CN113786826A - Preparation method of porous silicon-zinc oxide composite material for wastewater degradation - Google Patents
Preparation method of porous silicon-zinc oxide composite material for wastewater degradation Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002351 wastewater Substances 0.000 title claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 13
- 230000015556 catabolic process Effects 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 181
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 119
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 105
- 239000010703 silicon Substances 0.000 claims abstract description 105
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000008367 deionised water Substances 0.000 claims abstract description 87
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 87
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 87
- 239000010439 graphite Substances 0.000 claims abstract description 87
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 64
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 62
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 60
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 30
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 30
- 241000270722 Crocodylidae Species 0.000 claims abstract description 29
- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011550 stock solution Substances 0.000 claims description 61
- 238000001035 drying Methods 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 106
- 238000006243 chemical reaction Methods 0.000 abstract description 63
- 239000011787 zinc oxide Substances 0.000 abstract description 53
- 239000000463 material Substances 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 52
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 52
- 239000004810 polytetrafluoroethylene Substances 0.000 description 52
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 238000004528 spin coating Methods 0.000 description 26
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- 238000005406 washing Methods 0.000 description 26
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000001052 transient effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 229910003471 inorganic composite material Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention provides a preparation method of a porous silicon-zinc oxide composite material for wastewater degradation, which comprises the following steps: firstly, preparing graphite particles, hydrofluoric acid solution, hydrogen peroxide solution and deionized water into corrosive solution; then corroding the silicon wafer by using a corrosive solution to prepare a porous silicon wafer; then mixing the silver nitrate solution, the hexamethylenetetramine solution and the zinc nitrate solution with deionized water to obtain an electrolyte solution; and finally, fixing the porous silicon wafer and the aluminum sheet by using a double-head crocodile lead, and simultaneously immersing the porous silicon wafer and the aluminum sheet into an electrolyte solution to react to obtain the composite material. According to the invention, the porous silicon wafer is prepared by carbon catalytic etching, and then zinc oxide is covered on the surface of the porous silicon wafer by adopting an electrochemical deposition method, so that the method is normal temperature and normal pressure, simple in process and strong in operability. The composite material obviously improves the separation of electron and hole pairs at the interface of the material, increases the contact area of the composite material and reactants, improves the light absorption capacity and the reaction rate, and can be applied to the photocatalytic degradation of organic matters in wastewater.
Description
Technical Field
The invention belongs to the technical field of inorganic composite materials, and relates to a porous silicon-zinc oxide composite material and a preparation method thereof.
Background
The semiconductor photocatalytic material can be activated by photons under the irradiation of light to realize the flow of electrons or holes, and has strong oxidation or reduction effect on the surface, namely, a reaction system directly converts absorbed light energy into chemical energy under the photocatalysis, so that a plurality of reactions which are difficult to realize under the normal condition can be smoothly carried out under the mild condition, and the semiconductor photocatalytic material does not change before and after the reaction.
The zinc oxide is a direct wide band gap semiconductor, has good light absorption and response performance in the ultraviolet light range with the wavelength of 200-380nm, and the zinc oxide thin layer has very high transmittance in the visible light range, which can be up to more than 90%. The zinc oxide has rich sources of raw materials, no toxicity, low price, lower temperature required by growth and preparation and low requirement on experimental equipment, so that the application of the zinc oxide in the photoelectric field is more and more emphasized. However, the efficiency of pure zinc oxide as a photocatalyst is still relatively low, because the photogenerated carriers, i.e. electrons and holes, generated in the zinc oxide after illumination cannot be effectively separated, so that the electrons and the holes can be quickly compounded, and organic pollutants cannot be effectively catalyzed and degraded. Therefore, in practical application, zinc oxide and other materials are generally utilized to form a heterojunction, so that electrons and holes are effectively separated, the aim of improving photocatalysis is further fulfilled, and the photocatalysis is enhanced.
Silicon is a narrow bandgap semiconductor with good absorption response in the visible range of 400-800nm wavelength. In addition, the porous silicon has excellent physical and chemical properties and a large specific surface area, photons in a visible light region can be effectively absorbed, and photons can be effectively captured and photo-generated carriers can be quickly conducted to the surface of a reactant through a built-in electric field of a composite material interface by etching a porous structure on the surface of monocrystalline silicon, so that the porous silicon can be widely applied to the field of photocatalytic degradation of organic matters.
Therefore, it can be seen from the above that the composite material of porous silicon and zinc oxide should have good photon absorption capability and high photoelectric conversion efficiency in a broad spectral range of 200-800nm wavelength. Particularly, for the nano-scale porous silicon-zinc oxide composite material, the composite material has a large specific surface area and good electron mobility, so that the composite material has excellent performance in the aspect of photocatalysis application. Therefore, the photon-generated carriers generated by the nano-scale porous silicon-zinc oxide composite material under the excitation of light have strong oxidation reduction capability, main pollution components organic matters in wastewater can be effectively treated, the degraded products have no pollution to water, other reagents are not required to be additionally added in the degradation process, and the composite material is green and environment-friendly.
The porous silicon and the metal oxide material are compounded mainly in two types, namely a coating type and an embedding type. Most of the current composite methods not only have high cost, complex operation and harsh conditions, but also can not achieve the effects of energy conservation and environmental protection. The invention patent with the publication number of CN110277248B provides a zinc oxide-porous silicon composite material and a preparation method and application thereof, and the preparation method comprises the following steps: preparation of porous silicon: preparing a porous silicon structure on a monocrystalline silicon substrate by using an electrochemical anodic etching method; preparation of zinc oxide sol: preparing a sol capable of providing zinc ions; preparing a composite material: compounding a nano zinc oxide material on the surface of the porous silicon by utilizing a vacuum filtration and glue homogenizing method, and forming a zinc oxide-coated porous silicon-zinc oxide composite material, namely a zinc oxide-porous silicon composite material after heat treatment. The nano zinc oxide layer on the surface of the porous silicon is utilized to realize passivation on the surface of the porous silicon, and the synergistic effect of the pseudocapacitance characteristic of the zinc oxide and the double electric layer characteristic of the porous silicon is utilized to greatly improve the capacitance characteristic, the charge-discharge characteristic and the electrochemical stability of the porous silicon, improve the problem of active chemical characteristics of the surface of the porous silicon and widen the application prospect of the porous silicon in the related fields of luminescent materials, devices and the like; but the method has strict preparation conditions, adopts vacuum filtration combined with a glue homogenizing method and heat treatment, and has complex process; the zinc oxide-porous silicon composite material prepared by the method can be used for preparing electrodes, is applied to capacitors, and is not suitable for the field of wastewater degradation.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method of a porous silicon-zinc oxide composite material for wastewater degradation.
The technical scheme of the invention comprises the following steps:
(1) adding graphite particles into an etching stock solution prepared from hydrofluoric acid solution, hydrogen peroxide solution and deionized water, and performing ultrasonic dispersion for 10min at room temperature to obtain an etching solution;
(2) dripping the etching solution onto the cleaned silicon wafer by using a rubber head dropper, etching for 0.5-48h at room temperature, and cleaning and drying to obtain a porous silicon wafer;
(3) mixing 0.025mol/L silver nitrate solution, 0.025mol/L hexamethylenetetramine solution and 0.25mol/L zinc nitrate solution with deionized water according to the volume ratio of 1:10:5-15 in a beaker to obtain electrolyte solution;
(4) and (3) placing a beaker of the electrolyte solution in a water bath for preheating, fixing the corroded porous silicon wafer and the aluminum sheet by using a double-head crocodile lead, immersing the porous silicon wafer and the aluminum sheet into the electrolyte solution at the same time, and reacting for 1-10 hours to obtain the porous silicon-zinc oxide composite material.
Further, in the step (1), the graphite particles are micro-nano graphite particles, and the particle size range is 10nm-10 μm.
Further, in the step (1), the ratio of the weight of the graphite particles to the volume of the etching stock solution is 0.1g:5-20 mL. By adopting the proportion, the graphite particles can be fully mixed with the corrosive stock solution.
Further, in the step (1), the concentration of hydrofluoric acid in the etching stock solution is 0.8-40 wt%.
Further, in the step (1), the hydrogen peroxide concentration of the etching stock solution is 0.3-6 wt%.
Furthermore, in the step (4), the water bath temperature of the beaker of the electrolyte solution is 40-80 ℃, the water bath temperature is too low to decompose the zinc nitrate into zinc oxide to deposit on the surface of the porous silicon, and the appearance and the structure of the zinc oxide can be damaged when the water bath temperature is too high.
Further, in the step (4), the purity of the aluminum sheet is 99%, and the size of the aluminum sheet is 2-16cm2. The purity and the size of the aluminum sheet have certain influence on the appearance and the growth rate of the zinc oxide deposited on the porous silicon.
In the step (4), the reaction time is 1-10 h. If the reaction time is too short, the amount of zinc oxide covered on the surface of the porous silicon is too small, and if the reaction time is too long, the amount of zinc oxide covered on the surface of the porous silicon is too large, which is not favorable for exerting the excellent characteristics of the composite material.
Compared with the prior art, the preparation method has the advantages that the porous silicon wafer is prepared by utilizing carbon catalytic etching, then the surface of the porous silicon wafer is covered with zinc oxide by adopting an electrochemical deposition method, and the porous silicon-zinc oxide composite material is prepared by adopting a preparation method at normal temperature and normal pressure, so that the preparation method is simple in process and strong in operability. The porous silicon and the zinc oxide of the composite material are both semiconductor materials, a heterostructure is formed after the porous silicon and the zinc oxide are compounded, after the porous silicon and the zinc oxide are irradiated by light, electrons of a valence band are excited to a conduction band to generate holes, and OH-and H-are adsorbed2O is oxidized into OH free radicals, and the adsorbed organic wastewater is further oxidized due to the strong oxidizing property of the OH free radicals, the porous silicon in the OH free radicals also provides a large specific surface area in the reaction process, so that the composite material is easy to adsorb the organic wastewater, and in addition, the excellent conductivity of the composite material provides good transmission communication for photo-generated electronsTherefore, the porous silicon-zinc oxide composite material has the functions of photoelectric conversion and chemical catalytic degradation in a reaction system. The composite material obviously improves the separation of electron and hole pairs at the interface of the material, increases the contact area of the composite material and reactants, improves the light absorption capacity and the reaction rate, and can be applied to the photocatalytic degradation of organic matters in wastewater.
Drawings
FIG. 1 is an SEM image of the surface of porous silicon wafer nanoparticles.
Fig. 2 is a SEM image of the surface of the porous silicon-zinc oxide composite material.
Fig. 3 is a photocurrent-time curve of a porous silicon-zinc oxide composite electrode.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the embodiments are not limited to the invention, and the advantages of the invention will be understood more clearly by the description. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention. The positional relationships described in the embodiments are all the same as those shown in the drawings, and other portions not described in detail in the embodiments are all the related art.
Preparing raw materials: respectively preparing 0.025mol/L silver nitrate solution, 0.25mol/L zinc nitrate solution, 0.025mol/L hexamethylenetetramine solution, 40 wt% hydrofluoric acid solution and 30 wt% hydrogen peroxide solution; the prepared size was 4cm2、6cm2、8cm2、10cm2、12cm2、14cm2、16cm2The purity of the aluminum sheets is more than 99 percent; grinding to prepare graphite particles with the particle size range of 10nm-10 mu m.
Example 1
Preparing 10mL of corrosion stock solution by taking 2mL of the hydrofluoric acid solution, 1mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 24h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 10mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 70 ℃ water bath kettle for preheating for 10min, and then mixing the porous silicon wafer with the electrolyte solution with the size of 6cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 2
Preparing 15mL of corrosion stock solution by taking 3mL of the hydrofluoric acid solution, 1.5mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 20h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 10mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then adding the porous silicon and the deionized water with the size of 6cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 3
Preparing 12mL of corrosion stock solution by taking 2.5mL of the hydrofluoric acid solution, 1.5mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 18h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 119.2mL of electrolyte solution from 1.2mL of the prepared silver nitrate solution, 12mL of zinc nitrate solution, 12mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, preheating the beaker in a 70 ℃ water bath for 10min, and then adding the porous silicon and the electrolyte solution with the size of 8cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 4
Preparing 12mL of corrosive stock solution by taking 4mL of the hydrofluoric acid solution, 2.5mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 12h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 150mL of electrolyte solution from 1.5mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 15mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 10cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 5
Preparing 20mL of corrosion stock solution by taking 3.5mL of the hydrofluoric acid solution, 1.7mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.18g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 24h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 150mL of electrolyte solution from 1.5mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 15mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 8cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 6
Preparing 20mL of corrosive stock solution by taking 4mL of the hydrofluoric acid solution, 2.5mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.2g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 20h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 140mL of electrolyte solution from 1.4mL of the prepared silver nitrate solution, 14mL of zinc nitrate solution, 14mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 8cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 7
Preparing 10mL of corrosion stock solution by taking 1.5mL of the hydrofluoric acid solution, 1mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 24h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
0.5mL of the prepared silver nitrate solution, 5mL of the zinc nitrate solution and 5mL of the hexamethylenetetramine solution are takenPreparing the electrolyte solution and deionized water into 80mL electrolyte solution, adding into a beaker, placing the beaker in a 40 deg.C water bath to preheat for 10min, and adding the porous silicon with a size of 4cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 8
Preparing 12mL of corrosive stock solution by taking 5mL of the hydrofluoric acid solution, 3.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 15h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 0.8mL of the prepared silver nitrate solution, 8mL of the zinc nitrate solution, 8mL of the hexamethylenetetramine solution and deionized water into 100mL of electrolyte solution, adding the electrolyte solution into a beaker, placing the beaker in a 55 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the deionized water with the size of 10cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 4.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 9
Preparing 15mL of corrosion stock solution by taking 4mL of the hydrofluoric acid solution, 3.1mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 12h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 10mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, and placing the beaker in a 70 ℃ water bath kettlePreheating for 10min, and mixing the above porous silicon with a size of 8cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 10
Preparing 10mL of corrosion stock solution by taking 2.5mL of the hydrofluoric acid solution, 2mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 26h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 140mL of electrolyte solution from 1.1mL of the prepared silver nitrate solution, 11mL of zinc nitrate solution, 11mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 60 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 12cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 6 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 11
Preparing 20mL of corrosive stock solution by taking 5mL of the hydrofluoric acid solution, 3.5mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 30h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 130mL of electrolyte solution from 1.2mL of the prepared silver nitrate solution, 12mL of zinc nitrate solution, 12mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 65 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 10cm2Aluminum sheet passing double headAnd fixing the crocodile lead in an electrolyte solution for reaction for 5.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon to obtain the porous silicon-zinc oxide composite material.
Example 12
Preparing 15mL of corrosion stock solution by taking 6mL of the hydrofluoric acid solution, 3.5mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 25h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 120mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 10mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 85 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 12cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 13
Preparing 20mL of corrosive stock solution by taking 5mL of the hydrofluoric acid solution, 3.5mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 20h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 90mL of electrolyte solution from 0.9mL of the prepared silver nitrate solution, 9mL of zinc nitrate solution, 9mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 8cm2The aluminum sheet is fixed in the electrolyte solution through the double-head crocodile lead to react for 3.5 hours, so that the zinc oxide can uniformly grow for a plurality of timesAnd (4) obtaining the porous silicon-zinc oxide composite material on the surface of the porous silicon.
Example 14
Preparing 20mL of corrosive stock solution by taking 6mL of the hydrofluoric acid solution, 4.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.2g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 18h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 120mL of electrolyte solution from 1.5mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 15mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 12cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 4 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 15
Preparing 20mL of corrosive stock solution by taking 7mL of the hydrofluoric acid solution, 5.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.2g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 25h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 140mL of electrolyte solution from 1.5mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 15mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 12cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 16
Preparing 20mL of corrosion stock solution by taking 7.2mL of the hydrofluoric acid solution, 3.7mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.2g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 20h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 150mL of electrolyte solution from 1.5mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 15mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 14cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 17
Preparing 10mL of corrosion stock solution by taking 2mL of the hydrofluoric acid solution, 1.5mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 14h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 130mL of electrolyte solution from 1.2mL of the prepared silver nitrate solution, 12mL of zinc nitrate solution, 12mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 10cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 18
Preparing 15mL of corrosion stock solution by taking 3mL of the hydrofluoric acid solution, 1.7mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 18h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 135mL of electrolyte solution from 1.4mL of the prepared silver nitrate solution, 14mL of zinc nitrate solution, 14mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 85 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 10cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2.5 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 19
Preparing 12mL of corrosive stock solution by taking 2mL of the hydrofluoric acid solution, 1mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing for 10min at room temperature, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding for 24h at room temperature, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 0.9mL of the prepared silver nitrate solution, 9mL of the zinc nitrate solution, 9mL of the hexamethylenetetramine solution and deionized water into 100mL of electrolyte solution, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the deionized water with the size of 6cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 2 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 20
Preparing 18mL of corrosive stock solution by taking 6mL of the hydrofluoric acid solution, 4.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 20h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 125mL of electrolyte solution from 1.1mL of the prepared silver nitrate solution, 11mL of zinc nitrate solution, 11mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, preheating the beaker in a water bath kettle at 85 ℃ for 10min, and then adding the porous silicon and the electrolyte solution with the size of 8cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 21
Preparing 16mL of corrosive stock solution by taking 3mL of the hydrofluoric acid solution, 2.5mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 12h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 150mL of electrolyte solution from 1.3mL of the prepared silver nitrate solution, 13mL of zinc nitrate solution, 13mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, preheating the beaker in a 70 ℃ water bath kettle for 10min, fixing the porous silicon and an aluminum sheet with the size of 16cm2 in the electrolyte solution through a double-head crocodile lead, and reacting for 3h to enable zinc oxide to uniformly grow on the surface of the porous silicon to obtain the porous silicon-zinc oxide composite material.
Example 22
Preparing 20mL of corrosive stock solution by taking 7mL of the hydrofluoric acid solution, 5.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.1g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 22h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 0.8mL of the prepared silver nitrate solution, 8mL of the zinc nitrate solution, 8mL of the hexamethylenetetramine solution and deionized water into 100mL of electrolyte solution, adding the electrolyte solution into a beaker, placing the beaker in a 70 ℃ water bath kettle for preheating for 10min, and then fixing the porous silicon and an aluminum sheet with the size of 12cm2 in the electrolyte solution through a double-head crocodile lead to react for 2.5h, so that zinc oxide can uniformly grow on the surface of the porous silicon to obtain the porous silicon-zinc oxide composite material.
Example 23
Preparing 15mL of corrosion stock solution by taking 0.6mL of the hydrofluoric acid solution, 1mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.14g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 1h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 5mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 10cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
Example 24
Preparing 15mL of corrosion stock solution by taking 14mL of the hydrofluoric acid solution, 0.3mL of the hydrogen peroxide solution and deionized water, adding the corrosion stock solution into a polytetrafluoroethylene reaction container, then adding 0.13g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 0.5h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 1mL of the prepared silver nitrate solution, 8mL of the prepared zinc nitrate solution, 10mL of the prepared hexamethylenetetramine solution and deionized water into 100mL of electrolyte solution, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then fixing the porous silicon and an aluminum sheet with the size of 12cm2 in the electrolyte solution through a double-head crocodile lead to react for 3.5h, so that zinc oxide can uniformly grow on the surface of the porous silicon to obtain the porous silicon-zinc oxide composite material.
Example 25
Preparing 20mL of corrosive stock solution by taking 12mL of the hydrofluoric acid solution, 0.2mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.12g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing the graphite particles at room temperature for 10min, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding the silicon wafer at room temperature for 5h, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying the silicon wafer in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 12mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a 90 ℃ water bath kettle for preheating for 10min, fixing the porous silicon and an aluminum sheet with the size of 10cm2 in the electrolyte solution through a double-head crocodile lead, and reacting for 2.5h to enable the zinc oxide to uniformly grow on the surface of the porous silicon, thereby obtaining the porous silicon-zinc oxide composite material.
Example 26
Preparing 20mL of corrosive stock solution by taking 2mL of the hydrofluoric acid solution, 4mL of the hydrogen peroxide solution and deionized water, adding the corrosive stock solution into a polytetrafluoroethylene reaction container, then adding 0.15g of graphite particles into the polytetrafluoroethylene reaction container, ultrasonically dispersing for 10min at room temperature, sucking 1mL of the solution by using a rubber head dropper, uniformly spin-coating the solution on a cleaned silicon wafer, corroding for 8h at room temperature, washing the residual graphite particles on the surface of the silicon wafer by using the deionized water, and drying in a vacuum drying oven at 40 ℃ to obtain the porous silicon wafer.
Preparing 100mL of electrolyte solution from 1mL of the prepared silver nitrate solution, 15mL of zinc nitrate solution, 10mL of hexamethylenetetramine solution and deionized water, adding the electrolyte solution into a beaker, placing the beaker in a water bath kettle at 80 ℃ for preheating for 10min, and then adding the porous silicon and the electrolyte solution with the size of 12cm2The aluminum sheet is fixed in an electrolyte solution through a double-head crocodile lead and reacts for 3 hours, so that the zinc oxide can uniformly grow on the surface of the porous silicon, and the porous silicon-zinc oxide composite material is obtained.
The porous silicon wafer and the porous silicon-zinc oxide composite material prepared in example 1 were examined, and the surface of the material was observed under a scanning electron microscope. The scanning electron microscope image of the porous silicon wafer is shown in fig. 1, the surface of the silicon wafer is densely distributed with hole structures, and the microstructure uniformity of the porous silicon is better; the scanning electron microscope image of the porous silicon-zinc oxide composite material is shown in fig. 2, and the zinc oxide film is uniformly coated on the surface of the porous silicon to form the porous silicon-zinc oxide composite material.
The porous silicon-zinc oxide composite electrode prepared in example 1 was tested in 2.5X 10-5mol/L rhodamine B solution, and the photocurrent-time curve obtained is shown in FIG. 3, where on and off represent turning on and off the light source, respectively. As can be seen from FIG. 3, the electrode has a distinct transient photocurrent, indicating that the electrode is photoresponsive to degradation of the rhodamine B solution. The reason is that the porous silicon and the zinc oxide are both semiconductor materials, a heterostructure is formed after the porous silicon and the zinc oxide are compounded, and after the porous silicon and the zinc oxide are irradiated by light, electrons in a valence band are excited to a conduction band to generate holes, and OH-and H-are adsorbed2O is oxidized into OH free radicals, and the adsorbed rhodamine B is further oxidized due to the strong oxidizing property of the OH free radicals, the porous silicon in the O-. In addition, it is known from the figure that the transient photocurrent value of the porous silicon-zinc oxide composite electrode is about 55.7 muA/c at 250Vm2。
The porous silicon-zinc oxide composite material prepared by the invention obviously improves the separation of electron and hole pairs at the interface of the material, enlarges the contact area with reactants, and improves the light absorption capacity and the reaction rate.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings and specific examples, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (5)
1. A preparation method of a porous silicon-zinc oxide composite material for wastewater degradation is characterized by comprising the following steps:
(1) adding graphite particles into an etching stock solution prepared from hydrofluoric acid solution, hydrogen peroxide solution and deionized water, and performing ultrasonic dispersion for 10min at room temperature to obtain an etching solution;
(2) dripping the etching solution onto the cleaned silicon wafer by using a rubber head dropper, etching for 0.5-48h at room temperature, and cleaning and drying to obtain a porous silicon wafer;
(3) mixing 0.025mol/L silver nitrate solution, 0.025mol/L hexamethylenetetramine solution and 0.25mol/L zinc nitrate solution with deionized water according to the volume ratio of 1:10:5-15 in a beaker to obtain electrolyte solution;
(4) and (3) placing a beaker of the electrolyte solution in a water bath for preheating, fixing the corroded porous silicon wafer and the aluminum sheet by using a double-head crocodile lead, immersing the porous silicon wafer and the aluminum sheet into the electrolyte solution at the same time, and reacting for 1-10 hours to obtain the porous silicon-zinc oxide composite material.
2. The method for preparing the porous silicon-zinc oxide composite material for wastewater degradation according to claim 1, wherein the method comprises the following steps: in the step (1), the graphite particles are micro-nano graphite particles, and the particle size range is 10nm-10 μm.
3. The method for preparing the porous silicon-zinc oxide composite material for wastewater degradation according to claim 2, wherein the method comprises the following steps: in the step (1), the ratio of the weight of the graphite particles to the volume of the etching stock solution is 0.1g:5-20 mL.
4. The method for preparing the porous silicon-zinc oxide composite material for wastewater degradation according to claim 3, wherein the method comprises the following steps: in the step (1), the concentration of hydrofluoric acid in the etching stock solution is 0.8-40 wt%.
5. The method for preparing the porous silicon-zinc oxide composite material for wastewater degradation according to claim 4, wherein the method comprises the following steps: in the step (1), the hydrogen peroxide concentration of the etching stock solution is 0.3-6 wt%.
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