CN112680748A - A/B/Si ternary composite silicon-based photoelectrode with bionic structure and preparation method thereof - Google Patents
A/B/Si ternary composite silicon-based photoelectrode with bionic structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an A/B/Si ternary composite silicon-based photoelectrode with a bionic structure and a preparation method thereof, belonging to the field of photoelectrocatalysis. In the structure of the electrode material, if Si is a p-type semiconductor, B is an n-type metal oxide semiconductor, and A is a hydrogen evolution promoter; if Si is an n-type semiconductor, B is a p-type metal oxide semiconductor,a is an oxygen evolution catalyst promoter, and the metal oxide semiconductor and the catalyst promoter can be prepared by in-situ growth on a silicon wafer of the pyramid substrate, and the preparation method is simple. The electrode has good electrocatalytic performance, and H is prepared by electrolyzing water after 3 hours of electrolysis2The density of the glass can reach 23 mu mol cm‑2And the current can be stabilized for about 500 h.
Description
Technical Field
The invention relates to an A/B/Si ternary composite silicon-based photoelectrode with a bionic structure and a preparation method thereof, belonging to the field of energy materials.
Background
With the increasing demand of people for clean energy, the preparation of hydrogen and oxygen by Photoelectrochemical (PEC) water decomposition is an effective way to realize solar energy conversion and utilization, and is more and more paid attention by people. The principle of PEC water decomposition is that a photoelectrode absorbs incident light to generate electrons and holes, and then the photogenerated electrons and the holes are separated under the action of a built-in field and migrate to the surfaces of an electrode and a counter electrode to respectively initiate oxidation and reduction reactions of water. The photoelectrocatalysis water decomposition mainly comprises three processes: light absorption, photon-generated carrier separation and transfer, and surface reactions. How to design these processes is very important to achieve an efficient PEC.
One generally goes from three steps of the PEC water splitting process to achieve efficient solar hydrogen production: light absorption of semiconductor photoelectrode, separation and migration of photogenerated carriers, and surface reaction. To this end, a wide variety of wide bandgap semiconductor bodies (e.g., SnO2ZnO and WO3) Synthesized and studied, wide band gap semiconductors only absorb ultraviolet light, which greatly affects their solar conversion efficiency. To solve this problem, many efforts have been made to find suitable methods such as doping modification, plasmon resonance, narrow-band semiconductor recombination, etc. The composite modification strategy can widen the spectral absorption range of a semiconductor (such as Si) with a narrow band gap when the semiconductor is compounded, and can form a heterojunction when the two semiconductors are compounded, and the energy band position and the inclination of the energy band position at an interface are changed by the existence of the heterojunction in a proper heterostructure system, so that the migration of a photogenerated charge carrier through the heterojunction is accelerated, and the PEC performance is improved. However, compound semiconductors typically suffer from the limitation of the slow kinetics of the hydrogen evolution reaction of the material. The introduction of Hydrogen Evolution Reaction (HER) promoters is considered a promising approach to improve PEC performance. Transition metal sulfides (NiS, WS and MoS)2) Is a high-efficiency HER catalyst expected to replace noble metals (Pt, Pd and the like), in particular MoS2As a two-dimensional (2d) layered material, has a high degree ofThe unsaturated S atoms exposed out of the edge can be used as active centers, and have strong affinity to H ions in the solution, so that the photocatalyst has better photocatalytic hydrogen evolution performance.
In fact, the PEC performance of the photoelectrode is affected not only by the intrinsic properties of the material, but also by the microstructure of the electrode surface. Because the light trapping capability of a normally planar photoelectrode is relatively poor. It is reported that a photoelectrode having a hierarchical structure can increase light absorption by effective refractive index change and minimizing light reflection, while generating a large semiconductor/electrolyte contact area, having more surface active centers, accelerating surface reaction, compared to a planar photoelectrode.
Therefore, it is very desirable to construct an A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure to achieve high water decomposition performance.
Disclosure of Invention
The invention designs an A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure, constructs a dual ordered change system of materials and structures from top to bottom, and synergistically realizes the enhancement of light absorption, the reduction of carrier recombination and the improvement of photoelectric conversion efficiency.
Firstly, the invention provides an A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure, wherein if Si is a p-type semiconductor, B is an n-type metal oxide semiconductor, and A is a hydrogen evolution catalyst promoter; if Si is an n-type semiconductor, B is a p-type metal oxide semiconductor and A is an oxygen evolution promoter.
In one embodiment of the invention, the surface structure of the Si substrate is a pyramid structure, and the size of the bottom of the pyramid structure is 3-8 μm; b is a nanorod array with the diameter of 100-300 nm and the length of 200-1000 nm; a is a nano-sheet or a nano-particle, the diameter of the nano-sheet is 20-100 nm when the nano-sheet is a nano-particle, and the thickness of the nano-sheet is 20-100 nm when the nano-sheet is a nano-sheet.
In one embodiment of the present invention, when Si is a p-type semiconductor, B is ZnO, WO3、Fe2O3、SnO2A is MoS2、CoP、Mo2C、Fe2C、WS2One or more of (a).
In one embodiment of the present invention, when Si is an n-type semiconductor, B is CuO or Cu2O、NiO、Co3O4A is Co (OH)2CoP, NiFe LDH (NiFe hydrotalcite), Ni2O3、CoO、Co2O3One or more of (a).
The invention further provides a preparation method of the A/B/Si ternary composite silicon-based photoelectrode with the bionic hierarchical structure, and the method comprises the following steps:
(1) preparing a silicon pyramid substrate: etching the pyramid structure in alkali liquor;
(2) preparation of B/Si structure: growing a nanorod array of the B in situ on the silicon-gold tower substrate, wherein the diameter of the nanorod array is 100-300 nm, and the length of the nanorod array is 200-1000 nm;
(3) preparation of A/B/Si structure: and (3) growing the nano-plate or nano-particle of the A in situ on the B/Si structure.
In one embodiment of the present invention, the preparation of the silicon pyramid substrate comprises the following specific operations: and putting the cleaned silicon wafer into alkali liquor, heating to 80-90 ℃, and mechanically stirring and etching for 20-50 min.
In one embodiment of the present invention, in step (1), the cleaning is: sequentially performing ultrasonic treatment on the silicon wafer in acetone, chloroform, ethanol and water for 2-10 min.
In one embodiment of the present invention, in step (1), the alkali solution is KOH: h2O is 5.78 g: 100mL of the mixture.
In one embodiment of the present invention, in the step (1), the rotation speed of the mechanical stirring is 100-500 rpm.
In one embodiment of the present invention, the specific method for preparing the B/Si structure is: any method capable of preparing the nanorod array of B in the prior art.
In one embodiment of the present invention, the specific method for preparing the a/B/Si structure is as follows: any method capable of preparing the nanosheet or nanoparticle of a in the prior art, such as a hydrothermal method, a chemical vapor deposition method, an etching method, and the like.
In one embodiment of the present invention, the preparation method of the ZnO nanorod array is chemical vapor deposition, hydrothermal method, template-assisted method, etching method, or the like.
In one embodiment of the present invention, the WO is3The preparation method of the nanorod array comprises a chemical vapor deposition method, a hydrothermal method, a thermal evaporation method and the like.
In one embodiment of the present invention, the Fe2O3The preparation method of the nanorod array is a hydrothermal method and the like (see Chinese patent application CN 107268022A).
In one embodiment of the invention, the preparation method of the SnO2 nanorod array is high-temperature vapor phase growth, a microemulsion method, a thermal evaporation method, a hydrothermal method or the like.
In one embodiment of the present invention, the preparation method of the CuO or Cu2O nanorod array is a hydrothermal method, a chemical vapor deposition method, or the like.
In one embodiment of the present invention, the preparation method of the NiO nanorod array is a cation exchange method or the like.
In one embodiment of the invention, the preparation method of the Co3O4 nanorod array is a solvothermal method.
The invention has the beneficial effects that:
(1) the A/B/Si ternary composite silicon-based photoelectrode with the bionic hierarchical structure is simple in preparation method, can be prepared by growing the metal oxide semiconductor (nanorod array material) and the cocatalyst (nanoparticle material) on the silicon wafer of the pyramid substrate in situ, is easy to operate and is expected to expand production.
(2) The A/B/Si ternary composite silicon-based photoelectrode with the bionic hierarchical structure can obviously improve the water electrolysis process, has the bionic structure and the hierarchical structure, can increase more surface active centers through the bionic structure, generates large contact area of a semiconductor/electrolyte, and can maximally increase the light absorption through the hierarchical structure, thereby accelerating the surface reaction.
(3) The material of the invention is electrolyzed into H after 3H of electrolysis2The density of the glass can reach 23 mu mol cm-2And the current can be stabilized for about 500 h.
Drawings
FIG. 1 shows MoS prepared in example 12/SnO2SEM image of/p-Si photocathode composite material.
FIG. 2 shows MoS prepared in example 12/SnO2Hydrogen production profile of p-Si photocathode composite at-0.3V vs SCE bias with electrolyte of 0.5M H2SO4。
FIG. 3 is a graph of characterization results for silicon-based photoelectrodes of different structures; (a) polarization (J-V) curves of silicon-based photoelectrodes of different structures, and (b) diffuse reflection spectra of silicon-based photoelectrodes of different structures.
FIG. 4 is a graph showing a comparison between the performances of the electrode material obtained in comparative example 1 and the electrode material obtained in example 1; (a) P-Si/SnO2/MoS2And P-Si/MoS2Polarization (J-V) curve of photoelectrode, (b) P-Si/SnO2/MoS2And P-Si/MoS2Diffuse reflectance spectrum of photoelectrode.
FIG. 5 shows CoP/WO obtained in example 23Curve (a) and diffuse reflectance spectrum (b) for a/p-Si photocathode.
FIG. 6 shows Co (OH) obtained in example 32(J-V) curve for/NiO/n-Si photocathode.
FIG. 7 shows NiFe LDH/Co obtained in example 43O4(J-V) curve of/n-Si photocathode.
Detailed Description
Example 1MoS2/SnO2Preparation of/p-Si photocathode composite material
(1) preparing a p-silicon pyramid substrate: cleaning a p-silicon wafer (sequentially performing ultrasonic treatment in acetone, chloroform, ethanol and water for 5min respectively), heating an alkali solution (5.78 g of KOH and 100mL of water) to 85 ℃, then putting the silicon wafer into the alkali solution, and mechanically stirring and etching for 30 min;
(2)SnO2construction of the/p-Si Structure: 0.1M SnCl4 5H2ethanol/Water (1:1v/v) solution of OSpin coating the solution on etched silicon wafer (4000rpm, 60s, 2 times), calcining in a muffle furnace at 450 deg.C for 45min, cooling to room temperature, placing in a hydrothermal reaction kettle, and adding 50mL of growth solution (0.1M SnCl)4 5H2O and 1.5M NaOH) at 200 ℃ for 24h, then heating to 500 ℃ at a heating rate of 3 ℃/min, and calcining in air for 1 h.
(3)MoS2/SnO2Construction of the/p-Si Structure: 0.07g NaMoO4·2H2Dissolving O and 0.14g L-cysteine in 100mL of water, ultrasonically stirring until the mixture is clear, adding 200 mu L of concentrated HCl, uniformly stirring, adding into a hydrothermal reaction kettle, and simultaneously SnO2Putting a/Si sample into the reaction kettle, reacting for 9h at 180 ℃, washing the sample with deionized water, drying the sample with nitrogen, heating to 300 ℃ at 1 ℃/min under the protection of nitrogen, and calcining for 1h to obtain MoS2/SnO2The p-Si photocathode composite material.
For the prepared MoS2/SnO2Performing performance characterization on the/p-Si photocathode composite material:
determination of MoS2/SnO2Hydrogen production of p-Si photocathode composite material under the bias of-0.3V vs SCE, electrolyte is 0.5M H2SO4As shown in FIG. 2, it can be seen that H was produced by electrolyzing water after 3 hours of electrolysis2The density of the glass can reach 23 mu mol cm-2。
For the prepared MoS2/SnO2Carrying out structural characterization on the/p-Si photocathode composite material:
the SEM picture is shown in figure 1, and the size of the silicon pyramid structure is 3-8 mu m, and SnO is observed2The nano-rod has a diameter of 100nm, a length of 1000nm and MoS2The size of the substrate is 30-50 nm, the structure is a bionic mosquito eye structure, namely the structure that the substrate gradually reduces to the top end, and the utilization efficiency of light can be improved.
FIG. 3 shows silicon-based photoelectrode of different structures (planar structure F-Si/SnO)2Planar structure of F-Si/SnO2/MoS2Pyramid structure P-Si/SnO2/MoS2Pyramid structure P-Si/SnO2) Polarization (J-V) curve of (D) and corresponding diffusionA reflection spectrum. As can be seen, the current yield and the light absorption capacity of the ternary composite silicon-based photoelectrode material obtained in example 1 are both significantly improved compared with photoelectrode materials of other structures. Wherein, the planar structure is F-Si/SnO2The current yield of (A) is about-0.20J (mA · cm)-2) Pyramid-structured P-Si/SnO2The current yield of (A) is about-0.25J (mA · cm)-2) Of planar structure F-Si/SnO2/MoS2The current yield of (A) is about-1.48J (mA · cm)-2) Pyramid-structured P-Si/SnO2/MoS2The current yield of (A) is about-3.0J (mA · cm)-2) At the same time. P-Si/SnO with pyramid structure2/MoS2The reflectivity of the alloy is about 12 percent, and the F-Si/SnO is relatively planar structure2/MoS2About 10 percent reduction, compared with pyramid structure P-Si/SnO2About 16 percent reduction, and is compared with a plane structure F-Si/SnO2The reduction is about 16% or so and about 23%.
Comparative example 1 explores the hierarchical design impact of electrode materials
Preparation of an intermediate layer-free electrode material MoS2/p-Si：
With reference to example 1, step (2) was omitted:
(1) preparing a p-silicon pyramid substrate: cleaning a p-silicon wafer (sequentially performing ultrasonic treatment in acetone, chloroform, ethanol and water for 5min respectively), heating an alkali solution (5.78 g of KOH and 100mL of water) to 85 ℃, then putting the silicon wafer into the alkali solution, and mechanically stirring and etching for 30 min;
(2)MoS2construction of the/p-Si Structure: 0.07g NaMoO4·2H2Dissolving O and 0.14g L-cysteine in 100mL of water, ultrasonically stirring until the solution is clear, adding 200 mu L of concentrated HCl, uniformly stirring, adding the solution into a hydrothermal reaction kettle, simultaneously putting the silicon wafer sample etched in the step (1) into the hydrothermal reaction kettle, reacting for 9h at 180 ℃, washing the sample with deionized water, drying the sample with nitrogen, heating the sample to 300 ℃ at the speed of 1 ℃/min under the protection of nitrogen, and calcining for 1h to obtain MoS2The p-Si photocathode composite material.
MoS obtained in example 1 was measured2/SnO2p-Si photocathode composite and MoS obtained in comparative example 12Polarization of/P-Si structure photocathode composite material (J-V)) Curves and diffuse reflectance spectra, the results are shown in FIG. 4 (wherein, FIG. 4(a) is P-Si/SnO2/MoS2And P-Si/MoS2Polarization (J-V) curve of photoelectrode, FIG. 4(b) is P-Si/SnO2/MoS2And P-Si/MoS2Diffuse reflectance spectrum of photoelectrode). Thus, the photocathode composite material MoS without the intermediate layer2The light absorption capacity and the current yield of the/p-Si are both obviously reduced compared with the ternary composite silicon-based photoelectrode material obtained in the embodiment 1.
Example 2CoP/WO3Preparation of/p-Si photocathode composite material
(1) preparing a p-silicon pyramid substrate: cleaning a p-silicon wafer (sequentially performing ultrasonic treatment in acetone, chloroform, ethanol and water for 5min respectively), heating an alkali solution (5.78 g of KOH and 100mL of water) to 85 ℃, then putting the silicon wafer into the alkali solution, and mechanically stirring and etching for 30 min;
(2)WO3preparation of the/p-Si structure: collecting 8.25g of Na2WO4·2H2Dissolving O powder in 25mL deionized water, magnetically stirring to completely dissolve O powder, transferring hydrochloric acid solution (2M) to adjust pH to 2.0, diluting to 250mL, adding oxalic acid to adjust final pH to 2.0 to obtain precursor solution, adding 0.3g Rb into hydrothermal kettle2SO4Placing the etched silicon wafer into a hydrothermal kettle, adding 20mL of the precursor solution, sealing, carrying out hydrothermal reaction at 180 ℃ for 4h, naturally cooling after the reaction is finished, taking out, washing with deionized water, and drying;
(3)CoP/WO3preparation of the/p-Si structure: 3.003g of Co (NH) was taken2)2And 0.1g of cetyltrimethylammonium bromide (CTAB) dissolved in 60mL of deionized water, and 20mL of 0.5M Co (NO)3)2Gradually dropping 6H2O into the solution, stirring for 10min, and coating the mixed solution on the WO obtained in step (2)3And a/P-Si structure, transferring the structure to a 60mL polytetrafluoroethylene reaction kettle, reacting for 12h at 120 ℃, cooling and drying after the reaction is finished, and respectively placing a product and sodium hypophosphite at two sides of a porcelain boat, wherein the molar ratio of Co to P is 1: 10, heating to 300 ℃ at the speed of 5 ℃/min for reaction for 2h under the protection of nitrogen on a tube furnace, and then naturally cooling to a room under the protection of Ar gasWarm, then the CoP/WO can be obtained3The p-Si photocathode composite material.
For the prepared MoS2/SnO2The results of the measurement of the/p-Si photocathode composite material are shown in FIG. 5. Wherein the current yield is about-3.9J (mA cm)-2) The reflectance was about 12.8%.
Example 3Co (OH)2Preparation of/NiO/n-Si composite material
(1) Preparing an n-silicon pyramid substrate: cleaning an n-silicon wafer (sequentially performing ultrasonic treatment in acetone, chloroform, ethanol and water for 5min respectively), heating an alkali solution (5.78 g of KOH and 100mL of water) to 85 ℃, then putting the silicon wafer into the alkali solution, and mechanically stirring and etching for 30 min;
(2) preparation of NiO/n-Si structure: preparing a zinc oxide nanorod on an n-Si pyramid substrate by a hydrothermal method, then placing the n-Si pyramid substrate with the zinc oxide nanorod in the center of a tube furnace, and adding nickel chloride (NiCl)2) The powder was placed 4cm upstream of the center of the tube furnace. Keeping the temperature at 585 ℃ for 30 minutes under the protection of nitrogen, and then cooling to room temperature to obtain a NiO/n-Si structure;
(3)Co(OH)2preparation of/NiO/n-Si Structure: dissolving 1mmol of cobalt chloride hexahydrate in 8mL of deionized water, adding 4mL of 2M NaOH solution, then spin-coating the solution on a NiO/n-Si structure, putting the NiO/n-Si structure into a high-pressure reaction kettle, reacting at 160 ℃ for 10 hours, naturally cooling to room temperature, washing a sample with deionized water, and drying with nitrogen to obtain Co (OH)2the/NiO/n-Si composite material.
For the prepared Co (OH)2The results of the measurement of the/NiO/n-Si photoelectrode composite material are shown in FIG. 6. Wherein the current yield is about-0.46J (mA cm)-2)。
Example 4NiFe LDH/Co3O4Preparation of/n-Si composite material
(1) Preparing an n-silicon pyramid substrate: cleaning an n-silicon wafer (sequentially performing ultrasonic treatment in acetone, chloroform, ethanol and water for 5min respectively), heating an alkali solution (5.78 g of KOH and 100mL of water) to 85 ℃, then putting the silicon wafer into the alkali solution, and mechanically stirring and etching for 30 min;
(2)Co3O4preparation of the/n-Si structure: 2.5gCo (NO)3)2·6H2O was dissolved with 10mL of oleic acid, then 60mL of n-dodecane and 10mL of 30% H were added2O2Spin-coating on an etched silicon wafer (4000rpm, 60s, 2 times of spin-coating), then placing the silicon wafer into a 100mL polytetrafluoroethylene container, sealing, carrying out heat treatment at 160 ℃ for 10h, then naturally cooling to room temperature, sequentially washing with distilled water and absolute ethyl alcohol for three times respectively, and carrying out vacuum drying at 80 ℃ for 2 h;
40mL of NaCO with the concentration of 1.25mol/L is prepared3And 1.5mol of L-1NaOH, heating in water bath, stirring to 70 ℃, then stirring at constant temperature, and slowly dropwise adding 0.6mol of L-1 Ni (NO)2And FeCl340ml of mixed solution (the feeding ratio of nickel to iron is regulated to be 1: 1); stirring to be completely mixed, and coating the mixture on Co in the step (2)3O4On the structure of/n-Si, carrying out hydrothermal reaction for 24h at 70 ℃, cooling to room temperature, washing with distilled water to neutrality, and drying at room temperature to obtain NiFe LDH/Co3O4The composite material of the/n-Si photoelectrode.
For the prepared NiFe LDH/Co3O4The results of the measurement of the/n-Si photoelectrode composite material are shown in FIG. 7. Wherein the current yield is about-0.68J (mA cm)-2)。
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. An A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure is characterized in that if Si is a p-type semiconductor, B is an n-type metal oxide semiconductor, and A is a hydrogen evolution catalyst promoter; if Si is an n-type semiconductor, B is a p-type metal oxide semiconductor and A is an oxygen evolution promoter.
2. The A/B/Si ternary alloy with bionic hierarchical structure according to claim 1The composite silicon-based photoelectrode is characterized in that if Si is a p-type semiconductor, B is ZnO and WO3、Fe2O3、SnO2A is MoS2、CoP、Mo2C、Fe2C、WS2One or more of (a).
3. The A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure according to claim 1, wherein if Si is an n-type semiconductor, B is CuO or Cu2O、NiO、Co3O4A is Co (OH)2CoPi, NiFe LDH (NiFe hydrotalcite), Ni2O3、CoO、Co2O3One or more of (a).
4. The A/B/Si ternary composite silicon-based photoelectrode with a bionic hierarchical structure according to claims 1 to 3, wherein the surface structure of the Si substrate is a pyramid structure formed by anisotropic etching in alkali liquor, the size of the bottom is 3 to 8 μm, B is a nanorod array, the diameter of the nanorod array is 100 to 300nm, and the length of the nanorod array is 200 to 1000 nm; the morphology of A is nano-sheet or nano-particle, and the diameter is 20-100 nm.
5. The preparation method of the A/B/Si ternary composite silicon-based photoelectrode with the bionic hierarchical structure is characterized by comprising the following steps:
(1) preparing a silicon pyramid substrate: etching the pyramid structure in alkali liquor;
(2) preparation of B/Si structure: growing a nanorod array of the B in situ on the silicon-gold tower substrate, wherein the diameter of the nanorod array is 100-300 nm, and the length of the nanorod array is 200-1000 nm;
(3) preparation of A/B/Si structure: and (3) growing the nano-plate or nano-particle of the A in situ on the B/Si structure.
6. The preparation method according to claim 5, wherein the preparation of the silicon pyramid substrate is carried out by the following specific operations: adding the cleaned silicon wafer into alkali liquor, heating to 80-90 deg.C, mechanically stirring, and etching for 20-50 min.
7. The method according to claim 5 or 6, wherein the ZnO nanorod array is prepared by any one of chemical vapor deposition, hydrothermal method, template-assisted method or etching method; said WO3The preparation method of the nano-rod array is a chemical vapor deposition method, a hydrothermal method or a thermal evaporation method; said Fe2O3The preparation method of the nanorod array is a hydrothermal method.
8. The production method according to any one of claims 5 to 7, wherein the SnO is2The preparation method of the nanorod array is any one of high-temperature vapor phase growth, a microemulsion method, a thermal evaporation method or a hydrothermal method.
9. The method according to any one of claims 5 to 7, wherein the NiO nanorod array is prepared by a cation exchange method; the Co3O4The preparation method of the nanorod array is a solvothermal method.
10. The application of the A/B/Si ternary composite silicon-based photoelectrode with the bionic hierarchical structure in the field of photoelectric water decomposition is disclosed in claims 1-4.
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