CN110142037B - Preparation method of PSi/graphene photocatalytic composite material - Google Patents
Preparation method of PSi/graphene photocatalytic composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 235000019441 ethanol Nutrition 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 14
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 229910021426 porous silicon Inorganic materials 0.000 claims description 125
- 239000000843 powder Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J35/19—
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- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
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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
- 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
- C01B2203/1088—Non-supported catalysts
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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 discloses a preparation method of a PSi/graphene photocatalytic composite material, which comprises the following steps: uniformly dispersing PSi into absolute ethyl alcohol, adding a silane coupling agent into the absolute ethyl alcohol, uniformly mixing, adding a graphene ethanol solution, stirring for 4-6 hours, performing suction filtration, and drying in a vacuum environment to obtain a PSi/graphene photocatalytic composite material, wherein the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water; the ratio of the 3-aminopropyltriethoxysilane, the PSi to the graphene in the graphene ethanol solution in parts by mass is 0.03: 1: 0.0005. the preparation method is simple, and the performance of the PSi/graphene photocatalytic composite material for photolysis of water to produce hydrogen is 1.3 times that of the pure PSi photocatalytic material for photolysis of water to produce hydrogen.
Description
Technical Field
The invention belongs to the technical field of material preparation and photocatalysis, and particularly relates to a preparation method of a PSi/graphene photocatalytic composite material.
Background
In order to solve the problems of energy crisis and environmental deterioration, the development of green renewable energy sourcesThe hair has received a lot of attention. Solar energy has become an important component of energy utilization and is constantly being developed. Method for producing hydrogen (H) by hydrolyzing water by absorbing solar energy through photocatalyst2) Has become a hot research field. Numerous photocatalysts have been developed by many researchers, such as TiO2CdS and g-C3N4And the like. Compared with the photocatalyst, silicon (Si) is the second most abundant element in the earth crust, the band gap of Si is only 1.12eV, and the silicon (Si) can be well matched with the solar spectrum by utilizing the sunlight with the wavelength less than 1100 nm. Therefore, Si is an ideal visible light responsive photocatalyst. While bulk silicon is limited in photocatalytic performance primarily by energy bands and surface structure. The Porous Silicon (PSi) has adjustable band gap and high specific surface area, and the unique mesoporous structure enlarges the band gap of the silicon photocatalyst, and the conduction band edge of the porous silicon is changed into a more negative position due to the quantum confinement effect, thereby promoting the photocatalytic hydrogen production. However, silicon has been widely used in photocatalytic degradation and organic reactions, and the photolysis of water to produce hydrogen has not been fully explored.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a PSi/graphene photocatalytic composite material.
Therefore, the object of the present invention is achieved by the following means.
A preparation method of a PSi/graphene photocatalytic composite material comprises the following steps:
uniformly dispersing PSi into absolute ethyl alcohol, adding a silane coupling agent into the absolute ethyl alcohol, uniformly mixing, adding a graphene ethanol solution, stirring for 4-6 hours, performing suction filtration, and drying in a vacuum environment to obtain a PSi/graphene photocatalytic composite material, wherein the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water; the ratio of the 3-aminopropyltriethoxysilane, the PSi to the graphene in the graphene ethanol solution in parts by mass is 0.03: 1: 0.0005.
in the above technical scheme, the silane coupling agent contains 3-aminopropyltriethoxysilane, ethanol and water in a volume ratio of 10: 36: 4.
in the above technical scheme, the method for uniformly dispersing the PSi into the absolute ethyl alcohol comprises: and carrying out ultrasonic treatment on the PSi in absolute ethyl alcohol for 10-20 min.
In the technical scheme, the drying temperature is 30-50 ℃.
In the above technical scheme, the graphene is single-layer graphene.
In the technical scheme, the concentration of the graphene ethanol solution is 100-130 mg/L.
In the above technical scheme, the preparation method of the PSi comprises the following steps:
in the step 1, the heating speed of heating from room temperature of 20-25 ℃ to 750-850 ℃ is 8-12 ℃/min.
In the step 1, the inert gas is argon.
in the technical scheme, the acid solution is HCl with the concentration of 0.3-0.5M.
And 3, washing the black powder purified substance obtained in the step 2 with deionized water and/or ethanol for at least 3 times, and drying the black powder purified substance at 50-60 ℃ for at least 3 hours to obtain PSi.
In the above technical scheme, when the PSi is uniformly dispersed to the absolute ethyl alcohol, the ratio of the mass of the PSi to the volume of the absolute ethyl alcohol is 0.13: (45-55), the unit of the mass is g, and the unit of the volume is mL.
The PSi/graphene photocatalytic composite material is obtained by the preparation method of the PSi/graphene photocatalytic composite material.
The preparation method of the PSi/graphene photocatalytic composite material is applied to improving the performance of photolysis of water to produce hydrogen.
In the technical scheme, compared with a pure PSi photocatalytic material, the performance of the PSi/graphene photocatalytic composite material for photolysis of water to produce hydrogen is improved by 1.3 times.
Compared with the prior art, the preparation method is simple, and the performance of the PSi/graphene photocatalytic composite material for photolysis of water to produce hydrogen is 1.3 times that of the pure PSi photocatalytic material for photolysis of water to produce hydrogen.
Drawings
FIG. 1 is an XRD pattern of PSi prepared by the magnesiothermic reduction method in MCM-41 and example 1;
FIG. 2 is an SEM photograph of PSi prepared by magnesiothermic reduction method in example 1;
FIG. 3 is a TEM image of PSi prepared by magnesiothermic reduction method in example 1;
FIG. 4 is an XRD pattern of PSi/graphene-0.05 wt% prepared by a simple solution mixing method in example 1;
FIG. 5(a) is an XPS plot of Si 2p in PSi/graphene-0.5 wt% prepared by simple solution mixing as in example 3; FIG. 5(b) is an XPS plot of C1s in PSi/graphene-0.5 wt% prepared by simple solution mixing method for example 3;
FIG. 6 is an SEM image of PSi/graphene-0.5 wt% prepared by a simple solution mixing method in example 3;
FIG. 7 is a TEM image of PSi/graphene-0.5 wt% prepared by a simple solution mixing method in example 3;
FIG. 8 is a graph comparing the photocurrent measurements of PSi/graphene-0.05 wt% prepared by simple solution mixing method for PSi and example 1;
fig. 9 is a comparison graph of the performance of the PSi/graphene photocatalytic composite material prepared by the simple solution mixing method in the PSi and examples 1, 2 and 3 for the photolysis of water to produce hydrogen.
Detailed Description
In a specific embodiment of the present invention, the drug purchase sources are as follows:
the types and manufacturers of the related instruments are as follows:
in the following examples, the graphene is single-layer graphene and the inert gas is argon.
The following graphene ethanol solution has a concentration of 130mg/L, and the specific preparation method comprises the following steps: and (3) placing the graphene in ethanol to enable the concentration of the graphene in the graphene ethanol solution to reach 130mg/L, and performing ultrasonic dispersion for 6 hours to obtain the graphene ethanol solution.
The preparation method of the following silane coupling agent comprises the following steps: 3-aminopropyltriethoxysilane, ethanol and water are mixed evenly, and after mixing, the mixture is subjected to ultrasonic treatment for 15 minutes and used as a silane coupling agent.
The technical scheme of the invention is further explained by combining the drawings and the specific embodiment.
Example 1
A preparation method of a PSi/graphene photocatalytic composite material comprises the following steps:
performing ultrasonic treatment on 0.13g of PSi in 50mL of absolute ethyl alcohol for 15min to uniformly disperse the PSi in the absolute ethyl alcohol, adding 0.2mL of silane coupling agent into the absolute ethyl alcohol, uniformly mixing, stirring for 30min, adding 0.5mL of graphene ethanol solution, stirring for 5 h, performing suction filtration, and drying in a vacuum environment to obtain a PSi/graphene photocatalytic composite material (PSi/GR-0.05 wt% composite material), wherein the drying temperature is 50 ℃, the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water, and the volume ratio of the 3-aminopropyltriethoxysilane to the ethanol to the water is 10: 36: 4. the ratio of 3-aminopropyltriethoxysilane to PSi to graphene in the graphene ethanol solution in parts by mass is 0.03: 1: 0.0005.
the preparation method of the PSi comprises the following steps:
And 3, washing the black powder purified substance obtained in the step 2 by deionized water and ethanol for 3 times respectively, and drying the black powder purified substance in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain PSi.
As shown in fig. 1, the crystal structures of MCM-41 and PSi prepared in example 1 were investigated by XRD. PSi has distinct diffraction peaks at 28.3 °, 47.2 °, 56 °, 69 ° and 76.3 ° corresponding to the (111), (220), (311), (400) and (331) planes of cubic phase Si (JCPDS27-1402), respectively. In contrast, amorphous silica exhibits a very weak swelling. The diffraction peak of the PSi is narrow and sharp, and no obvious amorphous scattering diffraction peak exists, which indicates that pure PSi is successfully prepared by magnesium thermal reduction of the mesoporous MCM-41, and the prepared PSi has high purity and crystallinity.
As shown in fig. 2, it can be seen from the SEM image of the PSi prepared in example 1 that the obtained PSi exhibited irregular particle size with abundant porous structure.
Fig. 3 is a TEM image of PSi prepared by the magnesiothermic reduction method of example 1, and as shown in fig. 3, it can be seen from the TEM image that there is a significant mesoporous structure in PSi, and PSi is composed of crystalline Si nanoparticles cross-linked due to the fact that magnesium vapor captures O atoms in the mesoporous silica during the magnesiothermic reduction, and the porous structure of the mesoporous silica is maintained during the magnesiothermic reduction.
As shown in FIG. 4, the diffraction peak of PSi was clearly observed in the PSi/GR-0.05 wt% composite material prepared in example 1, and the position and shape of the diffraction peak were hardly changed from those of pure PSi, indicating that the composite maintained the structure of PSi well. Since the graphene used is single-layer graphene and the content of graphene in the composite material is small, a diffraction peak of graphene cannot be observed.
Example 2 comparison
A preparation method of a PSi/graphene photocatalytic composite material comprises the following steps:
performing ultrasonic treatment on 0.13g of PSi in 50mL of absolute ethyl alcohol for 15min to uniformly disperse the PSi in the absolute ethyl alcohol, adding 0.2mL of silane coupling agent into the absolute ethyl alcohol, uniformly mixing, stirring for 30min, adding 0.5mL of graphene ethanol solution, stirring for 5 h, performing suction filtration, and drying in a vacuum environment to obtain a PSi/graphene photocatalytic composite material (PSi/GR-0.10 wt% composite material), wherein the drying temperature is 50 ℃, the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water, and the volume ratio of the 3-aminopropyltriethoxysilane to the ethanol to the water is 10: 36: 4. the ratio of 3-aminopropyltriethoxysilane to PSi to graphene in the graphene ethanol solution in parts by mass is 0.03: 1: 0.001.
the preparation method of the PSi comprises the following steps:
And 3, washing the black powder purified substance obtained in the step 2 by deionized water and ethanol for 3 times respectively, and drying the black powder purified substance in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain PSi.
Example 3 comparison
A preparation method of a PSi/graphene photocatalytic composite material comprises the following steps:
performing ultrasonic treatment on 0.13g of PSi in 50mL of absolute ethyl alcohol for 15min to uniformly disperse the PSi in the absolute ethyl alcohol, adding 0.2mL of silane coupling agent into the absolute ethyl alcohol, uniformly mixing, stirring for 30min, adding 0.5mL of graphene ethanol solution, stirring for 5 h, performing suction filtration, and drying in a vacuum environment to obtain a PSi/graphene photocatalytic composite material (PSi/GR-0.50 wt% composite material), wherein the drying temperature is 50 ℃, the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water, and the volume ratio of the 3-aminopropyltriethoxysilane to the ethanol to the water is 10: 36: 4. the ratio of 3-aminopropyltriethoxysilane to PSi to graphene in the graphene ethanol solution in parts by mass is 0.03: 1: 0.005.
the preparation method of the PSi comprises the following steps:
And 3, washing the black powder purified substance obtained in the step 2 by deionized water and ethanol for 3 times respectively, and drying the black powder purified substance in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain PSi.
As shown in FIGS. 5(a) and 5(b), Gaussian fitting was performed on the PSi/GR-0.5 wt% composite high resolution spectra, where 5(a) is the XPS plot for Si 2p in PSi/graphene-0.5 wt% and 5(b) is the XPS plot for C1s in PSi/graphene-0.5 wt%. As shown in FIG. 5(a), the Si 2P is divided into several peaks corresponding to SiOx. The peak at 100.1eV indicates mesoporous SiO2PSi is obtained through magnesiothermic reduction. However, SiOxMay be present as oxides formed during the preparation of the aqueous solution and exposure to air of the PSi/GR-0.5 wt% composite. As shown in FIG. 5(b), C1s can be divided into several peaks by Gaussian fitting the C1s spectra286.1eV, 284.7eV, 282.4eV, of which 284.7eV is a characteristic peak of graphitic carbon. The successful preparation of the PSi/GR composite material (i.e., the PSi/graphene photocatalytic composite material) is known from XPS.
In the embodiment of the invention, the graphene is a single-layer layered structure, and the PSi is a granular structure, and by comparison, the existence of the graphene and the PSi can be judged by SEM shown in fig. 6, which further illustrates that the PSi/graphene composite material is successfully prepared.
As shown in fig. 7, compared with the TEM image of pure PSi, the nanoparticle and mesoporous structure of PSi in the PSi/graphene photocatalytic composite material (PSi/GR-0.5 wt% composite material) prepared in example 3 also became obscure, probably due to the presence of the silane coupling agent and the graphene composite material, filling the mesopores of PSi and masking the surface of PSi. SEM and TEM provided conclusive evidence that the PSi/GR composites were successfully prepared.
As shown in FIG. 8, it can be clearly seen that the photocurrent of the PSi/graphene photocatalytic composite material (PSi/GR-0.05 wt% composite material) prepared in example 1 is higher than that of pure PSi. The result shows that due to the good conductivity of the graphene, electrons generated by PSi in the photo-excited composite material can be rapidly transferred to the FTO substrate through the graphene sheet layer, so that the migration rate of the electrons in a composite system is accelerated, the recombination of photo-generated electron-hole pairs is effectively inhibited, the separation efficiency of photo-generated carriers is improved, and the photolysis water hydrogen production performance of the composite material is enhanced.
As shown in FIG. 9, from the comparison of the hydrogen performance test of photolysis water of pure PSi and PSi/GR composite material under visible light irradiation, it can be seen that the hydrogen production rate of pure PSi is 604.7 μmol h-1g-1When the GR (graphene) with proper content is compounded in the PSi/GR composite material, the performance of photolysis water-splitting hydrogen production of high-purity PSi can be effectively improved. Wherein the PSi/GR-0.05 wt% composite material (example 1) has the highest hydrogen production performance, and the rate is 813.6 mu mol h-1g-1Approximately 1.3 times the pure PSi. When the content of GR is more than 0.05 wt%, the hydrogen generation performance of the composite material is reduced and is lower than that of pure PSi. This is probably because excessive GR incorporation into the surface of PSi reduces the active sites on the surface of PSi.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a porous silicon/graphene photocatalytic composite material is characterized by comprising the following steps:
uniformly dispersing porous silicon into absolute ethyl alcohol, adding a silane coupling agent into the absolute ethyl alcohol, uniformly mixing, adding a graphene ethanol solution, stirring for 4-6 hours, performing suction filtration, and drying in a vacuum environment to obtain a porous silicon/graphene photocatalytic composite material, wherein the silane coupling agent is formed by uniformly mixing 3-aminopropyltriethoxysilane, ethanol and water; the mass part ratio of the 3-aminopropyltriethoxysilane to the porous silicon to the graphene in the graphene ethanol solution is 0.03: 1: 0.0005.
2. the preparation method of the porous silicon/graphene photocatalytic composite material as claimed in claim 1, wherein the silane coupling agent comprises 3-aminopropyltriethoxysilane, ethanol and water in a volume ratio of 10: 36: 4.
3. the preparation method of the porous silicon/graphene photocatalytic composite material according to claim 2, wherein the method for uniformly dispersing the porous silicon in the absolute ethyl alcohol comprises the following steps: and (3) carrying out ultrasonic treatment on the porous silicon in absolute ethyl alcohol for 10-20 min.
4. The preparation method of the porous silicon/graphene photocatalytic composite material according to claim 3, wherein the drying temperature is 30-50 ℃; the graphene is single-layer graphene.
5. The preparation method of the porous silicon/graphene photocatalytic composite material according to claim 4, wherein the concentration of the graphene ethanol solution is 100-130 mg/L.
6. The preparation method of the porous silicon/graphene photocatalytic composite material according to claim 5, wherein the preparation method of the porous silicon comprises the following steps:
step 1, uniformly mixing MCM-41 and excessive magnesium powder, heating the mixture to 750-850 ℃ from the room temperature of 20-25 ℃ in an inert gas environment, and preserving the heat for 9-12 hours to obtain black powder;
step 2, soaking the black powder obtained in the step 1 in acid liquor for 4-8 hours to remove MgO and Mg in the black powder2Si and the rest magnesium powder to obtain a black powder purified product;
and 3, washing the black powder purified substance obtained in the step 2 with deionized water and/or ethanol for at least 3 times, and drying the black powder purified substance at 50-60 ℃ for at least 3 hours to obtain the porous silicon.
7. The method for preparing the porous silicon/graphene photocatalytic composite material according to claim 6,
when the porous silicon is uniformly dispersed to the absolute ethyl alcohol, the ratio of the mass of the porous silicon to the volume of the absolute ethyl alcohol is 0.13: (45-55), wherein the unit of the mass is g, and the unit of the volume is mL;
in the step 1, the temperature is heated from room temperature of 20-25 ℃ to 750-850 ℃ at a heating rate of 8-12 ℃/min;
in the step 1, the inert gas is argon;
in the step 2, the acid solution is HCl with the concentration of 0.3-0.5M.
8. The porous silicon/graphene photocatalytic composite material prepared by the preparation method of the porous silicon/graphene photocatalytic composite material as claimed in any one of claims 1 to 7.
9. The application of the porous silicon/graphene photocatalytic composite material obtained by the preparation method according to any one of claims 1 to 7 in improving the performance of hydrogen production through water photolysis.
10. The application of the porous silicon/graphene photocatalytic composite material in the photolysis of water to produce hydrogen is 1.3 times of the performance of pure porous silicon photocatalytic material in the photolysis of water to produce hydrogen.
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