CN112221524B - Preparation method of supported gallium nitride catalyst with large specific surface area - Google Patents
Preparation method of supported gallium nitride catalyst with large specific surface area Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
The invention provides a preparation method of a supported large-specific-surface-area gallium nitride catalyst, which is characterized in that organic compounds containing gallium and nitrogen-containing gas are used as raw materials, a carrier with a large specific surface area is used as a carrier, an atomic layer deposition method is adopted, the temperature of the carrier is controlled to be 250-550 ℃, and the supported large-specific-surface-area gallium nitride catalyst is prepared through reaction. Compared with the prior art, the method of the invention can continuously introduce the precursor for a long time, realize the uniform deposition of the small-scale gallium nitride particles on the powder carrier with large specific surface area, and the gallium nitride loading capacity is accurate and controllable. The catalyst obtained by the method has a stable three-dimensional structure, enriches the catalyst structure, and improves the carbon deposition resistance and poisoning resistance of the catalyst. The obtained catalyst has a certain pore structure, and can effectively reduce particle sintering in the high-temperature catalysis process.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a supported catalyst, and particularly relates to a preparation method of a supported gallium nitride catalyst with a large specific surface area.
Background
Gallium nitride (GaN) as a typical representative of third-generation semiconductor materials has the characteristic of large forbidden bandwidth, has excellent performances which many silicon materials do not have, is not only a good short-wave photoelectron material, but also an excellent semiconductor material for high-frequency, high-voltage, high-temperature and high-power applications, and has wide application prospects in the civil and military fields. In addition, nitride is also an important catalyst in a heterogeneous catalytic system, the application of Gallium Nitride in the catalytic field is widely concerned by scholars at home and abroad, small-scale catalytic experiments and researches show that the Nitride catalyst has great industrial significance, has outstanding capability of activating C-H bonds in hydrocarbon molecules and is expected to become a nonmetal catalyst for replacing noble metals, wherein the Gallium Nitride catalyst shows excellent catalytic performance in the reactions of oxygen-free Aromatization of low-carbon alkane, preparation of propylene from propane and the like, and the specific surface area purchased by Lu Li et al (Lu Li, xiaoyue Mu, thermal Non-Oxidative Aromatization of Light Alkanes catalyst by ply galium Nitride) by Sigma-Aldrich is 6.73m 2 The commercial gallium nitride particles in the amount of/g are used as catalysts, and the high catalytic activity of gallium nitride in the oxygen-free aromatization reaction of light hydrocarbon is found for the first time. The existing gallium nitride catalysts are all gallium nitride particles with low specific surface area, have the defects of low specific surface area, serious carbon deposition phenomenon in catalyst reaction, low utilization rate of active components and the like, and if the large-surface-area supported GaN catalyst can be prepared, the large-surface-area supported GaN catalyst can be further preparedThe conversion rate and the selectivity of the alkane are improved.
There are many methods for preparing gallium nitride, including metal organic vapor phase epitaxy, metal organic chemical vapor deposition, plasma-enhanced atomic layer deposition, or preparing gallium nitride by performing post-treatment such as ammoniation on gallium oxide, but there are some defects in preparing gallium nitride catalysts with large specific surface area. The metal organic vapor phase epitaxy has the defects of complex growth process, difficult quality control, low yield and the like; the deposition temperature of the metal organic chemical vapor deposition method needs to be over 1000 ℃, the requirement on the substrate is strict, and the obtained gallium nitride has certain carbon pollution; the plasma-enhanced atomic layer deposition method is limited by plasma, and a surface modification process of a carrier with a large specific surface area cannot be realized.
Chinese patent application publication No. CN103205729A discloses a method for growing a gallium nitride film by using ALD equipment, which comprises the steps of performing surface treatment on a silicon carbide substrate, placing the silicon carbide substrate in deposition equipment, introducing gallium chloride to adsorb on the surface of the silicon carbide substrate, performing discharge ionization by using nitrogen plasma, forming nitrogen-hydrogen ions with hydrogen, introducing the nitrogen-hydrogen ions into a reaction cavity, reacting with chloride ions in the gallium chloride, and substituting nitrogen atoms for other functional groups except gallium in the gallium chloride to obtain the gallium nitride film. The method has low deposition temperature, but when the deposition is carried out on a carrier with large specific surface area, reaction precursors need to be introduced in a long time, the plasma deviates from thermodynamic equilibrium property, the stability is poor, the continuous long-time introduction cannot be carried out, the repeatability of a deposition experiment is poor, the deposition speed is low, the loading amount of active components cannot be accurately controlled, and the method is not suitable for the deposition of gallium nitride on a powder material with large specific surface area.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a supported gallium nitride catalyst with a large specific surface area, and solve the technical problem that the supported gallium nitride catalyst with the large specific surface area cannot be stably prepared in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a supported large specific surface area gallium nitride catalyst comprises the steps of taking gallium-containing organic compounds and nitrogen-containing gas as raw materials, taking a large specific surface area carrier as a carrier, adopting an atomic layer deposition method, controlling the temperature of the carrier to be 250-550 ℃, and reacting to obtain the supported large specific surface area gallium nitride catalyst.
The invention also has the following technical characteristics:
preferably, the carrier temperature is controlled to be 250-300 ℃, 300-350 ℃, 350-400 ℃, 400-450 ℃, 450-500 ℃ or 500-550 ℃; further preferably, the temperature of the carrier is controlled to be 400 to 500 ℃ or 450 to 550 ℃.
The specific surface area of the supported large specific surface area gallium nitride catalyst is 10.0000-2000.0000 m 2 (ii) in terms of/g. Preferably, the specific surface area is 100.0000-1000.0000 m 2 (ii)/g; more preferably, the specific surface area is 400.0000 to 915.0000m 2 (ii)/g; most preferably, the specific surface area is 415.5163-912.7906 m 2 /g；
The gallium-containing organic compound is Ga (CH) 3 ) 3 、Ga(C 2 H 5 ) 3 、GaCl 3 Or GaCl.
The nitrogen-containing gas is ammonia gas or nitrogen gas.
The carrier with large specific surface area is active carbon, pure silicon molecular sieve and Al 2 O 3 Or a silicon-aluminum mixed molecular sieve.
Specifically, the method comprises the following steps:
placing a carrier in a deposition reaction chamber of atomic layer deposition equipment, introducing inert gas into the deposition reaction chamber, vacuumizing, adjusting the pressure in the deposition reaction chamber to be 10-105 Pa, and heating the carrier;
introducing gallium-containing organic compound steam into the deposition reaction chamber, keeping the temperature of the carrier to perform gas-solid interface reaction to fix gallium on the surface of the carrier, subsequently introducing inert gas into the deposition reaction chamber to clean the deposition reaction chamber, removing excessive unreacted gallium-containing organic compound precursor, then introducing nitrogen-containing gas into the deposition reaction chamber, and performing displacement reaction with the gallium-containing organic compound chemically adsorbed on the surface of the carrier; finally, introducing inert gas into the deposition reaction chamber to purge the residual unreacted ammonia in the reaction chamber;
and step three, repeating the process of the step two until the gallium nitride catalyst with the required loading capacity is generated.
In the first step, the reaction equipment is an atomic layer deposition fixed bed, an atomic layer deposition rotating bed or an atomic layer deposition fluidized bed.
In the second step, the reaction time of the gas-solid interface reaction is 10-1000 s, the cleaning time of the inert gas is 10-1000 s, the reaction time of the displacement reaction is 10-4000 s, and the purging time of the inert gas is 10-1000 s.
Preferably, in the second step, the reaction time of the gas-solid interface reaction is 200 to 300s, the purge time of the inert gas is 200 to 300s, the reaction time of the displacement reaction is 800 to 1200s, and the purge time of the inert gas is 200 to 300s.
In the second step, the inert gas is helium, nitrogen or argon.
Compared with the prior art, the invention has the following technical effects:
compared with the prior art, the method of the invention can continuously introduce the precursor for a long time, realize the uniform deposition of the small-scale gallium nitride particles on the powder carrier with large specific surface area, and the gallium nitride carrying capacity is accurate and controllable.
The catalyst obtained by the method has a stable three-dimensional structure, enriches the catalyst structure, and improves the carbon deposition resistance and poisoning resistance of the catalyst. The obtained catalyst has a certain pore structure, and can effectively reduce particle sintering in the high-temperature catalysis process.
(III)) compared with the prior art, the deposition temperature is lower, gallium nitride particles in the catalyst are generated in one step in the loading process, and post-treatment, such as steps of high-temperature ammoniation, reduction and the like, is not needed, so that the preparation time and the cost are saved.
The process of the invention can be controlled by an automatic program, can realize large-scale production, has low production cost, completely seals the reaction process, and is easy to recycle and treat the generated waste.
Drawings
Fig. 1 is an SEM image of the catalyst prepared in example 1, in which fig. 1 (a) is an SEM image of the catalyst, fig. 1 (B) is a Ga element distribution diagram, fig. 1 (C) is an N element distribution diagram, fig. 1 (D) is a Si element distribution diagram, and fig. 1 (E) is an O element distribution diagram.
Fig. 2 is an XPS spectrum of the catalyst prepared in example 1.
Fig. 3 is an XRD spectrum of the catalyst, catalyst support and commercial gallium nitride powder prepared in example 3.
The present invention will be explained in further detail with reference to examples.
Detailed Description
In order to overcome the defects of small specific surface area, insufficient catalytic life and stability and the like of commercial gallium nitride particles, the invention provides a preparation method of a supported gallium nitride catalyst with large specific surface area. The method has high automation degree and simple operation steps, and is easy to realize large-scale production of products.
The invention solves the problems of low specific surface area, short service life, poor distribution uniformity of gallium nitride, large particle size, uncontrollable content and the like of the prior disclosed gallium nitride catalyst. The preparation method comprises the steps of depositing gallium nitride on catalyst carriers with large specific surface areas, such as MCM-41, alumina, activated carbon and the like, by an atomic layer deposition technology to obtain a supported gallium nitride catalyst with large specific surface area, and adjusting the supporting capacity and the crystal structure of active component gallium nitride by deposition cycles. The catalyst prepared by the method has the characteristics of three-dimensional nano structure, large specific surface area, high dispersion of gallium nitride particles, uniform distribution, uniform size and the like, shows excellent activity, selectivity and stability in the propane dehydrogenation catalytic reaction, and promotes the application of gallium nitride in the catalytic field.
It should be noted that, in the present invention, the gas-solid interface reaction, i.e., the reaction between the vapor of the organic compound containing gallium and the surface groups of the carrier, is a self-limiting gas-solid interface reaction, where the self-limiting gas-solid interface reaction refers to that, within a sufficient pulse time sequence, the vapor of the organic compound containing gallium is subjected to saturation chemisorption on the surface of the carrier, and the remaining unadsorbed excess precursor is discharged out of the reaction chamber along with the carrier gas.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
this example provides a preparation method of a supported large specific surface area gallium nitride catalyst, which comprises the following steps:
step one, placing 0.5g MCM-41 molecular sieve as a carrier in a quartz boat, placing the quartz boat in a deposition reaction chamber of an atomic layer deposition fixed bed, sealing the deposition reaction chamber, introducing inert gas nitrogen into the deposition reaction chamber, vacuumizing, adjusting the flow rate of the nitrogen to 50ml/min, adjusting the pressure in the deposition reaction chamber to be 100Pa, and heating to ensure that the temperature of the carrier is 400 ℃;
step two, enabling Ga (CH) to pass through a cooling device 3 ) 3 Cooling to-25 deg.C, and introducing Ga (CH) into the deposition reaction chamber 3 ) 3 Steam, keeping the temperature of the carrier to carry out gas-solid interface reaction, so that the gallium element is fixed on the surface of the carrier, namely saturated chemical adsorption is carried out on the outer surface of the carrier and the inner surface of the pore channel, and the reaction time of the gas-solid interface reaction is 200s; then introducing inert gas nitrogen into the deposition reaction chamber for cleaning, removing excessive unreacted gallium-containing organic compound precursor and surface reaction byproducts, wherein the cleaning time is 200s, then introducing ammonia gas into the deposition reaction chamber, carrying out a displacement reaction with the gallium-containing organic compound chemically adsorbed on the surface of the carrier, introducing ammonia gas, and carrying out chemical adsorption on the surface of the molecular sieveReplacing functional groups of gallium-containing organic matters on the surface for 800s; and finally, introducing inert gas nitrogen into the deposition reaction chamber to purge the residual unreacted ammonia gas and byproducts in the reaction chamber, wherein the cleaning time is 200s.
And step three, repeating the process of the step two once to generate the gallium nitride catalyst with the required loading capacity.
To generate the gallium nitride catalyst with required loading.
After the reaction is finished, when the temperature of the reaction cavity is reduced to be within 100 ℃, the vacuum pump is closed and carrier gas N is introduced 2 And recovering the positive pressure of the reaction cavity, and taking out a sample to finish the preparation of the GaN/MCM-41 catalyst.
The GaN/MCM-41 catalyst is marked as 400-1c-200-200-800-200sGaN/MCM-41, wherein:
400 represents the deposition temperature of active component gallium nitride at 400 ℃;
1c represents a deposition cycle number of 1
200-200-800-200s represent deposition timing sequences.
Catalyst characterization:
the BET physical adsorption test result showed that the specific surface area of the catalyst obtained in example 1 was 814.5558m 2 A specific surface area of about 6.73 m/g of commercial gallium nitride powder 2 /g) 120 times the specific surface area.
The content of gallium element is measured by inductively coupled plasma atomic emission spectrometry (ICP-AES) accurately to be 12.1wt%.
FIG. 1 is an SEM photograph of the catalyst 400-1c-200-200-800-200sGaN/MCM-41 prepared in example 1, wherein A is the SEM photograph of the catalyst, and B-E are distributions of Ga, N, si, and O elements in sequence.
FIG. 2 is a XPS of the catalyst and catalyst support MCM-41 of example 1 sufficient to demonstrate uniform deposition of GaN on pure Silicon (SiO) 2 ) Molecular sieve MCM-41.
The above characterization results show that the catalyst prepared in this example is a supported gallium nitride catalyst GaN/MCM-41 catalyst with a large specific surface area.
And (3) testing the catalytic performance:
50.6mg of the catalyst of example 1 and 406mg of stone were weighed outMixing quartz and sand, enhancing catalyst dispersibility, placing in a quartz tube with diameter of 4mm, fixing the catalyst with quartz cotton, bed height of 37mm, gradually heating to 550 deg.C under nitrogen, introducing 5% propane/95% argon gas mixture, performing catalytic experiment for propane anaerobic dehydrogenation to prepare propylene, and mass space velocity of 1h - The reaction product was monitored and analyzed on-line by gas chromatography, and after 1 hour of reaction, sampling was carried out to obtain a propane conversion of 14.0% and a propylene selectivity of 83.7%.
Example 2:
this example shows a preparation method of a supported gallium nitride catalyst with large specific surface area, referring to the method of example 1 to prepare 400-3c-200-200-800-200sGaN/MCM-41 catalyst, which is different from example 1 in that the deposition temperature is 400 ℃, and the number of deposition cycles is 3 cycles, and the method is specifically carried out according to the following steps:
step one, the same as the step one of the embodiment 1;
step two, the same as step two of example 1;
and step three, repeating the process of the step two for three times to generate the gallium nitride catalyst with the required loading capacity.
And after the reaction is finished, when the temperature of the reaction cavity is reduced to be within 100 ℃, closing the vacuum pump and introducing carrier gas to recover the positive pressure of the reaction cavity, taking out a sample, and finishing the preparation of the GaN/MCM-41 catalyst.
The GaN/MCM-41 catalyst is marked as 400-3c-200-200-800-200sGaN/MCM-41, wherein:
400 represents the deposition temperature of active component gallium nitride at 400 ℃;
3c represents a deposition cycle number of 3;
200-200-800-200s represent deposition timing sequences.
Characterization of the catalyst:
the BET physical adsorption test result showed that the specific surface area of the catalyst obtained in example 2 was 729.8319m 2 A specific surface area of about 6.73 m/g of commercial gallium nitride powder 2 /g) 108 times the specific surface area.
The content of Ga element was accurately determined to be 23.0wt% by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
The SEM picture result and XPS result of this example are substantially the same as those of example 1.
The above characterization results show that the catalyst prepared in this example is a supported gallium nitride catalyst GaN/MCM-41 catalyst with a large specific surface area.
And (3) testing the catalytic performance:
weighing 47.3mg of the catalyst in the example 2, mixing the catalyst with 400.6mg of quartz sand to enhance the dispersibility of the catalyst, placing the catalyst in a quartz tube with the diameter of 4mm, fixing the catalyst by using quartz wool, ensuring that the height of a bed layer is 36mm, gradually raising the temperature to 550 ℃ under nitrogen, introducing 5% propane/95% argon mixed gas, and carrying out a catalytic experiment for preparing propylene by propane anaerobic dehydrogenation at a mass space velocity of 1h - The reaction product was monitored and analyzed on-line by gas chromatography, and after 1 hour of reaction, sampling was carried out to obtain a propane conversion of 21.14% and a propylene selectivity of 78.19%.
Example 3:
this example shows a method for preparing a supported gallium nitride catalyst with large specific surface area, referring to the method of example 1 to prepare 500-3c-200-200-800-200sGaN/MCM-41 catalyst, which is different from example 1 in that the deposition temperature is 500 ℃, and the number of deposition cycles is 3 cycles, and the method is specifically carried out according to the following steps:
step one, which is different from step one of example 1 only in that in this example, the support temperature was brought to 500 ℃ by heating;
step two, the same as step two of example 1;
and step three, repeating the process of the step two for three times to generate the gallium nitride catalyst with the required loading capacity.
After the reaction is finished, when the temperature of the reaction cavity is reduced to be within 100 ℃, the vacuum pump is closed and carrier gas is introduced, so that the positive pressure of the reaction cavity is recovered, the sample is taken out, and the preparation of the GaN/MCM-41 catalyst is finished.
The GaN/MCM-41 catalyst is marked as 500-3c-200-200-800-200sGaN/MCM-41, wherein:
500 represents that the deposition temperature of the active component gallium nitride is 500 ℃;
3c represents a deposition cycle number of 3;
200-200-800-200s represent deposition timing sequences.
Catalyst characterization:
the BET physisorption test result showed that the specific surface area of the catalyst obtained in example 2 was 415.5163m 2 A specific surface area of about 6.73 m/g of commercial gallium nitride powder 2 /g) 62 times the specific surface area.
The content of Ga element was accurately determined to be 43.0wt% by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
The SEM picture result and XPS result of this example are substantially the same as those of example 1.
FIG. 3 is the XRD results of the catalyst carrier MCM-41 molecular sieve, the catalyst and the commercial GaN powder in example 3, and the diffraction peak of gallium nitride can be obviously seen in the XRD pattern of 500-3c-200-200-800-200sGaN/MCM-41, and the crystalline GaN active component is successfully deposited on the MCM-41 carrier.
The above characterization results show that the catalyst prepared in this example is a supported gallium nitride catalyst GaN/MCM-41 catalyst with a large specific surface area.
And (3) testing the catalytic performance:
weighing 52.1mg of the catalyst in the example 3, mixing the catalyst with 396.8mg of quartz sand to enhance the dispersibility of the catalyst, placing the catalyst in a quartz tube with the diameter of 4mm, fixing the catalyst by using quartz wool, ensuring the height of a bed layer to be 33mm, gradually raising the temperature to 500 ℃ under nitrogen, introducing 5% propane/95% argon mixed gas, and carrying out a catalytic experiment for preparing propylene by propane anaerobic dehydrogenation at a mass space velocity of 1h - The reaction product is monitored and analyzed on line by gas chromatography, and sampling is carried out after 1 hour of reaction, so that the conversion rate of the propane is 15.40 percent, and the selectivity of the propylene is 97.25 percent.
Example 4:
this example shows a preparation method of a supported large specific surface area gallium nitride catalyst, referring to the method of example 1 to prepare 400-1c-300-300-1200-300sGaN/AC catalyst, which is different from example 1 in that the deposition temperature is 400 ℃ and the number of deposition cycles is 1 cycle, and in that the support is activated carbon AC, the method is specifically carried out according to the following steps:
step one, the difference from step one of example 1 is only that in this example, the support temperature is activated carbon AC;
step two, ga (CH) is enabled to be cooled by a cooling device 3 ) 3 Cooling to-25 deg.C, and introducing Ga (CH) into the deposition reaction chamber 3 ) 3 Steam, keeping the temperature of the carrier to carry out gas-solid interface reaction, so that the gallium element is fixed on the surface of the carrier, namely saturated chemical adsorption is carried out on the outer surface of the carrier and the inner surface of the pore channel, and the reaction time of the gas-solid interface reaction is 300s; introducing inert gas nitrogen into the deposition reaction chamber for cleaning, removing excessive unreacted gallium-containing organic compound precursor and surface reaction byproducts, wherein the cleaning time is 300s, then introducing ammonia gas into the deposition reaction chamber, performing a displacement reaction with a gallium-containing organic compound chemically adsorbed on the surface of the carrier, and introducing ammonia gas for performing functional group displacement with the gallium-containing organic compound chemically adsorbed on the surface of the molecular sieve, wherein the reaction time is 120000s; and finally, introducing inert gas nitrogen into the deposition reaction chamber to purge the residual unreacted ammonia gas and byproducts in the reaction chamber, wherein the cleaning time is 300s.
And step three, repeating the process of the step two once to generate the gallium nitride catalyst with the required loading capacity.
And after the reaction is finished, when the temperature of the reaction cavity is reduced to be within 100 ℃, closing the vacuum pump and introducing carrier gas to recover the positive pressure of the reaction cavity, taking out the sample, and finishing the preparation of the GaN/AC catalyst.
The GaN/AC catalyst is marked as 400-1c-300-300-1200-300sGaN/AC, wherein:
400 represents the deposition temperature of active component gallium nitride as 400 ℃;
1c represents a deposition cycle number of 1;
300-300-1200-300s represent deposition timing.
Catalyst characterization:
the BET physical adsorption test result showed that the specific surface area of the catalyst obtained in example 2 was 912.7906m 2 In terms of/g, about commercial gallium nitride powder (specific surface area 6.73 m) 2 /g) 135 times the specific surface area.
The content of Ga element was accurately determined to be 15.6wt% by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
The above characterization results show that the catalyst prepared in this example is a supported GaN/AC catalyst with a large specific surface area.
And (3) testing the catalytic performance:
weighing 49.5mg of the catalyst in the example 4, mixing the catalyst with 400mg of quartz sand to enhance the dispersibility of the catalyst, placing the catalyst in a quartz tube with the diameter of 4mm, fixing the catalyst by using quartz wool, gradually raising the temperature to 550 ℃ under nitrogen, introducing 5% propane/95% argon mixed gas, and performing a catalytic experiment for preparing propylene by propane anaerobic dehydrogenation at the mass space velocity of 1h - The reaction product was monitored and analyzed on-line by gas chromatography, and after 1 hour of reaction, sampling was carried out to obtain a propane conversion of 14.61% and a propylene selectivity of 89.80%.
Example 5:
this example shows a method for preparing a supported gallium nitride catalyst with large specific surface area, which differs from example 1 only in that the gallium-containing organic compound is Ga (C) 2 H 5 ) 3 、GaCl 3 Or GaCl.
The characterization results and performance test results of this example are substantially the same as those of example 1.
Example 6:
this example shows a method for preparing a supported gallium nitride catalyst with large specific surface area, which is different from example 1 only in that the nitrogen-containing gas is nitrogen.
The characterization results and performance test results of this example are substantially the same as those of example 1.
Example 7:
this example shows a method for preparing a supported gallium nitride catalyst with large specific surface area, which is different from example 1 only in that the carrier with large specific surface area is Al 2 O 3 Or a silicon-aluminum mixed molecular sieve.
The characterization results and performance test results of this example are substantially the same as those of example 1.
Example 8:
this example shows a preparation method of a supported gallium nitride catalyst with large specific surface area, which is different from example 1 only in that the reaction equipment is an atomic layer deposition rotating bed or an atomic layer deposition fluidized bed.
The characterization results and performance test results of this example are substantially the same as those of example 1.
Example 9:
this example shows a preparation method of supported gallium nitride catalyst with large specific surface area, which is different from example 1 only in that the inert gas is helium or argon.
The characterization results and performance test results of this example are substantially the same as those of example 1.
Example 10:
this example shows a method for preparing a supported gallium nitride catalyst with a large specific surface area, which differs from example 3 only in that the support is heated to a temperature of 550 ℃;
the characterization results and performance test results of this example are substantially the same as those of example 3.
Claims (7)
1. A preparation method of a supported large-specific-surface-area gallium nitride catalyst is characterized in that organic compounds containing gallium and nitrogen-containing gas are used as raw materials, a carrier with large specific surface area is used as a carrier, an atomic layer deposition method is adopted, the temperature of the carrier is controlled to be 250-550 ℃, and the supported large-specific-surface-area gallium nitride catalyst is prepared through reaction;
the method realizes the uniform deposition of gallium nitride particles on the carrier with large specific surface area;
the specific surface area of the supported large specific surface area gallium nitride catalyst is 415.5163m 2 /g～912.7906m 2 /g；
The carrier with large specific surface area is active carbon, pure silicon molecular sieve and Al 2 O 3 Or a silicon-aluminum mixed molecular sieve;
the method comprises the following steps:
placing a carrier in a deposition reaction chamber of atomic layer deposition equipment, introducing inert gas into the deposition reaction chamber, vacuumizing, adjusting the pressure in the deposition reaction chamber to be 10-105 Pa, and heating the carrier;
introducing gallium-containing organic compound steam into the deposition reaction chamber, keeping the temperature of the carrier to perform gas-solid interface reaction to fix gallium on the surface of the carrier, subsequently introducing inert gas into the deposition reaction chamber to clean the deposition reaction chamber, removing excessive unreacted gallium-containing organic compound precursor, then introducing nitrogen-containing gas into the deposition reaction chamber, and performing displacement reaction with the gallium-containing organic compound chemically adsorbed on the surface of the carrier; finally, introducing inert gas into the deposition reaction chamber to purge the residual unreacted ammonia in the reaction chamber;
and step three, repeating the process of the step two until the gallium nitride catalyst with the required loading capacity is generated.
2. The method according to claim 1, wherein the gallium-containing organic compound is Ga (CH) 3 ) 3 、Ga(C 2 H 5 ) 3 、GaCl 3 Or GaCl.
3. The method according to claim 1, wherein the nitrogen-containing gas is ammonia or nitrogen.
4. The method for preparing the supported large-specific-surface-area gallium nitride catalyst according to claim 1, wherein in the first step, the reaction equipment is an atomic layer deposition fixed bed, an atomic layer deposition rotating bed or an atomic layer deposition fluidized bed.
5. The method for preparing the supported gallium nitride catalyst with large specific surface area according to claim 1, wherein in the second step, the reaction time of the gas-solid interface reaction is 10-1000 s, the cleaning time of the inert gas is 10-1000 s, the reaction time of the displacement reaction is 10-4000 s, and the purging time of the inert gas is 10-1000 s.
6. The method for preparing the supported gallium nitride catalyst with large specific surface area according to claim 5, wherein in the second step, the reaction time of the gas-solid interface reaction is 200-300s, the cleaning time of the inert gas is 200-300s, the reaction time of the displacement reaction is 800-1200 s, and the purging time of the inert gas is 200-300 s.
7. The method for preparing the supported large specific surface area gallium nitride catalyst according to claim 1, wherein in step two, the inert gas is helium, nitrogen or argon.
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