CN112359376A - Preparation method of metal oxide-insulator-semiconductor structure photo-anode - Google Patents
Preparation method of metal oxide-insulator-semiconductor structure photo-anode Download PDFInfo
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Abstract
The invention relates to a preparation method of a metal oxide-insulator-semiconductor structure photo-anode, which comprises the steps of firstly preparing a semiconductor substrate by a hydrothermal method, then depositing an insulating layer by atomic force, and then preparing high-dispersion metal oxide by a surface chemical grafting method, thereby constructing a metal oxide-insulator-semiconductor MIS structure electrode. The preparation method is simple and easy to operate, the production cost is low, and the stability of the prepared MIS structure electrode is good.
Description
Technical Field
The invention belongs to the technical field of electrode preparation, and particularly relates to a preparation method of a metal oxide-insulator-semiconductor structured photoanode.
Background
With the burning of fossil fuel, the problems of energy shortage and environmental pollution are imminent, and become the challenges facing people today. The development of sustainable energy has been listed as an important task by various countries. At present, light energy is a very promising solution, which is inspired by photosynthesis in the nature, and various forms of artificial photosynthesis germinate and are widely researched in various fields, wherein in the chemical field, a composite photocatalytic system is designed and constructed by using the photoelectric characteristics of inorganic semiconductor materials to realize hydrogen production by photolysis of water or organic matter production by reduction of carbon dioxide, and the method is a way for artificial photosynthesis.
In recent decades, the rapid development of photoelectrochemical technology, the research on photoelectric water oxidation is deepened gradually, the development of high-efficiency and stable photo-anode materials is concerned by domestic and foreign scientists, and at present, TiO is used as a material for the production of titanium dioxide2、ZnO、TaON、Fe3O4、WO3、BiVO4、Ta3N5The n-type semiconductor photoelectric anode material has been widely reported and studied, and metal oxide (TiO)2、ZnO、TaON、Fe3O4、WO3Etc.) with its unique advantages, such as no toxicity, low cost, stability, etc., it is the focus of research on photocatalysis and photoelectrocatalysis.
The patent CN108642513A discloses a preparation method of an Au @ InP nanopore array photo-anode material, which comprises the steps of firstly using an InP wafer as a substrate, preparing a one-dimensional ordered InP nanopore array by an electrochemical anodic oxidation method and combining wet etching, and then uniformly loading Au nanoparticles in the InP nanopore array by an immersion electrochemical deposition method by using the one-dimensional ordered InP nanopore array as a template, thereby constructing the Au @ InP nanopore array composite structure photo-splitting photo-anode material. The method is simple and convenient, but the cost is high.
Patent CN104988533A discloses a TiO2/BiVO4 photo-anode material and a preparation method thereof, which comprises a substrate, a TiO nanorod array vertically grown on the surface of the substrate, and a TiO nanorod array deposited on the surface of the TiO nanorod array2A layer of BiVO4 nanoparticles on the surface of the nanorods. The electrode prepared by the method has the advantage of enlarging the absorption spectrum range of visible light, but still has the problem of interface electron recombination, and the performance cannot be greatly improved.
Patent CN110902777A discloses a method for preparing an anion-doped cobalt-based photoanode material, which comprises the steps of firstly obtaining a sulfur-and nitrogen-doped cobalt-based anode material on an etched titanium sheet substrate through hydrothermal and high-temperature calcination processes. The method has simple process, does not introduce other new anions, but has low selectivity of the prepared electrode material.
Patent CN110257868A discloses a method for preparing a silicon/nickel iron vanadium photo-anode, which comprises dissolving nickel sulfate, ferrous sulfate and vanadyl sulfate in deionized water under inert gas atmosphere to obtain electrodeposition solution, preventing ferrous ions in the solution from being oxidized into ferric ions, immersing the packaged silicon photo-anode in the prepared electrodeposition solution, preparing a silicon/nickel iron vanadium photo-anode by electrodeposition, and immersing Ni in the electrodeposition solution2+、Fe2+、V4+The surface of the silicon electrode is reduced into a NiFeV alloy film which is coated on the surface of the silicon anode, thereby obtaining the target product silicon/nickel iron vanadium photo-anode. However, this method may introduce some impurities during the preparation process.
The above-disclosed patents have problems of high cost, low selectivity of electrode materials, possible introduction of other impurities, etc., to various degrees.
Disclosure of Invention
The invention aims to provide a preparation method of a metal oxide-insulator-semiconductor structured photo-anode, which has the advantages of simple operation, low production cost and good stability of the prepared MIS structured electrode.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a metal oxide-insulator-semiconductor structure photo-anode comprises the steps of firstly preparing a semiconductor substrate through a hydrothermal method, then depositing an insulating layer through atomic force, and then preparing high-dispersion metal oxide through a surface chemical grafting method, so that a metal oxide-insulator-semiconductor MIS structure electrode is constructed.
Further, the method specifically comprises the following steps:
(1) pouring the mixed solution prepared in the early stage for synthesizing the semiconductor material into a polytetrafluoroethylene lining, placing FTO in the polytetrafluoroethylene lining, transferring the whole kettle into a steel lining, carrying out a hydrothermal growth process for 300-2Drying; placing the prepared sample in an environment of 400-500 ℃ for 100-120 minutes to prepare a semiconductor electrode;
(2) placing the prepared electrode into a constant-temperature deposition cavity at 150 ℃, alternately pulsing the precursor, circularly depositing for 10-50 times, and obtaining insulating layer-wrapped semiconductor electrode samples with different thicknesses after deposition;
(3) and carrying out vacuum heat treatment on the prepared insulating layer-wrapped semiconductor electrode at 400 ℃ for more than 4 hours to expose enough surface hydroxyl, then injecting a grafting species solution, fully reacting at 150-180 ℃, and then calcining at 300 ℃ under oxygen to obtain the metal oxide-insulator-semiconductor MIS structure electrode.
Further, in the step (1), the mixed solution is FeCl3And NaNO3Or one of a mixed solution of HCL and ultrapure water and tetrabutyl titanate.
Further, in the step (1), the prepared semiconductor electrode is N-TiO2Electrodes or Sn-Fe2O3One of the electrodes.
Further, in the step (2), the precursor is trimethyl aluminum TMA and water, trimethyl gallium TMG and water or silicon chloride SiCl4And water.
Further, in the step (2), the deposition is respectively circulated for 10 times, 30 times and 50 times, and insulating layers with different thicknesses are obtained after the deposition to wrap the semiconductor electrode sample.
Further, in the step (3), the grafting species is one of ruthenocene, nickelocene or tetramethyl tin.
Compared with the prior art, the invention has the following beneficial effects: the metal oxide-insulator-semiconductor (MIS) structure electrode constructed by the preparation method has good stability, can provide strong driving force, and improves the photoelectric conversion efficiency and CO2Conversion to syngas efficiency. In addition, the preparation method is simple and easy to implement, has low requirements on equipment, cheap and easily-obtained raw materials, low production cost, easy industrialization and large-scale production, and has wide application prospects in the fields of energy, environmental protection, photoelectrocatalysis and the like.
Drawings
FIG. 1 is a flow chart of a method of making an embodiment of the present invention.
Fig. 2 is an SEM image of a metal oxide-insulator-semiconductor (MIS) structure electrode manufactured in example 1 of the present invention.
Fig. 3 is an XRD pattern of a metal oxide-insulator-semiconductor (MIS) structure electrode manufactured in example 1 of the present invention.
Fig. 4 is a linear scan graph of a metal oxide-insulator-semiconductor (MIS) structure electrode manufactured in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
Referring to fig. 1, the invention provides a method for preparing a metal oxide-insulator-semiconductor structure photoanode, which comprises the steps of firstly preparing a semiconductor substrate by a hydrothermal method, then depositing an insulating layer by atomic force, and then preparing a high-dispersion metal oxide by a surface chemical grafting method, thereby constructing a metal oxide-insulator-semiconductor (MIS) structure electrode. The method specifically comprises the following steps:
(1) pouring the mixed solution prepared in the early stage for synthesizing the semiconductor material into a polytetrafluoroethylene lining, placing FTO in the polytetrafluoroethylene lining, transferring the whole kettle into a steel lining, carrying out a hydrothermal growth process for 300-2Drying; placing the prepared sample in an environment of 400-500 ℃ for 100-120 minutes to prepare a semiconductor electrode;
wherein the mixed solution is FeCl3And NaNO3Or one of a mixed solution of HCL and ultrapure water and tetrabutyl titanate.
The prepared semiconductor electrode is N-TiO2Electrodes or Sn-Fe2O3One of the electrodes.
(2) And (3) putting the prepared electrode into a constant-temperature deposition cavity at 150 ℃, alternately pulsing the precursor, circularly depositing for 10-50 times, and obtaining insulating layer-wrapped semiconductor electrode samples with different thicknesses after deposition.
Wherein the precursor is trimethyl aluminum (TMA) and water, trimethyl gallium (TMG) and water or silicon chloride (SiCl)4) And water.
And in the circulating deposition, the circulating deposition is carried out for 10 times, 30 times and 50 times respectively, and insulating layers with different thicknesses are obtained after the deposition and are wrapped on the semiconductor electrode samples.
(3) And carrying out vacuum heat treatment on the prepared insulating layer-wrapped semiconductor electrode at 400 ℃ for more than 4 hours to expose enough surface hydroxyl, then injecting a grafting species solution, fully reacting at 150-180 ℃, and then calcining at 300 ℃ under oxygen to obtain the metal oxide-insulator-semiconductor MIS structure electrode.
Wherein the grafting species is one of ruthenocene, nickelocene or tetramethyl tin.
The following examples are given for further illustration.
Example 1
Will contain 0.1M FeCl3And 1.0M NaNO3The mixed solution of (a) was poured into a polytetrafluoroethylene liner, and the FTO was placed inside with the conductive surface facing downward. The entire kettle was transferred to a steel liner and the hydrothermal growth process was carried out in an oven at 100 ℃ for 300 minutes, then the electrodes were rinsed thoroughly with deionized water and N was used2And (5) drying. The prepared sample was further annealed at 500 ℃ for 120 minutes to prepare Fe2O3And an electrode. Adding a certain volume of SnCl4The solution (10 mM in ethanol) was added dropwise to Fe2O3On the surface of the electrode, and dried at room temperature, the prepared sample was calcined at 700 ℃ (30 minutes) to prepare Sn-doped Fe2O3Electrode (expressed as Sn-Fe)2O3). Mixing Sn-Fe2O3Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, performing cross pulse A1 source and water, performing cyclic deposition for 30 times to obtain Al after deposition2O3Wrapping Fe2O3And (3) sampling. Prepared Al2O3Coating Sn-Fe2O3The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-Al2O3-Sn-Fe2O3Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/Al2O3/Sn-Fe2O3And an electrode. Produced RuO2/Al2O3/Sn-Fe2O3SEM images, XRD images and linear scans of the electrodes are shown in FIGS. 2-4.
Example 2
A well-mixed solution containing 6.0mL of HCL and 6.0mL of ultrapure water was poured into a polytetrafluoroethylene reaction vessel, and after stirring in the vessel for 5 minutes, 0.16mL of tetrabutyl titanate was added to the well-mixed solution. After stirring for another 5 minutes, the FTO substrate was placed at an angle such that the conductive surface faced down and transferred to a stainless steel autoclave (20 mL). The reaction mixture was placed in an oven at 180 ℃ for 300 minutes. After the reaction is finished, taking out the FTO, repeatedly washing the FTO by deionized water and ethanol, and washing the FTO by N2And blowing and drying under the atmosphere. Finally, TiO2The nanorod array is calcined and crystallized for 2 hours at 400 ℃ in Ar atmosphere. Then, TiO is calcined at 500 ℃ in an ammonia atmosphere2The electrode was heated for 3 hours to obtain N-doped TiO2Electrode (shown as N-TiO)2). Adding N-TiO2Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, performing cross pulse A1 source and water, performing cyclic deposition for 30 times to obtain Al after deposition2O3Wrapped TiO2And (3) sampling. Prepared Al2O3Wrapping of N-TiO2The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-Al2O3-N-TiO2Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/Al2O3/N-TiO2And an electrode.
Example 3
Will contain 0.1M FeCl3And 1.0M NaNO3The mixed solution of (a) was poured into a polytetrafluoroethylene liner, and the FTO was placed inside with the conductive surface facing downward. The entire kettle was transferred to a steel liner and the hydrothermal growth process was carried out in an oven at 100 ℃ for 300 minutes, then the electrodes were rinsed thoroughly with deionized water and N was used2And (5) drying. The prepared sample was further annealed at 500 ℃ for 120 minutes to prepare Fe2O3And an electrode. Adding a certain volume of SnCl4The solution (10 mM in ethanol) was added dropwise to Fe2O3On the surface of the electrode, and dried at room temperature, the prepared sample was calcined at 700 ℃ (30 minutes) to prepare Sn-doped Fe2O3Electrode (expressed as Sn-Fe)2O3). Mixing Sn-Fe2O3Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, performing cross pulse A1 source and water, performing cyclic deposition for 30 times to obtain Al after deposition2O3Wrapping Fe2O3And (3) sampling. Prepared Al2O3Coating Sn-Fe2O3The electrode was first heat treated at 400 ℃ for 4 hours in vacuumExposing enough surface hydroxyl, injecting nickelocene solution, and fully reacting at 150 deg.C for 30 hr to obtain NiCp2-Al2O3-Sn-Fe2O3The electrode is calcined at 300 ℃ under oxygen to obtain NiO/Al2O3/Sn-Fe2O3And an electrode.
Example 4
A well-mixed solution containing 6.0mL of HCL and 6.0mL of ultrapure water was poured into a polytetrafluoroethylene reaction vessel, and after stirring in the vessel for 5 minutes, 0.16mL of tetrabutyl titanate was added to the well-mixed solution. After stirring for another 5 minutes, the FTO substrate was placed at an angle such that the conductive surface faced down and transferred to a stainless steel autoclave (20 mL). The reaction mixture was placed in an oven at 180 ℃ for 300 minutes. After the reaction is finished, taking out the FTO, repeatedly washing the FTO by deionized water and ethanol, and washing the FTO by N2And blowing and drying under the atmosphere. Finally, TiO2The nanorod array is calcined and crystallized for 2 hours at 400 ℃ in Ar atmosphere. Then, TiO is calcined at 500 ℃ in an ammonia atmosphere2The electrode was heated for 3 hours to obtain N-doped TiO2Electrode (shown as N-TiO)2). Adding N-TiO2Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, performing cross pulse A1 source and water, performing cyclic deposition for 30 times to obtain Al after deposition2O3Wrapped TiO2And (3) sampling. Prepared Al2O3Wrapping of N-TiO2The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl groups, then filled with nickelocene solution and reacted at 150 deg.c for 30 hr to obtain NiCp2-Al2O3-N-TiO2The electrode is calcined at 300 ℃ under oxygen to obtain NiO/Al2O3/N-TiO2And an electrode.
Example 5
Will contain 0.1M FeCl3And 1.0M NaNO3The mixed solution of (a) was poured into a polytetrafluoroethylene liner, and the FTO was placed inside with the conductive surface facing downward. The entire kettle was transferred to a steel liner, the hydrothermal growth process was carried out in an oven at 100 ℃ for 300 minutes, and then rinsed thoroughly with deionized waterUsing N in combination with electrodes2And (5) drying. The prepared sample was further annealed at 500 ℃ for 120 minutes to prepare Fe2O3And an electrode. Adding a certain volume of SnCl4The solution (10 mM in ethanol) was added dropwise to Fe2O3On the surface of the electrode, and dried at room temperature, the prepared sample was calcined at 700 ℃ (30 minutes) to prepare Sn-doped Fe2O3Electrode (expressed as Sn-Fe)2O3). Mixing Sn-Fe2O3Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, performing cross pulse A1 source and water, performing cyclic deposition for 30 times to obtain Al after deposition2O3Wrapping Fe2O3And (3) sampling. Prepared Al2O3Coating Sn-Fe2O3The electrode is first treated with heat treatment in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl groups, then poured with tetramethyl tin solution and reacted at 150 deg.c for 30 hr to obtain SnMe4-Al2O3-Sn-Fe2O3Electrode, then calcining at 300 ℃ under oxygen to obtain SnO2/Al2O3/Sn-Fe2O3And an electrode.
Example 6
A well-mixed solution containing 6.0mL of HCL and 6.0mL of ultrapure water was poured into a polytetrafluoroethylene reaction vessel, and after stirring in the vessel for 5 minutes, 0.16mL of tetrabutyl titanate was added to the well-mixed solution. After stirring for another 5 minutes, the FTO substrate was placed at an angle such that the conductive surface faced down and transferred to a stainless steel autoclave (20 mL). The reaction mixture was placed in an oven at 180 ℃ for 300 minutes. After the reaction is finished, taking out the FTO, repeatedly washing the FTO by deionized water and ethanol, and washing the FTO by N2And blowing and drying under the atmosphere. Finally, TiO2The nanorod array is calcined and crystallized for 2 hours at 400 ℃ in Ar atmosphere. Then, TiO is calcined at 500 ℃ in an ammonia atmosphere2The electrode was heated for 3 hours to obtain N-doped TiO2Electrode (shown as N-TiO)2). Adding N-TiO2Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl aluminum (TMA) and water as precursors, alternately pulsing A1 source and water, and circulatingDepositing for 30 times to obtain Al2O3Wrapped TiO2And (3) sampling. Prepared Al2O3Wrapping of N-TiO2The electrode is first treated with heat treatment in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl groups, then poured with tetramethyl tin solution and reacted at 150 deg.c for 30 hr to obtain SnMe4-Al2O3-N-TiO2Electrode, then calcining at 300 ℃ under oxygen to obtain SnO2/Al2O3/N-TiO2And an electrode.
Example 7
Will contain 0.1M FeCl3And 1.0M NaNO3The mixed solution of (a) was poured into a polytetrafluoroethylene liner, and the FTO was placed inside with the conductive surface facing downward. The entire kettle was transferred to a steel liner and the hydrothermal growth process was carried out in an oven at 100 ℃ for 300 minutes, then the electrodes were rinsed thoroughly with deionized water and N was used2And (5) drying. The prepared sample was further annealed at 500 ℃ for 120 minutes to prepare Fe2O3And an electrode. Adding a certain volume of SnCl4The solution (10 mM in ethanol) was added dropwise to Fe2O3On the surface of the electrode, and dried at room temperature, the prepared sample was calcined at 700 ℃ (30 minutes) to prepare Sn-doped Fe2O3Electrode (expressed as Sn-Fe)2O3). Mixing Sn-Fe2O3The electrode plate is put into a constant-temperature deposition cavity at 150 ℃ and is coated with silicon tetrachloride (SiCl)4) And water is taken as a precursor, a Si source and water are alternately pulsed, the deposition is carried out for 30 times in a circulating way, and SiO is obtained after the deposition2Wrapping Fe2O3And (3) sampling. Prepared SiO2Coating Sn-Fe2O3The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-SiO2-Sn-Fe2O3Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/SiO2/Sn-Fe2O3And an electrode.
Example 8
A solution containing 6.0mL of HCL and 6.0mL of ultrapure water was chargedThe mixed solution was poured into a polytetrafluoroethylene reaction kettle, and after stirring in the kettle for 5 minutes, 0.16mL of tetrabutyl titanate was added to the well-mixed solution. After stirring for another 5 minutes, the FTO substrate was placed at an angle such that the conductive surface faced down and transferred to a stainless steel autoclave (20 mL). The reaction mixture was placed in an oven at 180 ℃ for 300 minutes. After the reaction is finished, taking out the FTO, repeatedly washing the FTO by deionized water and ethanol, and washing the FTO by N2And blowing and drying under the atmosphere. Finally, TiO2The nanorod array is calcined and crystallized for 2 hours at 400 ℃ in Ar atmosphere. Then, TiO is calcined at 500 ℃ in an ammonia atmosphere2The electrode was heated for 3 hours to obtain N-doped TiO2Electrode (shown as N-TiO)2). Adding N-TiO2The electrode plate is put into a constant-temperature deposition cavity at 150 ℃ and is coated with silicon tetrachloride (SiCl)4) And water is taken as a precursor, a Si source and water are alternately pulsed, the deposition is carried out for 30 times in a circulating way, and SiO is obtained after the deposition2Wrapped TiO2And (3) sampling. Prepared SiO2Wrapping of N-TiO2The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-SiO2-N-TiO2Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/SiO2/N-TiO2And an electrode.
Example 9
Will contain 0.1M FeCl3And 1.0M NaNO3The mixed solution of (a) was poured into a polytetrafluoroethylene liner, and the FTO was placed inside with the conductive surface facing downward. The entire kettle was transferred to a steel liner and the hydrothermal growth process was carried out in an oven at 100 ℃ for 300 minutes, then the electrodes were rinsed thoroughly with deionized water and N was used2And (5) drying. The prepared sample was further annealed at 500 ℃ for 120 minutes to prepare Fe2O3And an electrode. Adding a certain volume of SnCl4The solution (10 mM in ethanol) was added dropwise to Fe2O3On the surface of the electrode, and dried at room temperature, the prepared sample was calcined at 700 ℃ (30 minutes) to prepare Sn-doped Fe2O3Electrode (expressed as Sn-Fe)2O3). Mixing Sn-Fe2O3Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl gallium (TMG) and water as precursors, alternately pulsing Ga source and water, circularly depositing for 30 times to obtain Ga after deposition2O3Wrapping Fe2O3And (3) sampling. Ga prepared2O3Coating Sn-Fe2O3The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-Ga2O3-Sn-Fe2O3Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/Ga2O3/Sn-Fe2O3And an electrode.
Example 10
A well-mixed solution containing 6.0mL of HCL and 6.0mL of ultrapure water was poured into a polytetrafluoroethylene reaction vessel, and after stirring in the vessel for 5 minutes, 0.16mL of tetrabutyl titanate was added to the well-mixed solution. After stirring for another 5 minutes, the FTO substrate was placed at an angle such that the conductive surface faced down and transferred to a stainless steel autoclave (20 mL). The reaction mixture was placed in an oven at 180 ℃ for 300 minutes. After the reaction is finished, taking out the FTO, repeatedly washing the FTO by deionized water and ethanol, and washing the FTO by N2And blowing and drying under the atmosphere. Finally, TiO2The nanorod array is calcined and crystallized for 2 hours at 400 ℃ in Ar atmosphere. Then, TiO is calcined at 500 ℃ in an ammonia atmosphere2The electrode was heated for 3 hours to obtain N-doped TiO2Electrode (shown as N-TiO)2). Adding N-TiO2Placing the electrode plate in a constant-temperature deposition cavity at 150 ℃, taking trimethyl gallium (TMG) and water as precursors, alternately pulsing Ga source and water, circularly depositing for 30 times to obtain Ga after deposition2O3Wrapped TiO2And (3) sampling. Ga prepared2O3Wrapping of N-TiO2The electrode is first treated in vacuum at 400 deg.c for 4 hr to expose enough surface hydroxyl radical, then filled with cyclopentadienyl ruthenium solution and reacted at 150 deg.c for 30 hr to obtain Ru (cp)2-Ga2O3-N-TiO2Electrode, then calcining at 300 ℃ under oxygen to obtain RuO2/Ga2O3/N-TiO2And an electrode.
Example 11
NiO/SiO2/Sn-Fe2O3The electrode was prepared in the same manner as in example 3, except that the precursor was changed to silicon tetrachloride (SiCl)4) And water.
Example 12
NiO/SiO2/N-TiO2The electrode was prepared in the same manner as in example 4, except that the precursor was changed to silicon tetrachloride (SiCl)4) And water.
Example 13
SnO2/SiO2/Sn-Fe2O3The electrode was prepared in the same manner as in example 5, except that the precursor was changed to silicon tetrachloride (SiCl)4) And water.
Example 14
SnO2/SiO2/N-TiO2The electrode was prepared in the same manner as in example 6, except that the precursor was changed to silicon tetrachloride (SiCl)4) And water.
Example 15
NiO/Ga2O3/Sn-Fe2O3The electrode was prepared in the same manner as in example 9, except that ruthenocene was changed to nickelocene.
Example 16
NiO/Ga2O3/N-TiO2The electrode was prepared in the same manner as in example 10, except that ruthenocene was changed to nickelocene.
Example 17
SnO2/Ga2O3/Sn-Fe2O3The electrode was prepared in the same manner as in example 5, except that the precursor was changed to Trimethylgallium (TMG) and water.
Example 18
SnO2/Ga2O3/N-TiO2The electrode was prepared in the same manner as in example 6, except that the precursor was changed to Trimethylgallium (TMG) and water.
The invention takes a semiconductor material as a research object, an insulating layer as a protective layer of a surface state, and an outer layer loaded with a metal oxide as an extractor of electrons to form a metal oxide-insulator-semiconductor (MIS) structure electrode. Compared with the prior art, the preparation method is simple and feasible, low in raw material price, high in efficiency, suitable for large-scale production and good in application prospect.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (7)
1. A preparation method of a metal oxide-insulator-semiconductor structure photo-anode is characterized in that a semiconductor substrate is prepared by a hydrothermal method, an insulating layer is deposited by atomic force, and then high-dispersion metal oxide is prepared by a surface chemical grafting method, so that a metal oxide-insulator-semiconductor MIS structure electrode is constructed.
2. The method for preparing a metal oxide-insulator-semiconductor structured photoanode according to claim 1, comprising the following steps:
(1) pouring the mixed solution prepared in the early stage for synthesizing the semiconductor material into a polytetrafluoroethylene lining, placing FTO in the polytetrafluoroethylene lining, transferring the whole kettle into a steel lining, carrying out a hydrothermal growth process for 300-2Drying; placing the prepared sample in an environment of 400-500 ℃ for 100-120 minutes to prepare a semiconductor electrode;
(2) placing the prepared electrode into a constant-temperature deposition cavity at 150 ℃, alternately pulsing the precursor, circularly depositing for 10-50 times, and obtaining insulating layer-wrapped semiconductor electrode samples with different thicknesses after deposition;
(3) and carrying out vacuum heat treatment on the prepared insulating layer-wrapped semiconductor electrode at 400 ℃ for more than 4 hours to expose enough surface hydroxyl, then injecting a grafting species solution, fully reacting at 150-180 ℃, and then calcining at 300 ℃ under oxygen to obtain the metal oxide-insulator-semiconductor MIS structure electrode.
3. The method as claimed in claim 2, wherein the mixed solution is FeCl in the step (1)3And NaNO3Or one of a mixed solution of HCL and ultrapure water and tetrabutyl titanate.
4. The method as claimed in claim 2, wherein the semiconductor electrode prepared in step (1) is N-TiO2Electrodes or Sn-Fe2O3One of the electrodes.
5. The method as claimed in claim 2, wherein in the step (2), the precursors are trimethyl aluminum TMA and water, trimethyl gallium TMG and water, or silicon chloride SiCl4And water.
6. The method for preparing a metal oxide-insulator-semiconductor structure photoanode as claimed in claim 2, wherein in the step (2), the deposition is performed for 10 times, 30 times and 50 times, respectively, and the insulation layer with different thickness is obtained to wrap the semiconductor electrode sample after the deposition.
7. The method as claimed in claim 2, wherein in the step (3), the grafting species is one of ruthenocene, nickelocene, or tetramethyltin.
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