CN113275002B - C/MoO 2 Porous photocatalyst and preparation method and application thereof - Google Patents

C/MoO 2 Porous photocatalyst and preparation method and application thereof Download PDF

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CN113275002B
CN113275002B CN202110540827.1A CN202110540827A CN113275002B CN 113275002 B CN113275002 B CN 113275002B CN 202110540827 A CN202110540827 A CN 202110540827A CN 113275002 B CN113275002 B CN 113275002B
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CN113275002A (en
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高鹏
邓苹
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Zhejiang Jiushi Biotechnology Co ltd
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Hangzhou Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of photocatalysis, and relates to C/MoO 2 Porous photocatalyst, and preparation method and application thereof. C in the photocatalyst is coated on MoO 2 A surface of (a); the photocatalyst is of a hollow structure, the particle size is less than 2000 nm, and the aperture of the composite catalyst is<20 nm; the photocatalyst is prepared by first utilizing NTA and MoCl 5 Preparing a precursor in a high-temperature reaction kettle, and preparing the C/MoO by a burning method 2 A porous photocatalyst. The catalyst provided by the invention has good adsorption performance and excellent photocatalytic performance, has a high specific area and a high-density catalytic active center, and the porous and hollow structure increases the specific surface area, can effectively improve the light absorption rate, delays the electron hole recombination, and can reduce the requirement of ammonia synthesis reaction in application; the synthesis method provided by the invention has the characteristics of mild conditions, simple and easily obtained synthesis conditions, high purity and the like, and is suitable for large-scale production and application.

Description

C/MoO 2 Porous photocatalyst and preparation method and application thereof
Technical Field
The invention relates to the field of photocatalysis, in particular to C/MoO 2 Porous photocatalyst, and preparation method and application thereof.
Background
In recent years, the problems of environmental pollution and shortage of energy have become increasingly serious, and research and development of various novel energy technologies and apparatuses have been intensively carried out. The photocatalytic technology has the advantages of environmental friendliness, high chemical energy and the like, and is widely considered as an important way for solving environmental pollution and energy crisis. With the development of industry and agriculture, ammonia has become an important chemical for fertilizer and chemical synthesis in agriculture and industry. At present, the synthesis of ammonia in industry is completed by the traditional Haber-Bosch process, and the reaction condition of the process is harsh and the energy consumption is large, namely under the conditions of pressure of 15-25MPa and temperature of 673-873K, the consumed energy accounts for more than 1 percent of the global energy. At present, the synthesis of ammonia in industry is completed by the traditional Haber-Bosch process, and the reaction condition of the process is harsh and the energy consumption is large, namely under the conditions of pressure of 15-25MPa and temperature of 673-873K, the consumed energy accounts for more than 1 percent of the global energy. Mo becomes one of the most hot research elements in the field of photocatalytic nitrogen fixation at present. However, in the Mo-containing catalyst, the photo-generated electron-hole pairs are easy to rapidly recombine, so that the photocatalytic performance of the Mo-containing catalyst is seriously influenced, and the Mo-containing catalyst becomes the most main defect of the Mo-containing catalyst; noble metal catalysts can well circumvent these drawbacks, however, their use is limited by the disadvantages of expensive price, uncontrollable content and destructive conjugated systems. Therefore, there is a need to find suitable photocatalysts to improve their photocatalytic performance.
Publication No. CN106976910A discloses a porous carbon-loaded molybdenum oxide nanoparticle composite material and a preparation method thereof. The preparation method comprises the following steps: (1) adsorbing molybdate by using porous carbon to obtain a precursor; (2) and carrying out heat treatment on the precursor in a hydrogen argon atmosphere to obtain the porous carbon loaded molybdenum oxide nanoparticle composite material. Compared with other methods, the method has the advantages of low cost, simple process, definite product, uniform particle size of the obtained molybdenum oxide nanoparticles, high dispersion, no agglomeration and suitability for large-scale production; the porous carbon loaded molybdenum oxide nanoparticle composite material has great potential application value in the fields of industrial catalysis, electrochemistry or other science.
Disclosure of Invention
In order to solve the technical problem, the invention provides a C/MoO 2 A porous photocatalyst. The porous and hollow structure increases the specific surface area, enables incident light to be reflected and scattered for multiple times in a pore channel, improves the light absorption rate, and slows down the electron hole recombination rate.
One aspect of the invention provides a C/MoO 2 A porous photocatalyst comprising a mixture of MoO 2 Hollow spherical structure constituting porous surface, and MoO 2 The particle surface is coated with C, the particle diameter of the catalyst particles is less than 2000nm, and the aperture of the composite catalyst<20nm。
The porous and hollow structure of the hollow sphere structure with the porous surface increases the specific surface area, so that the outer surface layer of the catalyst is equivalent to a porous film, the recombination of electron holes can be slowed down, and C in the photocatalyst is coated on MoO 2 Thus, the energy band structure is changed, and the recombination rate of electron holes can be reduced.
Preferably, the particle size of the photocatalyst is 1000-2000 nm; when the aperture size of the composite catalyst is 5-15nm and the particle size is small, the aperture/particle size value is too small, the refraction and reflection times of light become small, the light utilization rate is reduced, and the composite of electron holes is not prolonged; when the particle size is out of date, a shell structure is formed, and the stability is poor. Therefore, the preferred particle size of the present invention is 1000-2000 nm.
Secondly, the invention also provides a preparation method of the photocatalyst, which comprises the following steps:
(1) adding MoCl 5 Dispersing the powder in solvent, stirring at room temperature to dissolve, adding NTA, stirring to obtain uniform solution, mixing NTA and MoCl 5 The molar ratio of (a) to (b) is 3:1 to 1: 3;
(2) adding the solution in the step (1) into an autoclave, then placing the autoclave in an oven, and reacting for 5-7 h at 155-185 ℃ to obtain a reaction product;
(3) separating, cleaning and drying the reaction product obtained in the step (2) to obtain a precursor;
(4) and calcining the precursor at 450-550 ℃ for 2-3 h under the protection of gas, and cooling to room temperature to obtain the carbon/molybdenum dioxide nanosphere photocatalyst.
The key point of the method is to control the reaction temperature and time, in the reaction in the step (2), NAT has good coordination performance, four coordination bonds can be provided, a metal chelate can be formed, if the temperature is too high or the reaction time is too long, the chelate can be decomposed, and the yield of the precursor is too low in the process of too low temperature and too low reaction time, so that the preferable step (2) in the scheme needs to react for 5-7 hours at the temperature of 155-185 ℃. In the firing reaction in the step (4), the complex is decomposed to generate gas molecules and no substance is supplemented to enable the porous morphology to be generated, the morphology of the hollow sphere structure of the catalyst is dispersed due to overhigh temperature of the precursor, and the product is agglomerated due to overlow temperature; the catalyst particle aperture is too small due to too long reaction time, and the catalyst hollow sphere structure cannot be well formed due to too short reaction time, so that the expected effect is difficult to achieve, therefore, in the experiment, the calcination in the step (4) is preferably performed at 450-550 ℃ for 2-3 h.
Preferably, the solvent in step (1) is one or more of water, isopropanol, ethylene glycol and ethanol; the stirring is performed in a magnetic stirring mode and is performed through ultrasonic treatment.
In order to obtain a uniform solution, the invention selects magnetic stirring and ultrasonic treatment in the stirring and solution homogenizing processes.
Preferably, the temperature of the reaction in the step (2) is 160-180 ℃; the reaction time is 6-6.5 h.
In the invention, the precursor is prepared by strictly controlling the temperature of 160-180 ℃ and reacting for 6-6.5h, and the obtained product has better uniformity and yield.
Preferably, the washing in the step (3) is at least one water washing and one alcohol washing; the separation in the step (3) adopts centrifugal treatment; the rotation speed of the centrifugal treatment is 3500-; drying treatment is adopted for drying; the drying temperature is 55-65 ℃, and the drying time is 12-24 h.
The purpose of the alcohol wash is to dry more quickly and to carry away moisture during the alcohol wash.
Preferably, the protective gas is argon; the calcining equipment is a muffle furnace, the calcining temperature is 460-480 ℃, and the calcining time is 2.4-2.6 h.
The method can be carried out in a muffle furnace, argon is introduced for a period of time before the burning reaction to ensure that the air in the muffle furnace is evacuated, the calcination temperature is preferably 460-480 ℃, and the calcination time is 2.4-2.6 h.
Moreover, the catalyst can be used for the reaction for synthesizing ammonia, namely the invention provides the photocatalyst for synthesizing ammonia, the working temperature range of the catalyst comprises 25-40 ℃, and the working pressure range comprises 1-2 MPa.
The catalyst can be used for synthesizing ammonia gas in a lower temperature range and pressure range, and the invention slows down the rate of electron holes, promotes the ammonia synthesis reaction and reduces the conditions of the ammonia synthesis reaction.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst provided by the invention has good adsorption performance and excellent photocatalytic performance, has a high specific area and a high-density catalytic active center, and the porous and hollow structure increases the specific area, so that the light absorption rate can be effectively improved, and the electron hole recombination can be delayed;
2. the catalyst provided by the invention can reduce the requirement of the synthetic ammonia reaction;
3. the synthesis method provided by the invention has the characteristics of mild conditions, simple and easily obtained synthesis conditions, high purity and the like, and is suitable for large-scale production and application.
Drawings
FIG. 1 is an XRD picture of a catalyst provided by the present invention;
FIG. 2 is an SEM picture of a catalyst provided by the present invention;
fig. 3 is a TEM image of the catalyst provided by the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. The devices, materials and methods referred to in this application are those well known in the art, unless otherwise indicated.
General examples
C/MoO 2 The preparation method of the porous photocatalyst comprises the following steps:
(1) 0.2g of MoCl 5 Dispersing the powder in a mixed solution of 10ml of deionized water and 20ml of isopropanol, magnetically stirring and ultrasonically treating the mixed solution to obtain a uniform solution, adding 0.14g of NTA, magnetically stirring the mixed solution and ultrasonically treating the mixed solution to obtain a uniform solution;
(2) adding the solution obtained in the step (1) into an autoclave, then placing the autoclave in an oven, and reacting for 5-7 h at 155-185 ℃ to obtain a reaction product;
(3) separating the reaction product obtained in the step (2), centrifuging for 5min at the rotating speed of 4000r/min, washing the separated product with clear water for three times and alcohol for three times, and drying for 12h at the temperature of 60 ℃ to obtain a precursor;
(4) and (3) putting the precursor into a muffle furnace, calcining for 2-3 h at 450-550 ℃ under the protection of argon, and cooling to room temperature to obtain the carbon/molybdenum dioxide nanosphere photocatalyst.
Example 1
C/MoO 2 The preparation method of the porous photocatalyst comprises the following steps:
(1) 0.2g of MoCl 5 Dispersing the powder in a mixed solution of 10ml of deionized water and 20ml of isopropanol, magnetically stirring and ultrasonically treating the mixed solution to obtain a uniform solution, adding 0.14g of NTA, magnetically stirring the mixed solution and ultrasonically treating the mixed solution to obtain a uniform solution;
(2) adding the solution obtained in the step (1) into an autoclave, then placing the autoclave in an oven, and reacting for 5 hours at 155 ℃ to obtain a reaction product;
(3) separating the reaction product obtained in the step (2), centrifuging for 5min at the rotating speed of 4000r/min, washing the separated product with clear water for three times and alcohol for three times, and drying for 12h at the temperature of 60 ℃ to obtain a precursor;
(4) and putting the precursor into a muffle furnace, calcining for 2h at 450 ℃ under the protection of argon, and cooling to room temperature to obtain the carbon/molybdenum dioxide nanosphere photocatalyst.
Example 2
In comparison with example 1, this example is different in that the reaction temperature of step (2) is 170 ℃ and the other conditions are the same as example 1.
Example 3
This example is different from example 1 in that the reaction temperature in step (2) is 185 ℃ and the other conditions are the same as example 1.
Example 4
In comparison with example 1, this example is different in that the reaction temperature of step (4) is 500 ℃ and the other conditions are the same as example 1.
Example 5
In comparison with example 1, this example is different in that the reaction temperature of step (4) is 550 ℃ and the other conditions are the same as example 1.
Example 6
This example is distinguished by the fact that, in comparison with example 1, the reaction time in step (2) is 6h, the remaining conditions being the same as in example 1.
Example 7
This example is distinguished by the fact that, in comparison with example 1, the reaction time in step (2) is 7h, the remaining conditions being the same as in example 1.
Example 8
This example is distinguished by the fact that, in comparison with example 1, the reaction time in step (4) is 2.5h, the remaining conditions being the same as in example 1.
Example 9
This example is distinguished by the fact that, in comparison with example 1, the reaction time in step (4) is 3h, the remaining conditions being the same as in example 1.
Comparative example 1
In comparison with example 1, this comparative example is different in that the reaction temperature of step (2) is 130 ℃ and the remaining conditions are the same as in example 1.
Comparative example 2
In comparison with example 1, this comparative example is different in that the reaction temperature of step (2) is 210 ℃ and the remaining conditions are the same as in example 1.
Comparative example 3
In comparison with example 1, this comparative example is different in that the reaction time of step (2) is 3 hours, and the remaining conditions are the same as example 1.
Comparative example 4
In comparison with example 1, this comparative example is different in that the reaction time of step (2) is 10 hours, and the remaining conditions are the same as example 1.
Comparative example 5
In comparison with example 1, this comparative example is different in that the reaction temperature of step (4) is 300 ℃ and the remaining conditions are the same as in example 1.
Comparative example 6
In comparison with example 1, this comparative example is different in that the reaction temperature of step (4) is 500 ℃ and the remaining conditions are the same as in example 1.
Comparative example 7
In comparison with example 1, this comparative example is different in that the reaction time of step (4) is 1 hour, and the remaining conditions are the same as example 1.
Comparative example 8
In comparison with example 1, this comparative example is different in that the reaction time of step (4) is 5 hours, and the remaining conditions are the same as example 1.
Comparative example 9
In contrast to example 1, this comparative example differs in that it is MoO 2 Powder, the other conditions were the same as in example 1.
The samples obtained in examples 1 to 9 and comparative examples 1 to 9 were examined by the following methods:
1. observing the prepared sample by using SEM, and measuring the particle size, the pore diameter and the like;
2. and (3) testing the catalytic performance: mixing 40mg of the prepared photocatalyst with 60mL of deionized water, stirring uniformly, detecting by using ion chromatography before reaction to confirm whether ammonium pollution exists, putting a quartz container containing 40mg of a sample and 60mL of deionized water into a high-pressure reaction kettle under the condition of ensuring that the environment is free of ammonium pollution, introducing argon for half an hour to ensure that the environment is free of pollution, externally connecting an exhaust pipe to timely remove excessive nitrogen in the reaction kettle, bubbling by a bubbler to carry out ammonia synthesis reaction, sampling once every hour to detect the concentration of ammonium ions, and taking five times in total, wherein the temperature is kept between 25 and 40 ℃ in the reaction process.
Specific results are shown in table 1.
TABLE 1 test results
Figure BDA0003071726070000061
As can be seen from comparing examples 1-3 and comparative examples 1-2, the temperature during the preparation of the precursor has a large influence on the final performance of the catalyst, and the experimental values are not very different in terms of the diameter and the pore diameter of the catalyst particles, but the temperature influence is the yield of the precursor, so that under the condition of too high or low temperature, too low yield is a main factor influencing the test result.
Comparing example 1 with examples 4 to 5 and comparative examples 3 to 4, it can be seen that the reaction time during the preparation of the precursor has a large influence on the final performance of the catalyst, and the experimental values are not very different in terms of the particle diameter and pore diameter of the catalyst alone, and the influence of the reaction time is on the yield of the precursor, so that under too long and too short reaction time, too low yield is a main factor influencing the test result.
Comparing example 1 with examples 6-7 and comparative examples 5-6, it can be seen that temperature during the calcination reaction has a large effect on the final properties of the catalyst, that temperature affects particle size, pore size and pore size distribution, and that temperature also affects the decision of whether the reaction is complete, and that particle size, pore size and distribution, and whether the reaction is complete, all affect catalyst performance. Under the condition of low temperature, the particles have small size and large pore diameter, the reaction is incomplete, and the test result is poor, such as comparative example 5; under the condition of high temperature, the large pore diameter of the particles is small, and the distribution number of the surface micropores is small, resulting in poor test results, such as comparative example 6.
Comparing example 1 with examples 8-9 and comparative examples 7-8, it can be seen that during the calcination reaction, the reaction time has a large influence on the final properties of the catalyst, and the reaction time affects the particle size, pore size and pore size distribution, and the reaction time and the decision of whether the reaction is complete, and the particle size, pore size and distribution, and whether the reaction is complete, all affect the catalyst properties. Under the condition of short reaction time, the particles have small size, large pore diameter, incomplete reaction and poor test result, such as comparative example 7; under the condition of long reaction time, the large pore diameter of the particles is small, and the distribution number of the surface micropores is small, resulting in poor test results, such as comparative example 8.
As can be seen from comparative examples 1 to 9 and comparative example 9, the presence of C promotes NH 3 May be the result of the presence of C changing the band structure of the material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (8)

1. C/MoO 2 The preparation method of the porous photocatalyst is characterized by comprising the following steps: the photocatalyst comprises MoO 2 Hollow ball structure constituting porous surface, and MoO 2 Surface of the particlesHas C coating, the particle diameter of the catalyst particles is less than 2000 nm, and the aperture of the composite catalyst<20 nm；
The C/MoO 2 The preparation method of the porous photocatalyst comprises the following steps:
(1) adding MoCl 5 Dispersing the powder in solvent, stirring at room temperature to dissolve, adding NTA, stirring to obtain uniform solution, mixing NTA and MoCl 5 The molar ratio of (a) to (b) is 3:1 to 1: 3;
(2) adding the solution obtained in the step (1) into an autoclave, then placing the autoclave in an oven, and reacting for 5-7 h at 155-185 ℃ to obtain a reaction product;
(3) separating, cleaning and drying the reaction product obtained in the step (2) to obtain a precursor;
(4) and calcining the precursor at 450-550 ℃ for 2-3 h under the protection of gas, and cooling to room temperature to obtain the carbon/molybdenum dioxide nanosphere photocatalyst.
2. C/MoO according to claim 1 2 The preparation method of the porous photocatalyst is characterized in that the particle size of the photocatalyst is 1000-1500 nm.
3. The C/MoO of claim 1 2 The preparation method of the porous photocatalyst is characterized in that the aperture size of the composite catalyst is 5-15 nm.
4. The C/MoO of claim 1 2 The preparation method of the porous photocatalyst is characterized in that the solvent in the step (1) is one or more of water, isopropanol, ethylene glycol and ethanol; the stirring is performed in a magnetic stirring mode and is performed through ultrasonic treatment.
5. C/MoO according to claim 1 2 The preparation method of the porous photocatalyst is characterized in that the reaction temperature in the step (2) is 160-180 ℃; the reaction time is 6-6.5 h.
6. Such asC/MoO according to claim 1 2 The preparation method of the porous photocatalyst is characterized in that the cleaning in the step (3) is at least one water washing and one alcohol washing; the separation in the step (3) adopts centrifugal treatment; the rotation speed of the centrifugal treatment is 3500-; drying treatment is adopted for drying; the drying temperature is 55-65 ℃, and the drying time is 12-24 h.
7. C/MoO according to claim 1 2 The preparation method of the porous photocatalyst is characterized in that the protective gas is argon; the calcining equipment is a muffle furnace, the calcining temperature is 460-480 ℃, and the calcining time is 2.4-2.6 h.
8. Use of a photocatalyst prepared by the preparation method according to any one of claims 1 to 7 for ammonia synthesis, wherein the catalyst has a working temperature in the range of 25 to 40 ℃ and a working pressure in the range of 1 to 2 MPa.
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