CN110182808B - Preparation method of silicon-carbon alkene and method for preparing hydrogen by photolysis of water vapor - Google Patents
Preparation method of silicon-carbon alkene and method for preparing hydrogen by photolysis of water vapor Download PDFInfo
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- CN110182808B CN110182808B CN201910440907.2A CN201910440907A CN110182808B CN 110182808 B CN110182808 B CN 110182808B CN 201910440907 A CN201910440907 A CN 201910440907A CN 110182808 B CN110182808 B CN 110182808B
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000001257 hydrogen Substances 0.000 title claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- -1 silicon-carbon alkene Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 90
- 239000010703 silicon Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 19
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 50
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910020598 Co Fe Inorganic materials 0.000 claims description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- FTEPVGGPJFNOIK-UHFFFAOYSA-N [C].[C].[Si] Chemical compound [C].[C].[Si] FTEPVGGPJFNOIK-UHFFFAOYSA-N 0.000 description 1
- QZOVMCPHIQVUGV-UHFFFAOYSA-N [Si].[C].[Si] Chemical compound [Si].[C].[Si] QZOVMCPHIQVUGV-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
- C01B3/045—Decomposition of water in gaseous phase
-
- 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
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/984—Preparation from elemental silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of semiconductors and discloses a silicon-carbon alkene preparation method and a method for preparing hydrogen by photodecomposition of water vapor. After the sample reaction is carried out in the sample chamber, the laser power supply, the electric furnace heating power supply and the high-frequency electromagnetic field power supply are closed, natural cooling is carried out, and the product in the sample chamber is collected and is silicon-carbon alkene. The silicon-carbon alkene can be grown under the condition that laser radiation is carried out on the silicon alkene and graphene under the high-temperature condition and the silicon carbide is used as an induction factor and is further grown through radiation weakening of secondary laser, the silicon-carbon alkene is crystal growth of a basic unit layer of the silicon carbide, and the novel characteristic of the semiconductor material shows that the bandwidth changes along with component change.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method for preparing silicon-carbon alkene and a method for preparing hydrogen by photolysis of water vapor.
Background
Currently, the current state of the art commonly used in the industry is such that:
the silicon carbene is a crystal on earth in which the growth of a silicon carbide unit layer existing in natural crystals is not found. Currently, the population of the earth is expanded, the population of China possibly breaks through 16 hundred million in this century, the population of Africa possibly breaks through 15 hundred million, India possibly breaks through 15 hundred million, the life of human beings forms a challenge to the consumption of the existing resource reserves and the bearing capacity of the earth, and a large amount of waste gas is discharged, wherein the reserved quantity of automobiles of each country exceeds 10 hundred million, the tail gas discharged every day is the source of air pollution of the earth, the PM2.5 pollution is increasingly serious since the 21 st century, the pollution of the urban group in the northern China is increased, and the incidence rate of lung cancer is improved by 43 percent only in Beijing from 2004 to 2014. The society needs to develop non-mineral and petroleum-burning automobiles, and batteries of electric automobiles are always a difficult problem. Many countries attach great attention to it, but the effect is not good. The process of manufacturing the battery relates to the processes of ore digging, selection and metallurgy and chemical technology, the scrapped battery needs to be recycled, the chemical pollution is caused, and the hydrogen combustion or fuel cell automobile is developed. Among the technologies, broadband semiconductors are gaining importance because they are non-toxic, inexpensive, and efficient at decomposing water to produce hydrogen.
In the past, the industry and academia pay attention to titanium dioxide as a carrier raw material for preparing hydrogen generated by decomposing water, but the titanium dioxide only can absorb light in an ultraviolet ray utilizing region due to the bandwidth of 3.2eV, the quantum efficiency of electron hole generation generated under illumination is not high, the separation of electrons and holes is not enough, the efficiency of generating hydrogen is low, and the method is not practical in a large scale. The broadband semiconductor silicon carbide has excellent photoelectric property and mechanical property, has proper energy band gap, and the conduction band bottom and the valence band top of the silicon carbide are suitable for the position of an oxyhydrogen electrode in water, so that the efficiency of photoexcitation electron-hole pairs is higher, but due to high recombination rate, the graphene with strong conductivity is required to separate the photoproduction electron-hole, and the full separation of the electron and the hole pair is kept, so that the broadband semiconductor silicon carbide is the key for generating hydrogen by photolysis of water.
Although photocatalytic hydrogen production of nano silicon carbide has been a little work for a long time, the hydrogen production efficiency is very low. One is because the carborundum is indirect hold-up semiconductor, and photoproduction electron-hole efficiency is not high, involves the momentum conversion, and the two is because of, and cubic lattice carborundum has the hold-up at 2.8eV, and the carborundum of hexagonal lattice hold-up width is 3.2eV, can only utilize the ultraviolet wave band, and energy utilization is low. Solving this problem then involves reducing the silicon carbide bandgap by doping means but without changing the nature of the bandgap.
However, the unit material formed by laminating the single silicon atom layer and the single carbon atom layer as the silicon carbide is a potential novel semiconductor, and through calculation, the unit material is a direct-hold gap semiconductor, has the series advantages of the silicon carbide, and has the width of the gap reduced to 2.5 eV. Silene is a promising material. We synthesized this material. Although this material has a structure of silicon carbide and is composed of two atomic layers of silicon and graphene, silicon carbide is covalently bonded between the silicon atomic layer and the carbon atomic layer. One surface of the surface has the characteristics of graphene, the other surface has the characteristics of silicon alkene, and the nature of silicon carbide is arranged between the layers, so that the material is a broadband semiconductor with extremely high conductivity, transparency, strong toughness and hopefully. Its performance is superior to that of silicon carbide.
The silicon-carbon alkene of the nanometer silicon carbide with the forbidden band semiconductor characteristic is a new material. It has been known for a long time that the efficiency of decomposing water is not high enough, and that platinum is relied on, but rare, resulting in a high cost of the fuel cell. In fact, the problem behind this is that only the generation efficiency and separation effect of the photo-generated electron-hole pairs are taken into account, which is a concept of charge, and the present invention is to study the maximization of the spin electron-hole for exciting the electron-hole pairs, so that the spin electron and the spin hole generate very large efficiency.
The conventional problem of low efficiency in decomposing water is that there is not enough spin-electron-hole formation in decomposing water due to disorder of charges. Therefore, the number of the photogenerated electron-hole spin is maximized, measures are taken to enable the randomly moving charges to move regularly, namely, the spin property of the electrons and the holes is utilized, a magnetic field is applied for controlling, the separated electrons and holes participate in the oxidation-reduction process, and the effect of improving the water decomposition is achieved. This promotes the decomposition of water to increase the changing energy band, and hydrogen gas is generated with high efficiency. Experiments show that some dye-sensitized semiconductor systems doped with graphene have a good effect of decomposing water to generate hydrogen, but the graphene only has good conductivity, and has zero gap, so that the graphene can not provide photo-generated charges. Silicon carbide in wide band gap semiconductors has a wide band of energy, up to 2.8eV or more, however, the bulk material of silicon carbide is inactive and is an indirect semiconductor material, i.e. the photoexcited electrons transit from the valence band to the conduction band, and cannot be done directly, but must be assisted by an assisted momentum change, in other words, silicon-graphene with a graphene and silicon-graphene bilayer combination is a special substance, unlike silicon carbide, a unit layer of silicon carbide, which has some of the properties of silicon carbide, but has advantages not possessed by silicon carbide. Since one face is graphene and the other face is silylene, such a bilayer is covalently bonded by silicon and carbon atoms to form a silicon carbene. It is a direct band-gap semiconductor, has broadband properties, and easily controls its spintronics. Like graphene is a single atomic layer structural unit of graphite, silicon carbene is also the simplest silicon carbide unit of silicon carbide formed by combining a carbon atomic layer and a silicon atomic layer. Unlike graphene, where the electrons are charge dominant, silicon carbon is also a bulk material, silicon carbide, due to the creation of sp3 hybrid bonds. An external magnetic field is applied to control the spin-electrons to dominate. The spin direction of the generated photogenerated electrons is controlled, so that the photogenerated electrons can fully react with h ions to generate hydrogen. Increasing the intensity of external light is an effective way to increase the photo-generated electron-hole pairs. Thus, different application factors can be controlled to form comprehensive application, and effective results can be generated for photocatalytic decomposition of water-borne hydrogen.
In addition, the common semiconductor composite material systems are sulfide + semiconductors or dye sensitized semiconductors, and the systems are easy to decompose and fail in the system with the temperature of water higher than 30 ℃ and collapse. But the silicon carbene and graphene systems are stable at such temperatures. Can continuously decompose water to generate hydrogen without weakening the effect of the system in decomposing water to generate hydrogen.
In summary, the problems of the prior art are as follows:
(1) the conventional problem of low efficiency in decomposing water is that there is not enough spin-electron-hole formation in decomposing water due to disorder of charges.
(2) The general semiconductor composite material system is sulfide + semiconductor or dye sensitized semiconductor, and the systems are easy to decompose and fail and collapse in the system with the water temperature higher than 30 ℃.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing silicon-carbon alkene and a method for preparing hydrogen by photolysis of water vapor.
The invention is realized in such a way that the preparation method of the silicon carbide alkene comprises the following steps:
(1) weighing 500g of high-purity graphene and 500g of silicon alkene respectively, weighing 0.1g of nano silicon carbide powder and 1mg of gallium and iron nano powder respectively, placing the nano silicon carbide powder and the nano silicon carbide powder in a mechanical stirrer, adding acetone, sealing, stirring for 2 hours, standing for 72 hours, taking out, and drying for 24 hours in a vacuum drying oven at 100 ℃;
(2) placing the mixed sample in a graphite boat, and placing the graphite boat loaded with the mixture of the silicon alkene, the graphene and the nano silicon carbide on a sample seat of a sample reaction chamber;
(3) the reaction chamber is composed of a cylindrical stainless steel barrel with the diameter of 100cm and the height of 200cm, a sample seat is positioned in the center of the bottom of the steel barrel, a variable-frequency heating electric furnace is arranged at the lower part of the sample seat, a horizontal circle 20cm away from the bottom of the stainless steel barrel is provided with a window corresponding to the end points of four mutually vertical diameters, the window is sealed by glass, 4 femtosecond lasers with the wavelength of 300nm are configured, the gun ports of the lasers face the samples in a graphite boat in the center of the bottom of the reaction chamber, a light source is directly irradiated to the samples, a vacuum pump is configured in the reaction chamber, a stainless steel circular sample collector is placed on the sample seat in the reaction chamber, four magnet tiles are pasted in four quadrants which are divided by the cylindrical shape of the reaction chamber in the north, south, the north and the west direction horizontal plane to generate a static magnetic field, and a group of coils are added at the periphery to generate a high-frequency electromagnetic field;
(4) before the reaction chamber is reacted, firstly, the vacuum is pumped to 10-3Starting an electric furnace to heat, heating to 500-1000 ℃, simultaneously starting four lasers, and scanning point by point aiming at a sample, wherein light brown smoke dust is exploded on a sample seat;
(5) starting high-frequency plasma discharge and a high-frequency magnetic field, and restraining the flow direction by inertia to enable smoke dust to be repeatedly mixed and reacted in the air;
(6) the laser radiation continues to be aligned with the sample for scanning until the sample in the graphite boat is completely ablated by the laser, and the whole process lasts for about 5 minutes;
(7) maintaining the temperature of the reaction chamber at 500-1000 ℃ for ten minutes;
(8) and turning off a laser power supply and an electric furnace heating power supply, a high-frequency electromagnetic field power supply and a magnetic field, naturally cooling for 72 hours, and collecting a product of sample seed changing, which is the silicon-carbon alkene.
The silicon carbene is of a single-layer-like cubic silicon carbide structure formed by double layers of the silicon carbene and the graphene, one layer of carbon atoms are connected by covalent bonds to form a hexagonal ring shape, one layer of silicon atoms are also connected by covalent bonds to form a hexagonal ring shape, the silicon atom layer and the carbon atom layer are connected by the covalent bonds formed by the silicon atoms and the carbon atoms, and all the bonds are sp3 hybrid bonds; the chemical formula of the crystal structure is (Si)xC1-x)n，0<x<1 is atomic weight percent, n>The number of silicon carbide units formed of one carbon atom and one silicon atom represented by the structural formula (1).
The invention also aims to provide a silicon-carbon photoelectric material prepared by utilizing the silicon carbene.
The invention also aims to provide a method for preparing hydrogen by using the photolysis water vapor of the silicon carbene, which comprises the following steps:
depositing a cobalt-iron alloy layer on the surface of silicon-graphene particles by a photo-deposition method to obtain cobalt-iron-silicon-graphene nanoparticles with the cobalt-iron alloy layer mass fraction of 0.05-2.0%, then soaking the Co-Fe-silicon-graphene nanoparticles in a 0.05-0.5 mmol/L dye-methanol solution, standing in the dark for 48-72 hours for filtering, washing with deionized water for 5-10 times, standing in a vacuum drying box, and drying at 80-200 ℃ for 12-24 hours to obtain dye-sensitized Co-Fe-silicon-graphene nanoparticles;
adding the Co-Fe-silicon carbon alkene nano particles sensitized by dye into a triethanolamine TEOA with the volume concentration of 150ml or a reactor of a mixture water solution of methanol and triethanolamine with the volume concentration of 10-20%, ultrasonically treating a sample solution for 5-30 minutes by using ultrasonic waves, and introducing argon for 10-60 minutes to obtain a uniform Co-Fe-silicon carbon alkene nano particle colloidal suspension without oxygen;
applying a static magnetic field, adding a transparent all-optical condenser, and irradiating the photocatalytic reactor; starting magnetic stirring, and quantitatively measuring hydrogen generated in the reaction vessel by using a gas chromatograph to measure the photocatalytic activity.
Further, the generated hydrogen is quantitatively measured by a hydrogen detector; the hydrogen detector is a thermal conductivity detector, the carrier gas is argon, the separation column is 13X molecular sieve filler, the external standard method is used for calibration, and 0.5mL of gas is extracted from a silica gel pad of the reactor every 30-180 minutes and injected into a gas phase for detection.
Further, in the measurement of the photocatalytic activity, a dye-sensitized Cr-Fe-silicon carbon alkene nanoparticle porous film is used as a working electrode, a Pt filament counter electrode and Ag/AgCl are used as reference electrodes, the working electrode and the Pt filament counter electrode are placed in an aqueous solution of a sacrificial agent, argon gas is introduced into the solution for 15 minutes, and a condenser is used for gathering sunlight to irradiate a reaction system solution for electrochemical analysis reaction.
Further, the silicon carbene is used as a photo-generated electron hole pair electron transfer medium, the sensitizing dye is used as a connecting molecule, and the Co-Fe alloy nano particles loaded on the silicon carbene are subjected to in-situ photo-reduction and are used as a catalyst to form a dye-sensitized Co-Fe-silicon visible light response photocatalytic reduction water hydrogen production system.
In the invention, the doping of gallium and iron elements has high efficiency for preparing hydrogen by hydrolysis. The crystal structure is a sphalerite structure, a silicon atom is sandwiched between two layers of carbon atoms in a stacking mode of the silicon atoms and the carbon atoms, or a carbon atom is sandwiched between two layers of silicon atoms, the silicon atoms and the carbon atoms are connected by covalent bonds, and the outer surface of the crystal layer of the unit layer is an sp3 hybridized dangling bond. Has the properties and advantages of graphene and the properties of silicon carbide. In this structure the doping element acts to enhance the catalysis. The crystal face is the preparation method of or mutually superposed SiC and the hydrogen is prepared by photolysis of water.
In the invention, the silicon-carbon alkene is a semiconductor material, the forbidden bandwidth of the silicon-carbon alkene is different with the value of x in a crystal structure unit formula, the forbidden bandwidth of x is increased from small to close to 0.5, the forbidden bandwidth of the semiconductor is increased from 0.9eV to 3.1eV, the forbidden bandwidth of x is continuously increased, and when the forbidden bandwidth is close to 1, the forbidden bandwidth is reduced to 0.1 eV. Doping can be used to adjust the photoelectric characteristics and mechanical characteristics of the silicon carbon.
In summary, the advantages and positive effects of the invention are:
TABLE 1 Effect of the present invention on decomposing water to generate hydrogen gas under light condensing and white light irradiation
Out of 278 samples, 4 samples were selected for hydrogen evolution testing, and table 2 is the test data.
Table 2 the effect of TEOA pH and the concentration of silicon-carbon-ene, graphene in the silicon-carbon-ene composite on photocatalytic hydrogen production under concentrated light irradiation.
Table 2 shows that the hydrogen evolution rate is about 22.6(umol/h) under neutral condition and when the electron donor is used, the experimental result also shows that the strong acid-base environment is unfavorable for hydrogen evolution. The low hydrogen evolution rate with strong acids indicates that the state of TEOA, being fully protonated, makes it difficult to oxidize, reducing the ability of the semiconductor to provide electrons. Whereas the more alkaline conditions favor oxidation. The greater the hydrogen ion concentration, the faster the reduction rate and the greater the rate of hydrogen gas generation. High hydrogen evolution index.
TABLE 3 decomposition of concentrated radiation water under the action of static magnetic field and variable frequency magnetic field to generate hydrogen
Table 3 shows that the static magnetic field applied to the silicon-carbon graphene system subjected to the light-gathering irradiation can increase the hydrogen yield, and as the static magnetic field reaches the strong magnetic field from weak, the hydrogen generation rate is higher, and under the action of the variable frequency magnetic field, the hydrogen generation rate is correspondingly increased. Removing the condensation light, and under the irradiation of natural sunlight, applying a static magnetic field can also increase the rate of generating hydrogen; under the condition of light-gathering irradiation, a variable frequency magnetic field is applied, so that the effect of remarkably increasing generated gas is achieved. This shows that the combined application of static, alternating and intense magnetic fields can increase the recall rate of production under the application of megalight radiation.
The silicon carbene can be grown by laser irradiation of the silicon alkene and graphene under the conditions of silicon carbide serving as an induction primer and further growth weakening by irradiation of secondary laser under the high-temperature condition, is crystal growth of a basic unit layer of the silicon carbide, and the novel characteristic of the semiconductor material shows that the bandwidth changes along with the change of components.
Drawings
FIG. 1 is a flow chart of a method for preparing silicon-carbon alkene according to an embodiment of the invention.
FIG. 2 is a scanning electron micrograph of a silicon-carbon alkene provided by an embodiment of the present invention.
FIG. 3 is a RMAN light scattering diagram of the silicanenes provided in the examples of the present invention.
FIG. 4 is a graph showing the photocatalytic water splitting hydrogen production performance of the silylene + graphene system under the irradiation conditions of natural visible light and natural visible light (reaction conditions: pH7, 18% glycerol ethylamine (TEOA), 4mg of silylene, and optionally 0.1mg of graphene).
In the figure: f-only graphene, the hydrogen yield is zero; the E-silicon carbene and graphene system only irradiates by natural light, so that the hydrogen production rate is increased; d-silicon-carbon-alkene + graphene system, natural light gathering + weak magnetic field adding 20 Gs; c-silicon carbene + graphene system, condensing and applying a weak magnetic field of 20 Gs; b-silicon carbene + graphene system, condensing and 50Hz variable frequency magnetic field; a-silicon carbene + graphene system, light gathering + strong magnetic field.
FIG. 5 is a schematic diagram of the photocatalytic decomposition of water by silicon carbene to generate hydrogen according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The conventional problem of low efficiency in decomposing water is that there is not enough spin-electron-hole formation in decomposing water due to disorder of charges.
The common semiconductor composite material systems are sulfide + semiconductors or dye sensitized semiconductors, and the systems are easy to decompose and fail in the system with the temperature of water higher than 30 ℃ and collapse.
To solve the above problems, the present invention will be described in detail with reference to specific embodiments.
As shown in fig. 1, the method for preparing silicon carbide alkene provided by the embodiment of the invention comprises the following steps:
s101, weighing 500g of high-purity graphene and 500g of silicon alkene respectively, weighing 0.1g of nano silicon carbide powder and 1mg of gallium and iron nano powder respectively, placing the nano silicon carbide powder and the nano gallium and iron nano powder in a mechanical stirrer, adding acetone, sealing, stirring for 2 hours, standing for 72 hours, taking out the nano silicon carbide powder and the nano gallium and iron nano powder, and drying the nano silicon carbide powder for 24 hours in a vacuum drying oven at 100 ℃.
And S102, placing the mixed sample in a graphite boat, and placing the graphite boat loaded with the mixture of the silicon alkene, the graphene and the nano silicon carbide on a sample seat of a sample reaction chamber.
S103, the reaction chamber is composed of a cylindrical stainless steel barrel with the diameter of 100cm and the height of 200cm, a sample seat is positioned at the center of the bottom of the steel barrel, a variable-frequency heating electric furnace is arranged at the lower part of the sample seat, corresponding windows are arranged on four mutually vertical diameter end points on a horizontal circle with the height of 20cm away from the bottom of the stainless steel barrel, the windows are sealed by glass, 4 femtosecond lasers (Pharos yttrium-doped laser, 290fs, 1030nm laser wavelength and 15W power are arranged, a Hiro harmonic generator and an optical parameter amplifier are adopted, the frequency multiplication laser wavelength reaches 250nm), the gun mouths of the lasers face samples in a graphite boat at the center of the bottom of the reaction chamber, a light source is enabled to be directly irradiated to the samples, a vacuum pump is arranged in the reaction chamber, a stainless steel circular sample collector is arranged on the sample seat in the reaction chamber, four magnet tiles are arranged in four quadrants which are divided by a north-south-north-east-west horizontal plane, a static magnetic field is generated, and a set of coils are added at the periphery to generate a high-frequency electromagnetic field.
And S104, arranging points on the horizontal plane of the reaction chamber with the height of 300cm, wherein the points are the same as those of the first layer of laser, arranging a partition plate in the plane, arranging a circular hole with the diameter of 0.5mm in the center, and arranging another group of four femtosecond lasers, wherein the lasers and the bottom layer of laser have the same or different wavelengths.
S105: before the reaction chamber is reacted, firstly, the vacuum is pumped to 10-3And (3) starting an electric furnace to heat, and starting four lasers at 1500-2000 ℃ at the same time to scan the sample point by point, wherein light brown smog dust is exploded on the sample seat.
S106: the vacuum pump is started to form negative pressure for reaction below the partition plate for the space above the partition plate, the high-frequency magnetic field is started, the high-frequency plasma smoke dust can be inertially restrained to flow in the radial direction and the radial diameter of the flow direction, so that the random smoke dust body is guided by vacuum through the partition plate with a small hole in the center, the partition plate is also a sample collecting tank, the second layer of laser is started to cross irradiate the smoke dust in the plane on the horizontal plane of the partition plate with the hole, the smoke dust is repeatedly mixed and reacted in the air, the growth of silicon carbene nuclei is promoted in the process, and meanwhile, the further growth of silicon carbide is prevented.
And S107, continuing to scan the sample by the radiation of the bottom layer laser until the sample in the graphite boat is completely ablated by the laser, and continuing the whole process for about 15-120 minutes.
S108: the temperature of the reaction chamber is maintained at 1500-1900 ℃ for ten minutes.
S109: and turning off a laser power supply and an electric furnace heating power supply, a high-frequency electromagnetic field power supply and a magnetic field, naturally cooling for 72 hours, and collecting products in the sample ring. The product is a transparent, bluish, flaky crystal.
The structure of the silicon carbide crystal is identified by a Raman scattering spectrogram, and the appearance of the silicon carbide crystal is flexible and shown by the analysis of a high-resolution transmission electron microscope, and is shown in an attached figure 2. The measured thickness of the single layer of the silicon carbide is 0.69 nm. Observed by a scanning tunnel microscope, the silicon-based carbon nano-tube has a two-layer structure, wherein one surface is a silicon atomic layer, and the other surface is a carbon atomic layer (not shown in the attached drawing). The Rman scattering spectrum analysis showed the scattering pattern of silicon carbide, which is shown in fig. 3, and is silicon carbene. By STM photographic analysis of these samples, also a silicon-carbon-silicon or carbon-silicon-carbon solid phase appeared, with raman spectra identical to that of silicon carbide, as evidenced by x-ray diffraction analysis. The test analysis of the 270 samples synthesized in this manner all indicated the consistency of this result. The chemical structural formula is Si which can be obtained through the experimental result of chemical analysisxC1-x,0<x<1 and x is an atomic weight percentage value. If two carbon atoms are added with one silicon atom, the structural formula is Si3C7On the contrary, if two layers of silicon atoms sandwich one layer of carbon atoms, the structural formula is Si3C2Considered as cubic polytype lattice; when the silicon carbene is respectively stacked by a silicon carbon atom layer, the molecular structural formula is SiC, and the silicon carbene is a hexagonal multi-type lattice. The analysis experiment of atomic absorption spectrum shows that the silicon carbide alkene can appear light yellow to light blue color along with the difference of doped metal elements, if transition metal elements such as iron, cobalt and nickel are yellow, and lanthanide doped with trace rare earth elements is light yellow. Indicating that the color of the silicon carbide is controlled by the doping element and also by the crystal point defects.
The conductivity of the silicon carbene was tested at 103～105Sm-1Good conductivity.
In an embodiment of the present invention, a method for preparing hydrogen by photolysis of water vapor comprises:
depositing a cobalt-iron alloy layer on the surface of silicon-carbon olefin particles by using a photo-deposition method to obtain cobalt-iron-silicon-carbon olefin nano particles with the cobalt-iron alloy layer mass fraction of 0.05-2.0%, then soaking the Co-Fe-silicon-carbon olefin nano particles in 0.05-0.5 mmol/L dye-methanol solution, standing in the dark for 48-72 hours, filtering, washing with deionized water for 5-10 times, placing in a vacuum drying box, and drying at 80-200 ℃ for 12-24 hours to obtain dye-sensitized Co-Fe-silicon-carbon olefin nano particles;
adding the dye-sensitized Co-Fe-silicon carbon alkene nanoparticles into a triethanolamine TEOA or methanol and triethanolamine mixture aqueous solution reactor with the volume concentration of 10-20% and the volume of 150ml, ultrasonically treating a sample solution for 5-30 minutes by using ultrasonic waves, and introducing argon for 10-60 minutes to obtain a uniform Co-Fe-silicon carbon alkene nanoparticle colloidal suspension without oxygen;
applying a static magnetic field, adding a transparent all-optical condenser, and irradiating the photocatalytic reactor; starting magnetic stirring, and quantitatively measuring hydrogen generated in the reaction vessel by using a gas chromatograph to measure the photocatalytic activity.
Quantitatively measuring the generated hydrogen by using a hydrogen detector; the hydrogen detector is a thermal conductivity detector, the carrier gas is argon, the separation column is 13X molecular sieve filler, the external standard method is used for calibration, and 0.5mL of gas is extracted from a silica gel pad of the reactor every 30-180 minutes and injected into a gas phase for detection.
In the measurement of the photocatalytic activity, a dye-sensitized Cr-Fe-silicon-carbon-alkene nanoparticle porous film is used as a working electrode, a Pt filament counter electrode and Ag/AgCl are used as reference electrodes, the working electrode and the Pt filament counter electrode are placed in a water solution of a sacrificial agent, argon gas is introduced into the solution for 15 minutes, and a condensing lens is used for condensing sunlight to irradiate a reaction system solution for electrochemical analysis reaction.
The method comprises the steps of taking silicon carbene as a photo-generated electron hole pair electron transfer medium, taking sensitizing dye as a connecting molecule, and taking Co-Fe alloy nano particles loaded on the silicon carbene as a catalyst through in-situ photo-reduction to form a dye-sensitized Co-Fe-silicon visible light response photocatalytic reduction water hydrogen production system.
In the method for preparing hydrogen by photolysis of water vapor, an experimental system is irradiated by visible light.
Wherein, the experimental system is as follows: weighing 1g of silicon carbene and 1mg of graphene, and adding 1-15 mg of sacrificial agent (TEOA).
The sacrificial agent TEOA is added, after the system is prepared, the magnetic induction intensity is increased to 20G by applying a magnetic field, the system is irradiated by a condensing lens, the condensing intensity is increased, and after 300 minutes of attachment, the hydrogen generation rate of the system is increased by 380 percent. In this case, the intensity of the photocurrent is increased by more than 10 times compared with the dark current, which can be detected by an electrochemical device. The existence of the spin single electron enables the microwave applied outside to generate a transfer effect on water decomposition, so that the aquatic hydrogen is promoted to be decomposed, and the great improvement is realized.
The action of the light gathering and the magnetic field can improve the intensity of photocurrent and establish photovoltaic voltage making open-circuit potential. The mobility of the photoelectrons is increased. The establishment of a higher open circuit voltage is a factor. The cobalt-iron alloy nanoparticles adhere to the silicon carbene, which may be due to the principle that the contact surface reduces the surface potential, forming a p-type surface. The quantum efficiency of the photo-generated electron-hole pairs can be improved. The blending system of the silicon carbene and the nano silver and the constant magnetic field have obvious hydrogen generation effect on the mixture of silicon carbene and dye sensitization and the nano composite metal particle structure.
In the embodiment of the invention, fig. 3 is an RMAN light scattering pattern of the silacene provided in the embodiment of the invention. FIG. 4 is a graph showing the photocatalytic water splitting hydrogen production performance of the silylene + graphene system under the irradiation conditions of natural visible light and natural visible light (reaction conditions: pH7, 18% glycerol ethylamine (TEOA), 4mg of silylene, and optionally 0.1mg of graphene). In the figure: f-only graphene, with zero hydrogen yield; the E-silicon carbene and graphene system only irradiates by natural light, so that the hydrogen production rate is increased; d-silicon-carbon-alkene + graphene system, natural light gathering + weak magnetic field adding 20 Gs; c-silicon carbene + graphene system, condensing and applying a weak magnetic field of 20 Gs; b-silicon carbene + graphene system, condensing and 50Hz variable frequency magnetic field; a-silicon carbene + graphene system, light gathering + strong magnetic field.
The invention is further described below with reference to experiments and specific examples.
(1) Experimental reagent and instrument
Self-made silicon carbide (n-Bu4N)2-cis- [ Ru (dcbpy)2](SCN)2(N719, Solaronix, Switzerland), Tetracarboxylic acidPhenylporphyrin (TCPP) and tetrasulphonyl porphyrin (TPPS) (tokyo corporation, japan). The other reagents are analytical grade. The experimental water is deionized water. The reactor is a quartz reaction bottle with a plane window, the mouth of the reaction bottle is sealed by silicon rubber, and the illumination area is 10-20 cm2。
The condenser was selected from ZEISS full light transmission lens, fluorescence chromatograph, (F7000, Hitachi, Japan), ultraviolet-visible spectrophotometer (V-570-DS, Jasco, Japan), gas chromatograph (GC-8A),5A
Molecular sieves with argon as carrier gas, shimadzu japan). And (3) irradiating the silicon carbene-nano silver cobalt iron system by using solar light with a condenser. And the magnetic shoe is a permanent magnetic shoe with the curvature same as that of the stainless steel barrel reaction chamber. Four blocks, which are wrapped on the periphery of four quadrants of the divided reaction chamber in the same horizontal plane.
The silicon carbide is prepared first, and TEOA (triethanolamine) is added.
Example one
Depositing a cobalt-iron alloy layer on the surface of the silicon-carbon olefin particles by using a photo-deposition method to obtain cobalt-iron-silicon-carbon olefin nano particles with the cobalt-iron alloy layer mass fraction of 0.05-2.0%, then soaking the Co-Fe-silicon-carbon olefin nano particles in 0.05-0.5 mmol/L dye-methanol solution, standing in the dark for 48-72 hours, filtering, washing with deionized water for 5-10 times, placing in a vacuum drying box, and drying at 80-200 ℃ for 12-24 hours to obtain the dye-sensitized Co-Fe-silicon-carbon olefin nano particles. Adding dye-sensitized Co-Fe-silicon carbon alkene nanoparticles (0.002-0.005 g) into a Triethanolamine (TEOA) or methanol and triethanolamine mixture aqueous solution reactor with the volume concentration of 10-20% and the volume of 150ml, wherein the volume of the solution is 10-30 ml, ultrasonically treating a sample solution for 5-30 minutes by using ultrasonic waves, and introducing argon for 10-60 minutes to obtain the uniform Co-Fe-silicon carbon alkene nanoparticle colloidal suspension without oxygen. Applying a static magnetic field, placing under the sunlight, adding a transparent full light condenser, and irradiating the photocatalytic reactor. The magnetic stirring was started, and the hydrogen gas generated in the reaction vessel was quantitatively measured by a gas chromatograph, and the photocatalytic activity was also measured.
The hydrogen detector is a thermal conductivity detector, the carrier gas is argon, the separation column is 13X molecular sieve filler, the external standard method is used for calibration, and 0.5mL of gas is extracted from a silica gel pad of the reactor every 30-180 minutes and injected into a gas phase for detection.
Fluorescence quenching electrochemical assay
The dye-sensitized Cr-Fe-silicon-carbon-alkene nano-particle porous film is used as a working electrode, a Pt filament counter electrode and Ag/AgCl are used as reference electrodes, the three are placed in a water solution of a sacrificial agent, argon gas is introduced into the solution for 15 minutes, and a condenser is used for gathering sunlight to irradiate a reaction system solution for electrochemical analysis reaction.
The self-made silicon carbene is used as a photo-generated electron hole pair electron transfer medium, sensitizing dye is used as a connecting molecule, Co-Fe alloy nano particles loaded on the silicon carbene are subjected to in-situ photo-reduction and are used as a catalyst, and the dye-sensitized Co-Fe-silicon is a photocatalytic water reduction hydrogen production process with visible light response.
The experimental result proves that the system is a high-efficiency hydrogen production system.
Experiments show that when the condenser lens frame has the effects that one is to increase the number of photons per unit area, the generation efficiency of electron hole pairs is accelerated and improved, and the other is to increase the temperature of the condenser lens frame, improve the motion disturbance of particles in water, and enable the generated invitation card to exercise, which is beneficial to the decomposition of the condenser lens frame and the generation of hydrogen; third, light focusing irradiation allows for more efficient electron transfer between the silicon carbene and the nanoparticle. A variable frequency magnetic field is additionally arranged on an illumination decomposition water system, so that the greater disorder degree of the motion of electrons is caused, the hydrogen bonds are crushed too much, and the hydrogen atoms are combined to generate hydrogen. A region of maximum absorption at 430-700 nm was observed for the light emission of the silicon carbene.
EXAMPLE III
The doped preparation of the silicon carbene may be obtained by the following steps,
1) weighing 10G of prepared self-made silicon carbene, and dividing into 2G, 2G and 2G;
2) respectively injecting Cr, Fe, Ru, La and Yb into the 5 samples with the same weight by ion injection to obtain five samplesA doped silicon-carbon material. The doping amount of the elements is maintained at 1016cm3. Not more than 1018cm3。
3) Experiments of photocatalytic decomposition of water to generate hydrogen were performed with these 5 doped silicon-carbon-ene materials, respectively.
4) 2-5 mg of the 5 samples are respectively weighed, each sample has 30 samples, and a test for generating hydrogen by decomposing water through photocatalysis is carried out. The data show that La, Ru, Fe and Yb show high hydrogen production rate, while Cr shows the effect of hydrogen production, but the hydrogen production rate is greatly reduced compared with the former four.
TABLE 4 photocatalytic decomposition of water to produce hydrogen for elemental doped silcarbacene samples
FIG. 4 shows the photocatalytic water splitting hydrogen production performance of the silylene + graphene system under the irradiation conditions of natural visible light and natural visible light (reaction conditions: pH7, 18% of Triol Ethylamine (TEOA), 4mg of silylene, and optionally 0.1mg of graphene). FIG. 4 shows the photocatalytic water splitting hydrogen production performance of the silylene + graphene system under the irradiation conditions of natural visible light and natural visible light (reaction conditions: pH7, 18% of Triol Ethylamine (TEOA), 4mg of silylene, and optionally 0.1mg of graphene).
In fig. 4 the lines are from bottom to top, i.e. from f to a, respectively, f-is graphene only and the hydrogen yield is zero; the E-silicon carbene and graphene system only irradiates under natural light, and the hydrogen production rate is increased. D-silicon-carbon-alkene + graphene system, natural light gathering + weak magnetic field adding 20 Gs; therefore, the silicon-carbon-alkene + graphene system is an ideal system for decomposing water to generate hydrogen. The conduction band potential of the silicon carbene is higher than the electrode potential (H) of hydrogen+H2) more negative, (0V vs NHE, pH 0), and the valence band compares to the like electrode potential (O)2/H2O) correction (1.23V vs NHE, pH 0).
In an experiment, for a silicon carbene graphene system, the silicon carbene has a forbidden band width of 2.5Ev, and can efficiently generate electron-hole pairs under natural visible light illumination, and photo-generated electrons are in a spinning state and have an efficient reduction effect on protons. As shown in fig. 5. The reaction formula is as follows,
2H++2e-＝H2。
to further separate the photogenerated electrons and holes from the semiconducting silicon carbene, the conductivity of graphene from that number produces a good effect. Under the action of light gathering, the hydrogen generating rate is greatly increased under the action of a strong magnetic field along with the increase of the magnetic field intensity. This is because the forbidden bandwidth of 2.5eV and its conduction band electron and valence band hole are not limited by the defects of the traditional large number of crystal structures, the quantum efficiency of the photo-generated electron-hole pair is very high, thus the efficiency of generating hydrogen by decomposing water of the substance is remarkably improved, the strong magnetic field has a very great promotion effect on the generation of the electron and hole pairs, and the separation efficiency is very high, thus promoting the reaction.
Determination of quantum efficiency, number of photons received by the reaction system per unit time:
np＝t·S·Q
wherein t-reaction time (S, min or Hr), effective light area (m) of the S-reactor2) Number of incident photons (umol) measured by Q-radiometer-1m-2s-1) The wavelength range is 400-700nm and the sensitivity is 10-50umol by using an FU100 radiometer-1m-2s-1. The calculation of the apparent quantum efficiency is carried out,
assuming that the incident photons are all absorbed by the system, there is no scattering refraction correction, where
Hydrogen yield (umol), npIs the number of photons incident on the system.
If the weight percentage ratio of the graphene to the silicon alkene is changed, the two atomic weight percentages of the structural formula are changed according to the relative sizes of the silicon alkene and the graphene, the mixture is pure silicon carbon alkene, and a second phase cannot appear. Only silicon carbide scattering peaks appear in Raman plots.
The optical absorption data test proves that the energy band width of the material is 2.5-3.2 eV. Depending on the ratio of the reactants. This feature will be explained in the examples.
The invention is prepared by taking several types of silicon carbenes with forbidden band widths of 2.5eV, 2.8eV,3.0eV and 3.2eV respectively, and gives the water decomposition performance according to different doping elements.
The synthesized silicon-carbon alkene doped with gallium and iron elements is prepared into slurry, and under the irradiation of sunlight, water is decomposed, so that hydrogen is generated, and a sacrificial layer TEOA (methanol and amine propanol mixture) is provided.
Because the two-dimensional crystal has fewer defects compared with other crystals, the periodicity of the crystal can be destroyed only by doping, the specific surface area is large, and the catalytic activity reaction on the two-dimensional crystal enhances the water decomposition capability.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A preparation method of silicon carbene is characterized by comprising the following steps:
weighing high-purity graphene and silicon alkene, weighing nano silicon carbide powder and gallium and iron nano powder, placing the nano silicon carbide powder and the gallium and iron nano powder in a mechanical stirrer, adding acetone, sealing, stirring, standing, taking out, and drying in a vacuum drying oven;
placing the mixed sample in a graphite boat, and placing the graphite boat loaded with the mixture of the silicon alkene, the graphene and the nano silicon carbide on a sample seat of a sample reaction chamber;
thirdly, a variable-frequency heating electric furnace for heating is arranged at the lower part of a sample seat of the reaction chamber, the reaction chamber is provided with a femtosecond laser, a vacuum pump and a circular ring sample collector, a light source at the muzzle of the laser directly irradiates the sample, magnet tiles are pasted around the reaction chamber to generate a static magnetic field, and a coil is added outside the reaction chamber to generate a high-frequency electromagnetic field;
step four, before the reaction chamber reacts, the reaction chamber is firstly vacuumized to 10 degrees-3Starting an electric furnace to heat, and starting a laser at the temperature of 500-1000 ℃ at the same time to scan the sample point by point;
step five, starting high-frequency plasma discharge and a high-frequency magnetic field, and inertially constraining the flow direction to ensure that the smoke dust is repeatedly mixed and reacted in the air;
step six, continuing to scan the sample by aligning the laser radiation until the sample in the graphite boat is ablated by the laser;
seventhly, maintaining the temperature of the reaction chamber at 500-1000 ℃ for 10 minutes;
step eight, turning off a laser power supply and an electric furnace heating power supply, a high-frequency electromagnetic field power supply and a magnetic field, naturally cooling, and collecting a product of sample seed changing, wherein the product is silicon-carbon alkene;
the reaction chamber is composed of a cylindrical stainless steel barrel with the diameter of 100cm and the height of 200cm, a sample seat is positioned in the center of the bottom of the steel barrel, a variable-frequency heating electric furnace is arranged at the lower part of the sample seat, a horizontal circle with the height of 20cm away from the bottom of the stainless steel barrel is provided with corresponding windows at the end points of four mutually perpendicular diameters, the horizontal circle is sealed by glass, 4 femtosecond lasers with the wavelength of 300nm are configured, the gun ports of the lasers face the samples in a graphite boat at the center of the bottom of the reaction chamber, a light source directly irradiates the samples, the reaction chamber is provided with a vacuum pump, a stainless steel circular sample collector is placed on the sample seat in the reaction chamber, four magnet tiles are pasted in four quadrants which are divided by the cylindrical shape of the reaction chamber in the north, south, the west and the west directions of the four quadrants to generate a static magnetic field, and a group of coils are added at the periphery to generate a high-frequency electromagnetic field.
2. The silicon carbene prepared by the method of claim 1 is characterized in that the silicon carbene is a similar single-layer cubic silicon carbide structure formed by double layers of silicon carbene and graphene, one layer of carbon atoms are connected by covalent bonds to form a hexagonal ring shape, one layer of silicon atoms are also connected by covalent bonds to form a hexagonal ring shape, the silicon atom layer and the carbon atom layer are connected by covalent bonds formed by silicon atoms and carbon atoms, and all the bonds are sp3 hybridized bonds; the crystal structure has a chemical formula of (S)ixC1-x)n，0<x<1 is atomic weight percent, n>The number of silicon carbide units formed of one carbon atom and one silicon atom represented by the structural formula (1).
3. A silicon-carbon photovoltaic material prepared using the silicon carbene of claim 2.
4. A method for preparing hydrogen by using the photodecomposition water vapor of the silicon carbene in claim 2, wherein the method for preparing hydrogen by using the photodecomposition water vapor comprises the following steps:
depositing a cobalt-iron alloy layer on the surface of silicon-carbon olefin particles by using a photo-deposition method to obtain cobalt-iron-silicon-carbon olefin nano particles with the cobalt-iron alloy layer mass fraction of 0.05-2.0%, then soaking the Co-Fe-silicon-carbon olefin nano particles in 0.05-0.5 mmol/L dye-methanol solution, standing in the dark for 48-72 hours, filtering, washing with deionized water for 5-10 times, placing in a vacuum drying box, and drying at 80-200 ℃ for 12-24 hours to obtain dye-sensitized Co-Fe-silicon-carbon olefin nano particles;
adding the dye-sensitized Co-Fe-silicon carbon alkene nanoparticles into a triethanolamine TEOA or methanol and triethanolamine mixture aqueous solution reactor with the volume concentration of 10-20% and the volume of 150ml, ultrasonically treating a sample solution for 5-30 minutes by using ultrasonic waves, and introducing argon for 10-60 minutes to obtain a uniform Co-Fe-silicon carbon alkene nanoparticle colloidal suspension without oxygen;
applying a static magnetic field, adding a transparent all-optical condenser, and irradiating the photocatalytic reactor; starting magnetic stirring, and quantitatively measuring hydrogen generated in the reaction vessel by using a gas chromatograph to measure the photocatalytic activity.
5. The method for producing hydrogen gas by photodecomposition of water vapor according to claim 4, wherein the hydrogen gas produced is quantitatively measured by a hydrogen gas detector; the hydrogen detector is a thermal conductivity detector, the carrier gas is argon, the separation column is 13X molecular sieve filler, the external standard method is adopted for calibration, and 0.5mL of gas is extracted from a silica gel pad of the reactor every 30-180 minutes and injected into a gas phase for detection.
6. The method for preparing hydrogen by photolysis of water vapor as claimed in claim 4, wherein in the determination of photocatalytic activity, the porous film of dye-sensitized Co-Fe-silicon carbon alkene nanoparticles is used as a working electrode, the Pt filament is used as a counter electrode, the Ag/AgCl is used as a reference electrode, the porous film is placed in the aqueous solution of a sacrificial agent, argon gas is introduced into the solution for 15 minutes, and a condenser is used for collecting sunlight to irradiate the reaction system solution for electrochemical analysis reaction.
7. The method for preparing hydrogen by photolysis of water vapor as claimed in claim 4, wherein the dye-sensitized Co-Fe-silicon visible light-responsive photocatalytic reduction water hydrogen production system is formed by using silicon carbene as a photo-generated electron hole-centered electron transfer medium, using a sensitizing dye as a connecting molecule, and using in-situ photo-reduction of Co-Fe alloy nanoparticles supported on the silicon carbene as a catalyst.
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