CN115400774A - Method for preparing SiC/C photocatalyst by using biomass waste as raw material through two-step method and SiC/C photocatalyst - Google Patents
Method for preparing SiC/C photocatalyst by using biomass waste as raw material through two-step method and SiC/C photocatalyst Download PDFInfo
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/22—Carbides
- C07C2527/224—Silicon carbide
Abstract
The invention relates to the technical field of preparation of carbon dioxide reduction photocatalysts, and provides a method for preparing a high-light-reduction-performance SiC/C catalyst by using biomass waste as a raw material through a two-step method and the SiC/C catalyst. The method takes cheap biomass waste as a raw material, prepares a precursor silicon carbide-carbon composite material of the photocatalyst through high-temperature treatment in a protective atmosphere, and then puts the precursor material into plasma enhanced chemical vapor deposition equipment to continuously introduce gas for functional treatment, so as to prepare the photocatalyst material for reducing the photocatalytic carbon dioxide into carbon monoxide with high efficiency and high selectivity.
Description
Technical Field
The invention relates to the technical field of preparation of carbon dioxide reduction photocatalysts, in particular to a method for preparing a high-light-reduction-performance SiC/C catalyst by using biomass waste as a raw material through a two-step method and the SiC/C catalyst.
Background
3C-SiC is a non-toxic and inexpensive non-metal oxide semiconductor that has been used in photocatalytic decomposition of water to produce hydrogen, degradation, and photoreduction of CO 2 Etc. (Ginseng radix)See nature,1979,277,637-638; j Mater Sci,1990,25,3101-3104; appl.Catal.B: environ.2017, 206, 158-167). The forbidden bandwidth of the material is about 2.4eV, the conduction band potential is relatively negative, the thermal conductivity is high, and the carbon dioxide can be used for photoreducing the hydrocarbon fuel under the irradiation of visible light. Moreover, the SiC has abundant raw materials and is environment-friendly, so that the SiC has a bright prospect of large-scale application. However, siC itself is easily corroded by light and the recombination of photo-generated electrons and holes in the crystal lattice is fast, thereby preventing the application of SiC in the field of photoreduction. Therefore, how to make the photocatalytic activity of SiC semiconductors and the rapid transfer and separation of electron-hole become the key to the design of SiC semiconductors. There are still few reports on the photo-reduction of SiC powder to CO, and researchers have proposed various methods to improve the photocatalytic efficiency of SiC, and although the selectivity of the product is improved, there are disadvantages such as low yield (ACS appl.mater.interfaces,2021, 13,5073-5078 appl.surf. Sci.2020, 515, 145952).
Researchers find that the carbon material can improve the photocatalytic activity of semiconductors, and therefore, the introduction of a proper carbon source can also improve the photocatalytic performance of SiC materials to a certain extent, which is mainly attributed to the fact that the carbon material has large electron storage capacity, good electron conductivity, chemical stability, excellent mechanical strength and large specific surface area, can provide a rapid transmission channel for electron transfer, effectively reduce the carrier recombination efficiency, and extend an absorption band to a visible light region, thereby improving the photocatalytic performance (Nano Research,2016,9, 886-898 j. Mater. Chem.a,2015,3, 10999-11005; catal. Sci. Technol.,2015,5, 2798-2806. After the SiC semiconductor is introduced with carbon, the selectivity of a SiC product is obviously improved, but the performance and yield are improved slightly (Adv. Mater.2020, 32, 2001560). The preparation technology of the silicon carbide-carbon composite material still has the problems of complexity, high cost, low selectivity and low efficiency in photoreduction application. Therefore, intensive studies are required for simultaneously improving the photocatalytic activity and selectivity.
Disclosure of Invention
The invention aims to solve at least one of the technical problems, and provides a method for developing a high-efficiency photocatalytic material by using biomass waste as a raw material, preparing a silicon carbide-carbon composite material at high temperature of inert gas, and then utilizing plasma etching to overcome the defects of semiconductor manufacturing.
The invention aims at providing a method for preparing a SiC/C photocatalyst by using biomass waste as a raw material through a two-step method, which comprises the following steps:
s1, placing a porcelain boat filled with biomass waste into a tube furnace device, and introducing protective gas to exhaust air in the tube furnace device;
s2, keeping protective gas, heating the porcelain boat filled with the biomass waste to 600-1000 ℃, and synthesizing the silicon dioxide-carbon composite material; then stopping heating, continuing to introduce gas, slowly cooling to room temperature, and uniformly synthesizing the silicon dioxide-carbon composite material;
s3, continuously introducing protective gas and heating to 1100-1700 ℃ to generate a precursor silicon carbide-carbon composite material of the photocatalyst;
s4, turning off the heating power supply, continuously introducing protective gas, slowly cooling to room temperature, and uniformly synthesizing the silicon carbide-carbon composite material in the porcelain boat;
s5, spreading a layer of the silicon carbide-carbon composite material obtained in the step S4 on a porcelain boat, then transferring the porcelain boat to a fixed position of a plasma enhanced chemical vapor deposition device, vacuumizing, and then introducing gas;
and S6, continuously vacuumizing, opening the plasma generator, and performing bombardment functionalization treatment on the silicon carbide-carbon composite material to obtain the SiC/C photocatalyst.
The biomass is the most extensive substance existing on the earth, has the advantages of inexhaustibility and inexhaustibility, is the 4 th largest energy source except petroleum, coal and natural gas, and plays an important role in the whole energy system. The method not only plays an important role in reducing carbon emission, improving energy supply and demand, protecting the ecological environment, increasing income of farmers and the like, but also is an important component of the national development of new energy industries. Reasonably and efficiently recycling biomass waste to CO 2 The emission reduction has important significance. The biomass waste rice hulls containing a large amount of silicon and carbon are indispensable in the process of synthesizing the SiC/C photocatalystAnd is therefore the best raw material for preparing SiC/C composite materials.
Plasma etching has proven to be an effective method of introducing various inherent defects. Depending on the type, intensity and irradiation time of the plasma gas, the defect type and concentration can be effectively adjusted due to the difference in the formation energy of various defects. Surface defects of the material can effectively adjust the local atomic structure, optical properties, electronic structure or electrical conductivity of the material, thereby further influencing physicochemical pillar errors and photocatalytic properties.
The invention takes cheap biomass waste as a raw material, prepares a precursor silicon carbide-carbon composite material of a photocatalyst through high-temperature treatment in a protective atmosphere, and then puts the precursor material into plasma enhanced chemical vapor deposition equipment to continuously introduce gas for functional treatment, thereby preparing the photocatalyst material for reducing carbon dioxide into carbon monoxide through high-efficiency and high-selectivity photocatalysis.
Preferably, in step S1: the biomass waste comprises one or more of rice hulls, straws, wheat bran, corncobs, sawdust and bagasse, and/or the porcelain boat is made of alumina.
Preferably, in step S2: the heating rate is 5-25 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
Preferably, in step S3: the heating rate is 1-10 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
Preferably, in steps S1 to S4: the protective gas is one of nitrogen, argon and helium, and the flow rate is 40-150sccm.
Preferably, in step S5: the vacuum degree of the vacuum pumping is 0.01-10Pa, the gas is one of argon, hydrogen, oxygen and ammonia, and the gas is introduced at the flow rate of 3-25sccm.
Preferably, in step S6: the vacuum degree of the continuous vacuum pumping is 3-30Pa.
Preferably, in step S6: the time of the functionalization treatment is 3-25min, and the power is 20-180W.
In a second aspect of the invention, there is provided a SiC/C photocatalyst made according to the method of any one of the preceding claims.
In a third aspect of the invention, the invention provides an application of a SiC/C photocatalyst in catalyzing carbon dioxide reduction reaction.
The invention can achieve at least one of the following beneficial effects:
1) The raw materials used in the method have wide sources and low cost, and the biomass waste is recycled, thereby being beneficial to sustainable development;
2) The preparation process is simple, and disordered subsequent treatment can be used for large-scale production;
3) After plasma etching, a large number of defects can be constructed on the surface of the silicon carbide-carbon composite material and can be used as catalytic active sites, so that the photocatalytic activity and selectivity can be greatly improved;
4) The plasma etching process is controllable, and the type and concentration of defects can be effectively adjusted by controlling the plasma etching time, power and gas flow, so that the catalytic material with specific properties is finally obtained; the use of plasma etching to create defects in semiconductor materials has great potential for development.
Drawings
FIG. 1 is a schematic view of a PECVD apparatus;
FIG. 2 is a Raman spectrum of argon plasma etching of a silicon carbide, carbon composite at different powers for examples 2,3,4,5, 6;
FIG. 3 is a Raman spectrum of a silicon carbide-carbon composite etched in different gas plasmas of examples 4,7,8,9 at a power of 100W;
FIG. 4 is a SEM image of the SiC-C composite obtained in example 1;
FIG. 5 is a high resolution FES scanning electron microscope photograph of the silicon carbide-carbon composite obtained in example 1;
FIG. 6 is a TEM image of the silicon carbide-carbon composite obtained in example 1;
FIG. 7 is a high-resolution TEM image of the SiC-carbon composite obtained in example 1;
FIG. 8 is a graph showing the photo-reduction yield of the SiC-C composite obtained in example 1;
FIG. 9 is a graph showing the photoreduction yield of the SiC/C composite material obtained in example 2;
FIG. 10 is a graph showing the photo-reduction yield of the SiC/C composite obtained in example 3;
FIG. 11 is a graph showing the photoreduction yield of the SiC/C composite material obtained in example 4;
FIG. 12 is a graph showing the photoreduction yield of the SiC/C composite material obtained in example 5;
FIG. 13 is a graph showing the photo-reduction yield of the SiC/C composite obtained in example 6;
FIG. 14 is a graph showing the photo-reduction yield of the SiC/C composite obtained in example 7;
FIG. 15 is a graph showing the photoreduction yield of the SiC/C composite material obtained in example 8;
FIG. 16 is a graph showing the photoreduction yield of the SiC/C composite material obtained in example 9;
FIG. 17 is a graph showing the photocatalytic carbon dioxide reduction performance of the argon plasma etching of silicon carbide and carbon composites at different power levels for examples 2,3,4,5, 6;
FIG. 18 shows the photocatalytic carbon dioxide reduction performance of examples 4,7,8,9 after etching silicon carbide and carbon composite material with different gas plasmas and a power of 100W;
description of reference numerals: 1-gas inlet, 2-plasma generator, 3-heating zone, 4-composite material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 1, the preferred embodiment of the present invention employs a plasma enhanced chemical vapor deposition apparatus, which includes a plasma generator 2 and a heating zone 3, wherein one end of the plasma generator 2 has a gas inlet 1, the other end is connected to the heating zone 3, and a composite material 4 is placed in the heating zone 3 for plasma etching.
The preferred embodiment of the invention provides a method for preparing a SiC/C photocatalyst by using biomass waste as a raw material through a two-step method, which comprises the following steps:
s1, placing a porcelain boat filled with biomass waste into a tube furnace device, and introducing protective gas to exhaust air in the tube furnace device;
s2, keeping introducing protective gas, heating the porcelain boat filled with the biomass waste to 600-1000 ℃, and synthesizing the silicon dioxide-carbon composite material; then stopping heating, continuing to introduce gas, slowly cooling to room temperature, and uniformly synthesizing the silicon dioxide-carbon composite material;
s3, continuously introducing protective gas and heating to 1100-1700 ℃ to generate a precursor silicon carbide-carbon composite material of the photocatalyst;
s4, turning off the heating power supply, continuously introducing protective gas, slowly cooling to room temperature, and uniformly synthesizing the silicon carbide-carbon composite material in the porcelain boat;
s5, spreading a layer of the silicon carbide-carbon composite material obtained in the step S4 on a porcelain boat, then transferring the porcelain boat to a fixed position of plasma enhanced chemical vapor deposition equipment, vacuumizing, and then introducing gas;
and S6, continuously vacuumizing, starting a plasma generator, and performing bombardment functionalization treatment on the silicon carbide-carbon composite material to obtain the SiC/C photocatalyst.
In step S1: the biomass waste comprises one or more of rice hulls, straws, wheat bran, corncobs, sawdust and bagasse, and/or the porcelain boat is made of alumina.
In step S2: the heating rate is 5-25 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
In step S3: the heating rate is 1-10 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
In steps S1 to S4: the introduced gas is one of nitrogen, argon and helium, and the introduction flow is 40-150sccm.
In step S5: the vacuum degree of the vacuumizing is 0.01-10Pa, the gas is one of argon, hydrogen, oxygen and ammonia, and the gas is introduced at the flow rate of 3-25sccm.
In step S6: the vacuum degree of the continuous vacuum pumping is 3-30Pa; the time of the functionalization treatment is 3-25min, and the power is 20-180W.
The following is a specific example, and the biomass waste is exemplified by rice hulls.
Example 1
1) Washing biomass waste-rice hull with ultrapure water for 3 times, and then drying in an oven at the temperature of 60 ℃.
2) And (3) paving the dried rice hulls in a porcelain boat of high-purity alumina, then placing the porcelain boat in the middle of a high-temperature area of a tube furnace, continuously introducing argon for 30 minutes, wherein the gas flow is 80sccm, exhausting the air in the porcelain boat, and reacting the porcelain boat in an argon atmosphere.
3) And 2) after the step 2) is finished, heating the tubular furnace to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 1h, closing the heating, and then cooling the tubular furnace to room temperature, wherein argon is required to be introduced in the process, and the gas flow is also kept at 80sccm, so that the silicon dioxide-carbon composite material is obtained.
4) And 3) after the step 3) is finished, the sample is not taken out of the tube furnace, argon is continuously introduced for 30 minutes, the gas flow is 80sccm, the air in the tube is exhausted, and the argon atmosphere in the tube is kept.
5) And then heating the tubular furnace to 1400 ℃ at the heating rate of 5 ℃/min, keeping the temperature constant for 1h, closing the heating, and then cooling the tubular furnace to room temperature, wherein argon is required to be introduced in the process, and the gas flow is also kept at 80sccm, so that the silicon carbide and carbon composite material is obtained.
The field emission electron microscope photograph of the silicon carbide-carbon composite material is shown in fig. 4 and 5, and it can be observed that the fiber-shaped silicon carbide and the carbon are crossed and intertwined together; as shown in fig. 6 and 7, the transmission microscope photograph of the silicon carbide-carbon composite material shows that the surface of the fiber-shaped silicon carbide has a thin carbon layer.
Example 2
1) Washing biomass waste-rice hull with ultrapure water for 3 times, and then drying in an oven at the temperature of 60 ℃.
2) And paving the dried rice husks in a porcelain boat of high-purity alumina, then placing the porcelain boat in the middle of a high-temperature area of a tubular furnace, continuously introducing argon for 30 minutes, wherein the gas flow is 80sccm, exhausting the air in the porcelain boat, and reacting the porcelain boat in the argon atmosphere.
3) And 2) after the step 2) is finished, heating the tubular furnace to 800 ℃ at the heating rate of 10 ℃/min, keeping the temperature constant at the temperature for 1h, closing the heating, and then cooling the tubular furnace to room temperature, wherein argon is required to be introduced in the process, and the gas flow is also kept at 80sccm, so that the silicon dioxide-carbon composite material is obtained.
4) And 3) after the step 3) is finished, taking out the sample from the tubular furnace, continuously introducing argon for 30 minutes at the gas flow of 80sccm, exhausting the air in the sample, and keeping the argon atmosphere in the tube.
5) And then heating the tubular furnace to 1400 ℃ at the heating rate of 5 ℃/min, keeping the temperature constant for 1h at the temperature, closing the heating, and then cooling the tubular furnace to room temperature, wherein argon is required to be introduced in the process, and the gas flow is also kept at 80sccm, so that the silicon carbide and carbon composite material is obtained.
6) Spreading a thin layer of the silicon carbide and carbon composite material obtained in the step 5) on the bottom of the porcelain boat, then transferring the composite material to a position, close to the front end of a heating area of a plasma generator, of a plasma enhanced chemical vapor deposition device, and vacuumizing the device, wherein the vacuum degree is 2Pa.
7) Then argon gas is introduced, the gas flow is 10sccm, and the vacuum pumping is continued.
8) And starting to turn on the plasma generator with the power of 100W and the processing time of 10min after the vacuum degree is stabilized at 10Pa, and turning off the plasma to obtain the functionalized silicon carbide and carbon composite photocatalyst.
Example 3
The preparation method is basically the same as example 2, except that: step 8) the plasma power was 40W.
Example 4
The preparation method is basically the same as example 2, except that: step 8) the plasma power was 80W.
Example 5
The preparation method is basically the same as example 2, except that: step 8) the plasma power was 120W.
Example 6
The preparation method is basically the same as example 2, except that: step 8) the plasma power was 140W.
Example 7
The preparation method is basically the same as example 2, except that: the gas introduced in the step 7) is oxygen.
Example 8
The preparation method is basically the same as example 2, except that: the gas introduced in the step 7) is hydrogen.
Example 9
The preparation method is basically the same as example 2, except that: the gas introduced in the step 7) is ammonia gas.
The Raman spectrogram of the silicon carbide-carbon composite material treated by the argon plasma is shown in figure 2, and it can be seen that the defect concentrations caused by etching materials with different powers are different; the raman spectra of the different types of plasma treated silicon carbide, carbon composites are shown in fig. 3, and it can be seen that the different types of plasmas cause different defect concentrations to the materials.
FIG. 8 is a graph of the light reduction yield of the SiC-C composite material obtained in example 1, FIGS. 9 to 13 are graphs of the light reduction yield of the functionalized SiC/C composite material obtained in examples 2 to 6, and FIGS. 14 to 16 are graphs of the light reduction yield of the functionalized SiC/C composite material obtained in examples 7 to 9. FIG. 17 is a graph of photocatalytic carbon dioxide reduction performance of functionalized SiC/C composites obtained by argon plasma treatment at different powers. FIG. 18 is a graph of photocatalytic carbon dioxide reduction performance of functionalized SiC/C composites obtained by plasma treatment with different gases. As can be seen from FIGS. 8-13 and 17, when the power of the Ar plasma is 100W, the photoreduction performance of the etched SiC/C composite material is maximized, and the CO yield is 185.54 mu mol g -1 ,CH 4 The yield can reach 15.31 mu mol g -1 . It can be said from FIGS. 14-16 and 18It is clear that when the SiC/C composite material is treated in four gas plasmas, the material treated by the argon plasma has the best performance, and the yield of CO is 1.39 times that of oxygen, 2.88 times that of hydrogen and 4.24 times that of ammonia respectively.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing a SiC/C photocatalyst by using biomass waste as a raw material through a two-step method is characterized by comprising the following steps:
s1, placing a porcelain boat filled with biomass waste into a tube furnace device, and introducing protective gas to exhaust air in the tube furnace device;
s2, keeping protective gas, heating the porcelain boat filled with the biomass waste to 600-1000 ℃, and synthesizing the silicon dioxide-carbon composite material; then stopping heating, continuing to introduce gas, slowly cooling to room temperature, and uniformly synthesizing the silicon dioxide-carbon composite material;
s3, continuously introducing protective gas and heating to 1100-1700 ℃ to generate a precursor silicon carbide-carbon composite material of the photocatalyst;
s4, turning off a heating power supply, continuously introducing protective gas, slowly cooling to room temperature, and uniformly synthesizing the silicon carbide-carbon composite material in the porcelain boat;
s5, spreading a layer of the silicon carbide-carbon composite material obtained in the step S4 on a porcelain boat, transferring the porcelain boat into plasma enhanced chemical vapor deposition equipment, vacuumizing, and introducing gas;
and S6, continuously vacuumizing, opening the plasma generator, and performing bombardment functionalization treatment on the silicon carbide-carbon composite material to obtain the SiC/C photocatalyst.
2. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S1: the biomass waste comprises one or more of rice hulls, straws, wheat bran, corncobs, sawdust and bagasse, and/or the porcelain boat is made of alumina.
3. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S2: the heating rate is 5-25 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
4. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S3: the heating rate is 1-10 ℃/min, and the temperature is kept for 0.5-2h after the heating is carried out to the specified temperature.
5. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the steps S1 to S4: the protective gas is one of nitrogen, argon and helium, and the flow rate is 40-150sccm.
6. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S5: the vacuum degree of the vacuumizing is 0.01-10Pa, the gas is one of argon, hydrogen, oxygen and ammonia, and the gas is introduced at the flow rate of 3-25sccm.
7. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S6: the vacuum degree of the continuous vacuum pumping is 3-30Pa.
8. The method for preparing the SiC/C photocatalyst by using the biomass waste as the raw material through the two-step method according to claim 1, wherein in the step S6: the time of the functionalization treatment is 3-25min, and the power is 20-180W.
9. A SiC/C photocatalyst, characterized by being produced according to the method of any one of claims 1 to 8.
10. Use of a SiC/C photocatalyst according to claim 9 in catalysing the reduction of carbon dioxide.
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