CN112195483A - Method for constructing Z-type heterojunction photo-anode and Z-type heterojunction photo-anode - Google Patents

Method for constructing Z-type heterojunction photo-anode and Z-type heterojunction photo-anode Download PDF

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CN112195483A
CN112195483A CN202010998614.9A CN202010998614A CN112195483A CN 112195483 A CN112195483 A CN 112195483A CN 202010998614 A CN202010998614 A CN 202010998614A CN 112195483 A CN112195483 A CN 112195483A
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tio
photoanode
glass substrate
anode
photo
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CN112195483B (en
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张闪闪
马明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The method for constructing the Z-type heterojunction photoanode provided by the invention grows the core-shell structure TiO taking the Rutile phase as the core and the Brookite phase as the shell on the surface of the FTO glass substrate2Nano-pillar array and obtaining TiO therefrom2Photoanode, then TiO2Depositing a layer of ultrathin MoO on the photo-anodexNyLayer, synthesis of MoOxNy/TiO2The photoanode forms a unique Z-shaped heterojunction structure taking N atoms as a leading factor, promotes a charge separation process, improves photoresponse current, and has the advantages of simplicity in operation, cleanness, high efficiency, large-scale production and the like. In addition, the invention also provides a Z-type heterojunction photo-anode.

Description

Method for constructing Z-type heterojunction photo-anode and Z-type heterojunction photo-anode
Technical Field
The invention relates to the technical field of photoelectrocatalysis, in particular to a method for constructing a Z-shaped heterojunction photo-anode and the Z-shaped heterojunction photo-anode.
Background
In order to solve the energy and environmental crisis, hydrogen attracts the attention of the world with cleanness, high efficiency and huge development potential. TiO since 19722For the first time as a photocatalyst, Photoelectrochemical (PEC) cells are considered to be a very promising system for hydrogen production. Through the development of more than 40 years, the types of photocatalysts and cell design strategies are infinite, but in general, the photoelectrocatalysis solar energy conversion efficiency is still low at present, so that the photoelectrocatalysis solar energy conversion efficiency cannot be applied on a large scale. How to improve the lightThe catalytic activity of electrocatalysts is a subject of considerable interest in this field.
A variety of materials have been explored for photoanode design, e.g. conventional WO3、Fe2O3Or novel C3N4MOFs materials, and the like. In contrast to the above materials, TiO has a larger band gap value (3.2eV)2Still, a great deal of research is being conducted on the basis of its specific inherent properties, such as high light stability, long-lasting stable activity, low cost, and environmental friendliness. At the same time, TiO has poor light absorption capacity2The rapid electron-hole recombination still exists at the interface between the electrode and the electrolyte, which limits the photoelectrocatalysis performance of the electrode and needs a proper strategy to solve.
The cocatalyst is generally used for solving the problem of surface reaction retardation, and the cocatalyst can be prepared on the surface of the photocatalyst so as to reduce charge carrier recombination and accelerate the surface reaction process. Noble metals (such as Pt, Ru, Au, and the like) have been used as effective promoters, which can significantly improve the catalytic water decomposition performance of the photocatalysts. However, the practical application of noble metals is limited by their scarcity and high cost. Therefore, transition metal compounds are generated, and particularly the promoters consisting of metal oxides and chalcogenides can effectively accelerate the surface catalytic reaction process of the photocatalysts. However, the above strategies still face complicated preparation processes (such as photo-assisted deposition) or dangerous synthesis conditions (such as sulfidation, ammoniation, etc.), which hinder the industrial application of the photocatalysts.
Disclosure of Invention
In view of the above, there is a need for a method for constructing a Z-type heterojunction photo-anode with simple preparation process and with industrial prospect.
A method for constructing a Z-type heterojunction photo-anode comprises the following steps:
pretreating the FTO glass substrate;
obtaining TiO with core-shell structure2A nanopillar array photoanode;
subjecting the TiO to a reaction2Soaking the nano-column array photoanode in ammonium molybdate precursor solution and continuously stirring under heating condition；
Taking out the TiO2Cooling the photo-anode to room temperature, and then subjecting the TiO2Cleaning the surface of the photo-anode and drying;
drying the TiO2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2Photoanode material, wherein, 0<X<3，0<Y<2。
In some embodiments, the step of pretreating the FTO glass substrate specifically includes the following steps:
cutting the FTO glass substrate into 2 x 4cm2Size;
immersing the cut FTO glass substrate into a mixed solution of acetone and absolute ethyl alcohol for ultrasonic treatment for 10-20 min, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1-1: 2;
and soaking the FTO glass substrate subjected to ultrasonic treatment in a mixed solution of hydrogen peroxide and concentrated sulfuric acid, and standing for 5-15 min, wherein the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 1-4: 1;
and soaking the standing FTO glass substrate in absolute ethyl alcohol for 10-20 min, and then drying.
In some embodiments, the thickness of the FTO glass substrate is 2.0-2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6-7 omega, and the thickness of the FTO film layer is 300-350 nm.
In some of these embodiments, the TiO having a core-shell structure is obtained2The method for preparing the nano-pillar array photoanode specifically comprises the following steps:
placing the pretreated FTO glass substrate into a reaction kettle with the conductive surface facing downwards, wherein the reaction kettle takes polytetrafluoroethylene as a lining;
uniformly stirring 20ml of deionized water, 20ml of concentrated hydrochloric acid and 500 mu l of tetrabutyl titanate solution, adding into the reaction kettle, carrying out hydrothermal reaction at 150-200 ℃ for 15-20 h, and cooling to room temperature to obtain a reacted FTO glass substrate;
cleaning and drying the reacted FTO glass substrate, calcining the FTO glass substrate at 400-600 ℃ for 2-3 h, and cooling the FTO glass substrate to room temperatureTo obtain TiO with a core-shell structure2And (4) a nano-pillar array photo-anode.
In some of the embodiments, the concentrated hydrochloric acid has a density of 1.18g/ml at 20 ℃ and an HCl content of 36-38%.
In some of these embodiments, the TiO is added2Soaking the nano-column array photoanode in an ammonium molybdate precursor solution and continuously stirring under a heating condition;
the ammonium molybdate precursor solution is prepared by dissolving 10-300 mg of ammonium molybdate tetrahydrate powder in 100ml of deionized water serving as a basic solvent respectively, heating at 50-100 ℃, maintaining for 2-2.5 h and stirring at a rotating speed of 100-500 r/min.
In some of these embodiments, the TiO is added2Cooling the photo-anode to room temperature, and then subjecting the TiO2The surface of the photo-anode is cleaned and then dried;
subjecting the TiO to a reaction2The photoanode is cooled to room temperature, and the TiO is treated by absolute ethyl alcohol and deionized water2Cleaning the surface of the photo-anode, and then washing the TiO2And drying the photo-anode at 60-80 ℃ for 20-30 min.
In some of these embodiments, the TiO after drying is2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2The steps of the photo-anode material are as follows:
drying the TiO2Calcining the photoanode at 100-500 ℃ in argon atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2A photoanode material.
In addition, the invention also provides a Z-type heterojunction photo-anode which is prepared by the method for constructing the Z-type heterojunction photo-anode.
The method for constructing the Z-type heterojunction photoanode provided by the invention grows the core-shell structure TiO taking the Rutile phase as the core and the Brookite phase as the shell on the surface of the FTO glass substrate2Nano-pillar array and obtaining TiO therefrom2Photoanode, then TiO2Depositing a layer of ultrathin MoO on the photo-anodexNyLayer, synthesis of MoOxNy/TiO2The photoanode forms a unique Z-shaped heterojunction structure taking N atoms as a leading factor, promotes a charge separation process, improves photoresponse current, and has the advantages of simplicity in operation, cleanness, high efficiency, large-scale production and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention or in the description of the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the steps of a method of constructing a Z-type heterojunction photoanode provided by the present invention;
FIG. 2 shows TiO prepared in example 1 of the present invention2SEM image of photo-anode;
FIG. 3 shows TiO prepared in example 1 of the present invention2XRD pattern of photoanode;
FIG. 4 shows the MoO prepared in example 2 of the present inventionxNy/TiO2STEM and FFT diffraction patterns of the photoanode;
FIG. 5 shows the MoO prepared in example 2 of the present inventionxNy/TiO2XPS plot of photoanode;
FIG. 6 shows the MoO prepared in example 3 of the present inventionxNy/TiO2Graph of the photo-response current J-V of the photo-anode.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "horizontal", "inside", "outside", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The construction of the heterojunction with matched energy bands is an attractive strategy for improving the water decomposition capacity of solar energy and realizing the efficient generation of hydrogen. The conventional type II heterojunction has some unique advantages such as formation of a fast charge transfer path, thereby inhibiting recombination of photogenerated electron-hole pairs, promoting charge spatial separation, and improving the light conversion efficiency, but it still faces a problem of relatively low redox capability of charge carriers. The defect is made up by the appearance of the Z-shaped heterojunction, a unique Z-shaped photon-generated carrier transport channel is formed under illumination, and photo-generated electrons with strong reducibility and holes with strong oxidizing capability are reserved. Whereas Z-type heterojunctions are more difficult to implement in PEC (photoelectrochemical) devices due to energy band problems.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments.
Referring to fig. 1, a flowchart of steps of a method for constructing a Z-type heterojunction photo-anode according to an embodiment of the invention includes the following steps:
step S110: and pretreating the FTO glass substrate.
In some embodiments, the thickness of the FTO glass substrate is 2.0-2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6-7 omega, and the thickness of the FTO film layer is 300-350 nm.
In some embodiments, the step of pretreating the FTO glass substrate specifically includes the following steps:
step S111: cutting the FTO glass substrate into 2 x 4cm2Size;
step S112: immersing the cut FTO glass substrate into a mixed solution of acetone and absolute ethyl alcohol for ultrasonic treatment for 10-20 min, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1-1: 2;
step S113: and soaking the FTO glass substrate subjected to ultrasonic treatment in a mixed solution of hydrogen peroxide and concentrated sulfuric acid, and standing for 5-15 min, wherein the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 1-4: 1;
step S114: and soaking the standing FTO glass substrate in absolute ethyl alcohol for 10-20 min, and then drying.
Specifically, the FTO glass substrate is subjected to a drying process with nitrogen gas, which is high-purity nitrogen gas having a purity of 99.999%.
It can be understood that the invention can remove the pollutants attached to the surface of the FTO glass substrate by pretreating the FTO glass substrate, ensure the surface of the substrate to be smooth and clean, and improve the hydrophilicity of the conductive side of the substrate, thereby being beneficial to TiO2And (4) uniformly growing the nano-pillars on the surface of the substrate.
Step S120: obtaining TiO with core-shell structure2And (4) a nano-pillar array photo-anode.
In some of these embodiments, the TiO having a core-shell structure is obtained2The method for preparing the nano-pillar array photoanode specifically comprises the following steps:
step S121: placing the pretreated FTO glass substrate into a reaction kettle with the conductive surface facing downwards, wherein the reaction kettle takes polytetrafluoroethylene as a lining;
step S122: 20ml of deionized water, 20ml of concentrated hydrochloric acid and 500 mul of tetrabutyl titanate solution are added into the reaction kettle after being uniformly stirred, and are cooled to room temperature after hydrothermal reaction for 15-20 h at 150-200 ℃ to obtain a reacted FTO glass substrate;
specifically, the density of the concentrated hydrochloric acid at 20 ℃ is 1.18g/ml, and the HCl content is 36-38%.
Furthermore, the optimal temperature of the hydrothermal reaction is 180 DEG C
Step S123: cleaning and drying the reacted FTO glass substrate, calcining the FTO glass substrate at 400-600 ℃ for 2-3 h, and cooling the FTO glass substrate to room temperature to obtain TiO with a core-shell structure2A nanopillar array photoanode;
preferably, the calcination temperature is 500 ℃ and the temperature rise rate is 5 ℃/min.
In the above embodiment of the invention, a core-shell structure TiO with Rutile phase as core and Brookite phase as shell is grown on the surface of the FTO glass substrate by using a one-step hydrothermal method2The obtained product is high in purity, uniform and regular, and has light color and good conductivity after being calcined. Because the band edge positions on two sides of the homojunction are different, a built-in electric field is formed through energy band matching to inhibit the photoelectric electron-hole recombination, the space separation of charges is promoted, the light conversion efficiency is improved, and the water decomposition capability of PEC is enhanced.
Step S130: subjecting the TiO to a reaction2And soaking the nano-column array photoanode in an ammonium molybdate precursor solution and continuously stirring under a heating condition.
Specifically, the ammonium molybdate precursor solution is prepared by dissolving 10-300 mg of ammonium molybdate tetrahydrate powder in 100ml of deionized water serving as a basic solvent respectively, heating at 50-100 ℃, maintaining for 2-2.5 h, and stirring at a rotating speed of 100-500 r/min.
Step S140: subjecting the TiO to a reaction2Cooling the photo-anode to room temperature, and then subjecting the TiO2And cleaning the surface of the photo-anode and drying.
In some of these embodiments, the TiO is added2Cooling the photo-anode to room temperature, and then subjecting the TiO2The steps of cleaning and drying the surface of the photo-anode specifically comprise:
subjecting the TiO to a reaction2The photoanode is cooled to room temperature, and the TiO is treated by absolute ethyl alcohol and deionized water2Cleaning the surface of the photo-anode, and then washing the TiO2And drying the photo-anode at 60-80 ℃ for 20-30 min.
Step S150:drying the TiO2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2Photoanode material, wherein, 0<X<3，0<Y<2。
In some of these embodiments, the TiO after drying is2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2The steps of the photo-anode material are as follows:
drying the TiO2Calcining the photoanode at 100-500 ℃ in argon atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2A photoanode material.
Preferably, the above calcination temperature is 300 ℃.
In the above embodiment of the invention, in-situ chemical wet method is adopted to treat TiO2A layer of ultrathin MoO is deposited on the photo-anodexNy layer, synthesis of MoOxNyThe layer plays an important role in improving the solar conversion process, TiO2Valence band and MoOxNyThe conduction bands of the layers are matched through energy bands to generate charge channels, and a special Z-shaped heterojunction structure with N atoms as interface pivots is formed, so that MoO is promotedxNyOxidation reaction on the surface of the layer to effectively improve TiO2The photoelectrocatalytic activity of the photoanode.
The method for constructing the Z-type heterojunction photoanode provided by the invention grows the core-shell structure TiO taking the Rutile phase as the core and the Brookite phase as the shell on the surface of the FTO glass substrate2Nano-pillar array and obtaining TiO therefrom2Photoanode, then TiO2Depositing a layer of ultrathin MoO on the photo-anodexNyLayer, synthesis of MoOxNy/TiO2The photoanode forms a unique Z-shaped heterojunction structure taking N atoms as a leading factor, promotes a charge separation process, improves photoresponse current, and has the advantages of simplicity in operation, cleanness, high efficiency, large-scale production and the like.
In addition, the invention provides the Z-type heterojunction photoanode constructed by the in-situ chemical wet method, which is characterized in that the Z-type heterojunction photoanode is formed by a unique Z-type charge transfer mechanismThe process exhibits excellent PEC activity in water splitting. Optimized MoOxNy/TiO2The photocurrent generated by the photo-anode is about pure TiO22.4 times of the total amount of the element, realizes the effect that 1+1 is more than 2 of a single element, has stable product quality, is beneficial to realizing large-batch and industrial production, and opens up new possibility for device construction strategies.
Example 1
Core-shell structure TiO2Preparation of nano-pillar array photo-anode
(1) The method for pretreating the FTO glass substrate specifically comprises the following steps:
a. cutting FTO glass substrate into 2 × 4cm by using glass cutter2Size;
b. and (3) immersing the cut FTO glass substrate into acetone and absolute ethyl alcohol 1:1, mixing the solution, and carrying out ultrasonic treatment for 15 min;
c. and then soaking the FTO glass substrate in hydrogen peroxide and concentrated sulfuric acid 3: 1, standing the mixed solution for 10 min;
d. then soaking the FTO glass substrate in absolute ethyl alcohol, and standing for 15 min;
e. finally using high-purity nitrogen (N)299.999%) was dried on the FTO glass substrate.
(2) Adding 20ml of deionized water, 20ml of concentrated hydrochloric acid and 0.5ml of tetrabutyl titanate into a beaker, and stirring for 30min at room temperature to obtain a mixed solution;
(3) putting the FTO glass substrate pretreated in the step (1) into a high-temperature reaction kettle with polytetrafluoroethylene as a lining in a way that the conductive surface faces downwards, adding the mixed solution obtained in the step (2) into the lining, carrying out hydrothermal reaction in an oven at 180 ℃ for 20 hours, and cooling to room temperature.
(4) Taking out the sample reacted in the step (3) from the lining, washing with deionized water, drying, calcining in a muffle furnace at 500 ℃ for 2h, and cooling to room temperature to obtain the TiO with the core-shell structure2And (4) a nano-pillar array photo-anode.
TiO assay by SEM, as shown in FIG. 22From a top view of the microstructure of the photoanode, uniform, square TiO consisting of smaller nano-pillars can be observed2And (4) array.
As shown in FIG. 3, TiO was determined by XRD diffraction pattern2Crystal structure of the photo-anode. Peaks at 27.4 °, 41.2 °, 44.1 °, 54.3 °, 62.7 °, 69.0 °, and 69.7 ° in the spectrum correspond to the Rutile phase crystal planes (JCPDS nos. 21-1276) of (110), (111), (210), (211), (002), (301), and (112), respectively. Six asterisk labeled peaks 26.4 °, 33.7 °, 37.8 °, 51.5 °, 61.6 °, and 65.6 ° can be classified as FTO glass substrates. In addition, three distinct peaks of 30.8 °, 42.3 ° and 55.7 ° were observed, which peaks, using the # notation, were retrieved as the (121), (221) and (151) planes of the Brookite phase.
Example 2
Construction strategy of Z-shaped heterojunction photo-anode
(A) The TiO prepared by the method of example 12Soaking the photoanode in an ammonium molybdate precursor solution prepared by dissolving 100mg of ammonium molybdate tetrahydrate powder by taking 100ml of deionized water as a basic solvent, and continuously stirring for 2 hours at 70 ℃ at 100 r/min;
(B) TiO obtained in the step (A)2Cooling the photoanode to room temperature, cleaning the surface of the photoanode with absolute ethyl alcohol and deionized water, and drying the material in an oven at 80 ℃ for 30 min;
(C) TiO treated in the step (B)2Calcining the photoanode for 1h at 300 ℃ in the argon atmosphere of a tube furnace to obtain MoO with the special Z-shaped heterojunctionxNy/TiO2A photoanode material.
As shown in FIG. 4, MoOxNy/TiO2The lattice constant measured inside the photoanode was 0.325nm, corresponding to the (110) plane of the Rutile phase. The FFT diffraction of the inner region also shows a lattice constant matching Rutile. At the same time, the FFT diffraction is used for measuring TiO2The edges of the nano-pillars to obtain a more accurate crystal structure, and the lattice constant in the image shows the TiO2The edge part of the nano-column is a Brookite phase with the thickness less than 10 nm. Thus, in combination with the XRD results discussed above, TiO can be determined2The core-shell structure of the nano-column is that a Rutile phase is a core, and a Brookite phase is a shell. In addition, a blurred region was observed from the STEM image, and the region was recognizedIs MoO without obvious crystallizationxNyAnd (3) a layer.
As shown in FIG. 5, to determine the chemical composition of the MoOxNy layer, for TiO2And MoOxNy/TiO2The photoanode was subjected to XPS measurements. The deposition of the MoOxNy layer introduces Mo and N elements at the same time, and the Mo peak can correspond to Mo6+(peaks at 235.9 and 232.7 eV) and Mo4+(peak at 233.0 eV). An additional peak of Mo-N bonds was also found at 231.9 eV. N1 s-Mo 3p3/2The peaks can be subdivided into 401.2, 399.7, 398.5 and 397.3eV four peaks, belonging to the N-O, Mo-O-N, Mo-O and Mo-N bonds, respectively. In summary, MoOxNyThe layer is composed of molybdenum-based oxides, nitrides and oxynitrides.
Example 3
Z-type heterojunction MoOxNy/TiO2Photoanode photoelectrochemical test
1. All photoelectrochemical measurements were performed in a typical three electrode cell at room temperature using a CHI660e potentiostat, with the photoanode (sample prepared as described above) being the working electrode, the Pt foil being the counter electrode and the Ag/AgCl being the reference electrode.
2. The electrolyte is 0.5M Na2SO4Buffered to pH 7.
3. The prepared TiO is mixed with2And MoOxNy/TiO2The photo-anode is cut to 1 × 2cm2Electrode sheet inserted into the electrolyte and having a test area of 1 × 1cm2。
4. Photoelectrochemical measurements were performed using a peccell PEC-L01 solar simulator integrating a 100W xenon arc lamp and an AM 1.5 filter under 1 simulated sunlight exposure.
5. For photocurrent measurements, Linear Sweep Voltammetry (LSV) was used, with the sweep rate being maintained at 0.05V/s.
6. According to Nernst equation (E)RHE＝EAg/AgCl+0.0591pH+E0 Ag/Cl) Converting the measured potential of the Ag/AgCl electrode (saturated KCl solution) into a reversible hydrogen electrode (V)RHE) An electrical potential.
As shown in FIG. 6, MoO can be seen from the J-V curvexNy/TiO2The photocurrent of the photoanode is about 1.2mA/cm at 1.23V2RHE, pure TiO22.4 times that of the photoanode, excellent PEC performance was exhibited, confirming MoOxNyThe layer has a useful role in improving the solar conversion process.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented merely for purposes of illustration and description of the principles of the invention and is not intended to limit the scope of the invention in any way. Any modifications, equivalents and improvements made within the spirit and principles of the invention and other embodiments of the invention without the creative effort of those skilled in the art are included in the protection scope of the invention based on the explanation here.

Claims (9)

1. A method for constructing a Z-type heterojunction photoanode is characterized by comprising the following steps:
pretreating the FTO glass substrate;
obtaining TiO with core-shell structure2A nanopillar array photoanode;
subjecting the TiO to a reaction2Soaking the nano-pillar array photoanode in an ammonium molybdate precursor solution and continuously stirring under a heating condition;
taking out the TiO2Cooling the photo-anode to room temperature, and then subjecting the TiO2Cleaning the surface of the photo-anode and drying;
drying the TiO2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2Photoanode material, wherein, 0<X<3，0<Y<2。
2. The method for constructing a Z-type heterojunction photoanode of claim 1, wherein the step of pretreating the FTO glass substrate comprises the following steps:
cutting the FTO glass substrate into 2 x 4cm2Size;
immersing the cut FTO glass substrate into a mixed solution of acetone and absolute ethyl alcohol for ultrasonic treatment for 10-20 min, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1-1: 2;
and soaking the FTO glass substrate subjected to ultrasonic treatment in a mixed solution of hydrogen peroxide and concentrated sulfuric acid, and standing for 5-15 min, wherein the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 1-4: 1;
and soaking the standing FTO glass substrate in absolute ethyl alcohol for 10-20 min, and then drying.
3. The method for constructing a Z-type heterojunction photoanode according to claim 2, wherein the thickness of the FTO glass substrate is 2.0-2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6-7 Ω, and the thickness of the FTO film layer is 300-350 nm.
4. The method of claim 1, wherein the core-shell structure of TiO is obtained2The method for preparing the nano-pillar array photoanode specifically comprises the following steps:
placing the pretreated FTO glass substrate into a reaction kettle with the conductive surface facing downwards, wherein the reaction kettle takes polytetrafluoroethylene as a lining;
uniformly stirring 20ml of deionized water, 20ml of concentrated hydrochloric acid and 500 mu l of tetrabutyl titanate solution, adding into the reaction kettle, carrying out hydrothermal reaction at 150-200 ℃ for 15-20 h, and cooling to room temperature to obtain a reacted FTO glass substrate;
cleaning and drying the reacted FTO glass substrate, calcining the FTO glass substrate at 400-600 ℃ for 2-3 h, and cooling the FTO glass substrate to room temperature to obtain TiO with a core-shell structure2And (4) a nano-pillar array photo-anode.
5. The method according to claim 4, wherein the concentrated hydrochloric acid has a density of 1.18g/ml at 20 ℃ and an HCl content of 36-38%.
6. The method of claim 1 for constructing a Z-type heterojunction photoanodeCharacterized in that the TiO is added2Soaking the nano-column array photoanode in an ammonium molybdate precursor solution and continuously stirring under a heating condition;
the ammonium molybdate precursor solution is prepared by dissolving 10-300 mg of ammonium molybdate tetrahydrate powder in 100ml of deionized water serving as a basic solvent respectively, heating at 50-100 ℃, maintaining for 2-2.5 h and stirring at a rotating speed of 100-500 r/min.
7. The method of claim 1, wherein the TiO is added to the solution to form a Z-type heterojunction photoanode2Cooling the photo-anode to room temperature, and then subjecting the TiO2The surface of the photo-anode is cleaned and then dried;
subjecting the TiO to a reaction2The photoanode is cooled to room temperature, and the TiO is treated by absolute ethyl alcohol and deionized water2Cleaning the surface of the photo-anode, and then washing the TiO2And drying the photo-anode at 60-80 ℃ for 20-30 min.
8. The method of claim 1, wherein the TiO after drying is used in the fabrication of a Z-type heterojunction photoanode2The photoanode is calcined at high temperature in an inert atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2The steps of the photo-anode material are as follows:
drying the TiO2Calcining the photoanode at 100-500 ℃ in argon atmosphere to obtain MoO with Z-type heterojunctionxNy/TiO2A photoanode material.
9. A Z-type heterojunction photoanode, prepared by the method of any one of claims 1 to 8 for constructing a Z-type heterojunction photoanode.
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