-CoPc/12% CeO2In TEM images of/OMC (fig. 1b, 1c, 1d and 1e) it is evident that dark black spots are concentrated on the catalyst surface, indicating that ceria has been successfully loaded onto OMC. In addition, as can be seen from fig. 1c to fig. 1e, the edge of the material has a layered substance, because the Bi-CoPc molecules are large and wrap around the OMC, which also proves that the Bi-CoPc is loaded on the catalyst; in fig. 1e, it can be seen that the pore structure of the carrier is not obvious, because the carrier is completely wrapped by the cerium nitrate with too large doping amount.
The materials obtained in examples 1, 3 and 5 to 7 were subjected to small-angle X-ray diffraction analysis using a Smartlab model X-ray diffractometer, japan physics corporation. The small-angle X-ray diffraction patterns of the materials obtained in examples 1, 3 and 5 to 7 are shown in FIG. 2.
As can be seen from FIG. 2, the OMC support (curve a) has a strong and distinct diffraction peak, 6% CeO after calcination2(curve b) of/OMC, Bi-CoPc/3% CeO2OMC (Curve c) and Bi-CoPc/6% CeO2The diffraction peak of the/OMC (curve d) catalyst is also obviously reduced, which shows that the mesoporous structure is not obvious after heating and along with the increase of the doping amount, but still shows that the surface of the catalyst still has a naked mesoporous structure. However, Bi-CoPc/12% CeO2The diffraction peak intensity of the/OMC (curve e) becomes particularly weak, because the doping amount of cerium nitrate is too large, and the ordered mesoporous carbon is completely wrapped, which is also consistent with the transmission electron micrograph of the catalyst.
The elemental analysis of Ce and Co in the materials obtained in examples 3 and 5 to 7 was carried out using an atomic absorption spectrophotometer (Hitachi Z-2000 type). The results of the analysis of Co and Ce elements in the materials obtained in examples 3 and 5 to 7 are shown in Table 1.
TABLE 1 analysis results of Co and Ce elements in the materials obtained in example 3 and examples 5 to 7
As can be seen from Table 1, in the materials obtained in examples 3 and 5 to 7, the cobalt content was substantially constant within the range of 1.0 to 1.1%, because the addition amount of cobalt dinuclear phthalocyanine remained unchanged during the synthesis process, while the measured amount of cerium showed a doubling trend with the increase of the addition amount of cerium nitrate, indicating that there was substantially no loss of cerium nitrate during the synthesis process.
The above embodiments are only 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 simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (5)
1. A preparation method of an ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material is characterized by comprising the following steps:
(1) adding an ordered mesoporous carbon material into deionized water, a cerium nitrate solution and a sodium hydroxide solution, mixing, stirring for 3-4 hours, filtering, washing, drying at 100-120 ℃ for 1-3 hours, and roasting to obtain a cerium dioxide doped ordered mesoporous carbon material; the ordered mesoporous carbon material is prepared by the following steps:
(1-1) mixing a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, deionized water and a hydrochloric acid solution, stirring for 4-5 hours at 40-60 ℃, then adding tetraethoxysilane, and continuously stirring for 18-22 hours to obtain a white suspension; the mass ratio of the polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer to the deionized water to the hydrochloric acid solution to the ethyl orthosilicate is 3.5-4.0: 30: 110-130: 8.5; the concentration of the hydrochloric acid solution is 1-2 mol/L;
(1-2) adding the white suspension into a polypropylene bottle, crystallizing at 80-100 ℃ for 48-60 hours, filtering, washing, drying at 60-90 ℃ for 10-14 hours, and roasting the dried solid at 400-600 ℃ for 5-7 hours to obtain a white solid;
(1-3) adding sucrose, deionized water and concentrated sulfuric acid into the white solid, uniformly mixing, drying at 80-100 ℃ for 6-8 hours, and then heating to 150-160 ℃ for carbonization for 5-6 hours to obtain brown solid; the mass ratio of the white solid to the sucrose to the deionized water to the concentrated sulfuric acid is 1: 1.25-1.5: 4-5: 0.14; the concentration of the concentrated sulfuric acid is 16 mol/L;
(1-4) fully grinding the brown solid, adding sucrose, deionized water and concentrated sulfuric acid again, uniformly mixing, drying at 80-100 ℃ for 6-8 hours, heating to 150-160 ℃ for carbonization for 5-6 hours, and roasting at 800-1000 ℃ for 3-4 hours to obtain a black solid; the mass ratio of the brown solid to the sucrose to the deionized water to the concentrated sulfuric acid is 0.3-0.5: 0.8:5: 0.09; the concentration of the concentrated sulfuric acid is 16 mol/L;
(1-5) heating and refluxing the black solid in a sodium hydroxide solution at the temperature of 90-100 ℃ for 6-8 hours to remove the template, washing the product, and drying at the temperature of 90-100 ℃ for 6-8 hours to obtain the ordered mesoporous carbon material; the solvent of the sodium hydroxide solution is a mixed solvent of ethanol and water with equal volume, and the concentration of the sodium hydroxide solution is 1-2 mol/L;
(2) mixing the cerium dioxide-doped ordered mesoporous carbon material, deionized water and binuclear cobalt phthalocyanine, performing ultrasonic treatment for 4-6 hours, and drying at 60-80 ℃ for 10-15 hours to obtain the ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material.
2. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the ordered mesoporous carbon material, the deionized water, the cerium nitrate solution and the sodium hydroxide solution is 0.5:150: 1.9-7.6: 16-20; the concentration of the cerium nitrate solution is 0.046 mol/L; the concentration of the sodium hydroxide solution is 1-2 mol/L.
3. The method according to claim 1, wherein in the step (1), the calcination is carried out at 300 to 450 ℃ for 2 to 4 hours in a nitrogen atmosphere.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the ceria-doped ordered mesoporous carbon material, the deionized water and the cobalt binuclear phthalocyanine is 0.5: 90-110: 0.25.
5. The ordered mesoporous carbon co-supported cerium dioxide and binuclear cobalt phthalocyanine material prepared by the preparation method of any one of claims 1 to 4.
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| Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable,Mesoporous Silica Structures;Dongyuan Zhao等;《Journal of The American Chemical Society》;19980609;第120卷(第24期);第 6024-6036页 * |
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