Three-dimensional ordered hollow cuprous oxide nano-array and preparation method and application thereof

Abstract

The application discloses a kind of three-dimensional ordered hollow cuprous oxide nano array and its preparation method and application, it is related to photoelectric detection technical field.Preparation method includes: impurity aluminum is oxidized, and the aluminum oxide template with the hole formed on surface is obtained, and after reaming, the three-dimensional porous aluminum oxide template with back aluminum is obtained;With three-dimensional porous aluminum oxide template as cathode, graphite is anode, in Cu electrodeposition liquid, constant current electrodeposition is carried out, and the three-dimensional porous aluminum oxide template with back aluminum loaded with copper nanowire is obtained;Three-dimensional porous aluminum oxide template with back aluminum is removed using alkali solution, and three-dimensional interconnected self-supporting copper nanowire array is obtained;Three-dimensional interconnected self-supporting copper nanowire array is annealed under local hypoxia environment, and three-dimensional highly ordered hollow cuprous oxide nano array is obtained by cooling down.The self-powered photoelectrochemical type photoelectric detector prepared by using the hollow cuprous oxide nano array has high light absorption rate, high specific surface area and high ion transmission rate, and is suitable for ultraviolet light detection.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hollow cuprous oxide nanometer array photoelectric detection, and particularly relates to a three-dimensional ordered hollow cuprous oxide nanometer array and a preparation method and application thereof. BACKGROUND

[0002] With the continuous progress of information communication technology, light has become an important medium for information acquisition, recording, analysis and transmission. As a kind of photoelectric device that uses photoelectric effect to detect and measure the characteristics of light, photoelectric detector has been widely used in optical communication, radar monitoring, satellite remote sensing, health monitoring, solar cells and other fields. As a new type of photoelectric detector, photoelectrochemical photoelectric detector is based on the semiconductor-liquid contact mechanism, has a unique solid-liquid heterojunction structure, and a semiconductor material and an electrolyte liquid surface contact form an approximate Schottky diode interface. The built-in electric field formed at the interface separates the electron-hole pairs. When light is irradiated on the semiconductor material on the photoanode, the semiconductor absorbs light energy to generate electron-hole pairs, which are separated under the action of the built-in electric field, and finally captured and transmitted to the counter electrode by the FTO (fluorine-doped tin oxide) conductive glass, with high response speed and response degree. Due to its working mechanism, the photoelectrochemical photoelectric detector can be directly used in marine underwater communication and detection without packaging. Compared with the traditional photoelectric detector which needs external power supply, the photoelectrochemical photoelectric detector can realize self-powered independent work under zero or low bias voltage, realize the functions of photoelectric detector optical sensing and long-time operation, effectively cope with underwater emergencies, have strong risk resistance, and greatly ensure the safety and efficiency of underwater detection communication.

[0003] In order to obtain a high-performance photoelectrochemical photoelectric detector, in the design of photoelectrode semiconductor materials, researchers usually select and prepare semiconductor materials with excellent light absorption, high specific surface area and good chemical stability. Among them, metal oxide semiconductor materials have become an important choice for underwater photoelectrochemical photoelectric detector semiconductor materials due to their good photoelectrochemical performance, high chemical stability and low cost. Cuprous oxide Cu2O as a kind of metal oxide semiconductor material, its raw material copper metal has abundant reserves in nature, and it is simple to prepare and has good photoelectric response performance in a specific light wave band. However, the research on Cu2O-based photoelectric detector is still in its infancy, and mainly focuses on traditional solid-state photoelectric detectors, and there is little research on Cu2O photoelectrochemical photoelectric detector.

[0004] At present, the photoelectrochemical type photoelectric detectors designed by researchers are mostly sandwich structures, in which the photoelectrode is mostly in the form of powder coated on conductive glass, and the counter electrode is platinum sheet or platinum wire. Due to the powder coating of the photoelectrode of the traditional semiconductor material, the semiconductor material particles are stacked with each other, the contact area with the electrolyte is small, the electron-hole pairs generated at the interface are limited, and in actual application, the semiconductor material gradually falls off with the corrosion of seawater. Due to the planar disordered structure, the specific surface area of the electrolyte in contact with the material surface is small, and the ion transmission is seriously limited in the complex disordered structure. In addition, due to the planar structure, when the light directly irradiates on the material surface, the semiconductor material cannot fully absorb the light energy, and reflection occurs, so the light utilization rate is low. In actual application, under the dim seabed, the light utilization rate is seriously insufficient, the response speed and responsivity of the material are reduced, which seriously restricts the photoelectric sensing performance of the material under the complex conditions of the seabed. The traditional nanomaterial array is usually composed of independent nanowires or nanosheets, and the wires and the sheets are independent of each other, which is prone to lodging phenomenon, which not only blocks the propagation path of light, but also hinders the rapid transmission channel of ions, causing serious recombination of carriers, and the structure and working stability of the material are also greatly affected.

[0005] Based on the problems existing in the prior art, the present application develops a self-powered photoelectrochemical type photoelectric detector based on a three-dimensional highly ordered hollow cuprous oxide nanometer array structure to realize the photoelectric sensing function in a low light power environment. SUMMARY

[0006] The present application aims to at least solve one of the technical problems existing in the prior art;

[0007] To this end, the present application proposes a three-dimensional ordered hollow cuprous oxide nanometer array and a preparation method and application thereof, the method comprising:

[0008] S1, electrochemically anodizing impurity aluminum to obtain an aluminum oxide template with a plurality of vertical holes having a plurality of transverse holes on the inner wall, and the vertical holes are not connected between the vertical holes, and after hole expansion, the plurality of vertical holes are connected through the transverse holes two by two to obtain a three-dimensional porous aluminum oxide template with back aluminum; the impurity aluminum is an aluminum alloy material containing controllable impurities;

[0009] S2, using the three-dimensional porous aluminum oxide template with back aluminum as a cathode and graphite as an anode, constant current electrodeposition in a Cu electrodeposition solution to obtain a three-dimensional porous aluminum oxide template with back aluminum loaded with copper nanowires;

[0010] S3, removing the three-dimensional porous aluminum oxide template with back aluminum by using an alkali solution to obtain a three-dimensional interconnected self-supporting copper nanowire array;

[0011] S4, annealing the three-dimensional interconnected self-supporting copper nanowire array under a local oxygen-deficient environment at 180-220 DEG C, and naturally cooling to obtain a three-dimensional highly ordered hollow cuprous oxide nanometer array.

[0012] Further, in S1, the conditions for electrochemically anodizing the impure aluminum are as follows: the impure aluminum is placed in a phosphoric acid electrolyte for anodization, the electrolyte is a 0.25-0.35 M phosphoric acid solution, the solvent of the phosphoric acid solution is a mixture of anhydrous ethanol and water; the anodization voltage is 190-200 V, the temperature is 4-6 DEG C, and the oxidation time is 18-22 h.

[0013] Further, in S1, the impurities in the impure aluminum are copper, and the impurity content is 1%;

[0014] The conditions for electrochemically anodizing the impure aluminum are as follows: the impure aluminum is placed in a phosphoric acid electrolyte for anodization, the electrolyte is a 0.3 M phosphoric acid solution, the solvent of the phosphoric acid solution is a mixture of anhydrous ethanol and pure water in a volume ratio of 1:9; the anodization voltage is 195 V, the temperature is 5 DEG C, and the oxidation time is 20 h.

[0015] Further, in S1, the reaming treatment method is as follows:

[0016] After the anodized aluminum template is dried, it is immersed in a 4-6 wt% phosphoric acid solution at 38-45 DEG C for 30-50 min to ream the vertical holes in the template that are not connected to each other, so that the vertical holes are enlarged and connected to each other through the horizontal holes. After being washed with pure water, a three-dimensional porous anodized aluminum template with a back aluminum layer is obtained, which is stored for use.

[0017] Further, in S2, the Cu electrodeposition solution contains 90-100 g / L of CuSO4 and 40-50 g / L of H2SO4.

[0018] Further, in S3, the alkaline solution is a 3-5 M NaOH solution.

[0019] After being washed with pure water for several times and dried, a three-dimensional interconnected self-supporting copper nanowire array is obtained.

[0020] Further, in S4, the three-dimensional interconnected self-supporting copper nanowire array prepared in S3 is placed between two flat copper foams to obtain a local oxygen-deficient environment. The three-dimensional interconnected self-supporting copper nanowire array and the copper foams are placed in a furnace, and the whole is kept at 200 DEG C in an air atmosphere for 15 h, and then naturally cooled to obtain a three-dimensional ordered hollow cuprous oxide nanometer array.

[0021] A three-dimensional ordered hollow cuprous oxide nanometer array is prepared by the above method.

[0022] A self-powered photoelectrochemical photodetector comprises FTO conductive glass and the aforementioned three-dimensional ordered hollow cuprous oxide nanometer array; the three-dimensional ordered hollow cuprous oxide nanometer array is combined to the surface of the FTO conductive glass.

[0023] The application of the aforementioned three-dimensional ordered hollow cuprous oxide nanometer array in preparing a photodetector.

[0024] Compared with the prior art, the self-powered photoelectrochemical photodetector has the following beneficial effects:

[0025] The preparation method of the self-powered photoelectrochemical photodetector provided by the application is as follows: three-dimensional highly ordered copper nanowires are directly annealed into three-dimensional highly ordered hollow cuprous oxide nanometer arrays by one-step annealing, the process is simple, the experimental operation is greatly simplified, and the preparation process is environmentally friendly; the raw material used is a non-noble metal, which is cheap and easy to obtain, and the production cost is greatly reduced.

[0026] The three-dimensional highly ordered hollow cuprous oxide nanometer array is used to confine light in the nanometer slits of the nanowire array and continuously reflect the light, thereby improving the utilization efficiency of light and achieving a high photocurrent density in a weak light environment. 2 In a 0.1 mol / L NaSO4 electrolyte solution, under the irradiation of light with a wavelength of 365 nm and a power of 0.7 mW / cm 2 , the photocurrent reaches 2.4 uA / cm , and the responsivity is 3.43 mA / W, so that the self-powered photoelectrochemical photodetector has higher imaging clarity and sensitivity in underwater detection, and solves the problem of low responsivity caused by low light utilization efficiency of the traditional photoelectrochemical photodetector.

[0027] Due to the three-dimensional highly ordered hollow cuprous oxide nanometer array structure, the material has a very high specific surface area, fully contacts with the electrolyte solution, and has a rich solid-liquid contact interface, which is beneficial to the separation of carriers. At the same time, under the highly ordered structure, the ion transmission speed is significantly improved, and the response speed of the photodetector is improved; under the irradiation of light with a wavelength of 365 nm and a power of 0.7 mW / cm 2 , the photoelectric response speed of the photodetector is 46 ms / 0.2 s, and the photodetector has very high sensitivity under weak light conditions, and is suitable for a wide range of scenes. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 It is a scanning electron microscope magnified image of the side of the three-dimensional highly ordered hollow cuprous oxide nanometer array material of the application;

[0029] Figure 2 It is a scanning electron microscope magnified image of the side of the three-dimensional highly ordered hollow cuprous oxide nanometer array material of the application;

[0030] Figure 3 The scanning electron microscope magnified image of the front surface of the three-dimensional highly-ordered hollow cuprous oxide nanometer array material of the present application;

[0031] Figure 4 The scanning electron microscope magnified image of the back surface of the three-dimensional highly-ordered hollow cuprous oxide nanometer array material of the present application;

[0032] Figure 5 The X-ray diffraction pattern of the three-dimensional highly-ordered hollow cuprous oxide nanometer array of the present application;

[0033] Figure 6 The X-ray photoelectron spectrum of the Cu2p orbit of the three-dimensional highly-ordered hollow cuprous oxide nanometer array of the present application;

[0034] Figure 7 The Auger electron spectrum of Cu of the three-dimensional highly-ordered hollow cuprous oxide nanometer array of the present application;

[0035] Figure 8 The ultraviolet-visible absorption spectrum of the three-dimensional highly-ordered hollow cuprous oxide nanometer array of the present application and the corresponding Tacu curve;

[0036] Figure 9 The photocurrent curve of the three-dimensional highly-ordered hollow cuprous oxide nanometer array applied to a photodetector under the irradiation of 365nm pulsed light with a power intensity of 0.7mW / cm 2

[0037] Figure 10 The effect diagram of different bias on photocurrent of the three-dimensional highly-ordered hollow cuprous oxide nanometer array applied to a photodetector under the irradiation of 365nm pulsed light with a power intensity of 0.7mW / cm 2

[0038] Figure 11 The response time curve of the three-dimensional highly-ordered hollow cuprous oxide nanometer array applied to a photodetector under the irradiation of 365nm pulsed light with a power intensity of 0.7mW / cm 2

[0039] Figure 12 The schematic diagram of the vertical hole disconnected alumina template before the hole expansion of the present application;

[0040] Figure 13 The schematic diagram of the vertical hole connected alumina template after the hole expansion of the present application. DETAILED DESCRIPTION

[0041] ​​​The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0042] See also Figures 1-11 , the present application provides a method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray;

[0043] Example 1

[0044] As embodiment 1 of the present application, the method specifically includes:

[0045] The impurity aluminum is electrochemically oxidized and the pores are expanded to obtain a three-dimensional porous alumina template with back aluminum.

[0046] Using the back aluminum of three-dimensional porous alumina as cathode and graphite as anode, constant current electrodeposition was performed in a Cu electrodeposition solution to obtain copper nanowires with a three-dimensional porous alumina template and back aluminum.

[0047] The aluminum oxide template and back aluminum were removed using NaOH to obtain three-dimensional interconnected copper nanowires;

[0048] The three-dimensional interconnected self-supporting copper nanowires were placed in a tube furnace and maintained at 200°C in air for 15 hours to directly anneal the copper into a hollow cuprous oxide structure, obtaining a three-dimensional highly ordered hollow cuprous oxide nanoarray.

[0049] Example 2

[0050] As a second embodiment of the present application, the method specifically includes:

[0051] Step 1: Anodize the impure aluminum in a phosphoric acid electrolyte to obtain an alumina template with disconnected transverse pores on the surface of the impure aluminum; the alumina template with disconnected transverse pores refers to the alumina template having a plurality of vertical pores, the inner walls of the vertical pores having pits formed by a plurality of transverse pores, and the transverse pores of the vertical pores are not connected to the transverse pores of other vertical pores;

[0052] The reasons for the formation of vertical holes and transverse holes are as follows: first, when pure aluminum is oxidized, smooth vertical holes will be formed. However, when impure aluminum is oxidized, due to the presence of impure copper, the impure aluminum will form several holes on its originally smooth inner wall while forming vertical holes. Figure 12 As shown in the figure; these holes are the transverse holes before expansion. After expansion, the transverse holes will be horizontally connected with the adjacent vertical holes. Figure 13 As shown;

[0053] The purity of the impurity aluminum is 99%, the impurity is copper, the phosphoric acid electrolyte is a 0.3 mol / L phosphoric acid solution, and the solvent ratio of the phosphoric acid electrolyte is anhydrous ethanol: pure water = 1:9;

[0054] The anodic oxidation conditions are: the voltage is 195 V, the temperature is 5°C, and the oxidation time is 20 h;

[0055] After taking out, drying, and soaking in a 5wt% phosphoric acid solution at 40°C for 40 min, the disconnected transverse holes in the aluminum oxide template are connected;

[0056] After multiple cleanings with pure water, a three-dimensional porous aluminum oxide template (3D-AAO) with a back aluminum is obtained and stored in pure water for later use.

[0057] Step two, copper electrodeposition is carried out on the 3D-AAO with a back aluminum, the Cu electrodeposition solution contains 95 g / L of CuSO4 and 45 g / L of H2SO4, the back aluminum of the 3D-AAO serves as the cathode, and the graphite sheet serves as the anode, the constant current electrodeposition is carried out at a current of 3 mA for 2.5 h; a copper nanowire with a 3D-AAO template and a back aluminum is obtained;

[0058] Step three, the copper nanowire with a 3D-AAO template and a back aluminum obtained after electrodeposition is placed in 3 mol / L NaOH to remove the 3D-AAO and the back aluminum, and after multiple pure water rinsing and drying, a three-dimensional interconnected self-supporting copper nanowire array with a thickness of about 20 µm is obtained;

[0059] Step four, the prepared three-dimensional interconnected self-supporting Cu nanowire is placed between two flat foam coppers in a tube furnace to obtain a local oxygen-deficient environment, the heating rate is 1°C / min, and the temperature is maintained at 200°C in an air atmosphere for 15 h, and then naturally cooled down, to obtain a three-dimensional highly ordered hollow cuprous oxide nanometer array;

[0060] Example 3

[0061] As an embodiment of the present application, the three-dimensional highly ordered hollow cuprous oxide nanometer array mentioned in Example One and Example Two is used to prepare a self-powered photoelectrochemical type photoelectric detector in combination with FTO conductive glass, and the specific preparation method is as follows:

[0062] The FTO conductive glass is ultrasonically cleaned in acetone, ethanol, water, and ethanol in sequence for 15 min each time, and then placed in ethanol for standby;

[0063] The binder is PVDF and DMF configured in a ratio of 1:9; DMF is N,N-dimethylformamide, PVDF is polyvinylidene fluoride, and DMF is used to dissolve PVDF; after mixing, the two are used as a binder to bond the material to the FTO conductive glass;

[0064] The three-dimensional interconnected self-supporting copper oxide hollow nanometer array is placed on the FTO conductive glass, flattened and dropped with a binder to obtain a three-dimensional highly ordered hollow cuprous oxide nanometer array self-powered photoelectrochemical type photoelectric detector.

[0065] Based on the problems existing in the prior art, the three-dimensional highly ordered hollow cuprous oxide nanometer array structure is used to solve the existing problems. When light is irradiated on the three-dimensional highly ordered array, the light will pass through the slits of the hollow Cu2O nanometer array, enter the inside of the three-dimensional highly ordered array, be reflected inside the ordered array, and be continuously absorbed in the reflection, greatly improving the light absorption rate of the material and enhancing the light response degree in a weak light environment.

[0066] The three-dimensional ordered hollow cuprous oxide nanometer array has a three-dimensional ordered hollow structure, a large number of micropores exist on the surface of the array unit, the electrolyte can enter the inside of the hollow nanometer array through the micropores, has a very high specific surface area and a rich solid-liquid interface. Compared with ordinary low-order nanometer arrays, the hollow nanometer rods are connected by hollow nanometer channels at equal distances, the hollow nanometer array does not have stacking phenomenon, has high order and structural stability, improves the ion transmission speed and the light response speed.

[0067] In summary, the three-dimensional ordered hollow cuprous oxide nanometer array solves the problems of low light utilization rate, slow ion transmission speed and low specific surface area of the traditional photoelectrochemical type photoelectric detector by constructing a highly ordered three-dimensional hollow nanometer array, and improves the light response degree and the light response speed of the photoelectrochemical type photoelectric detector.

[0068] The three-dimensional ordered hollow cuprous oxide nanometer array mentioned in the present application has excellent material structure and photoelectric performance, and can be applied to the fields of photoelectric water splitting, photoelectric reduction of CO2 and the like by being compounded with other metal nanoparticles (such as Pt, Au, Ru and the like).

[0069] As shown in Figure 1 , Figure 2 shown in the magnified image of the scanning electron microscope, the thickness of the three-dimensional highly ordered hollow cuprous oxide nanometer array material is about 20 pm, which is a highly ordered hollow porous structure, has a micrometer-level thickness and an ordered hollow porous structure, can be more fully contacted with the electrolyte compared with conventional two-dimensional materials, avoids the lodging of nanowires through lateral connection, ensures the three-dimensional stable structure and the ion fast transmission channel, makes the light multiple reflection in the process of entering the three-dimensional highly ordered hollow cuprous oxide nanometer array material, improves the light utilization rate of the photoelectric detector under weak light conditions, and improves the photoelectric detection ability of the material under weak light conditions.

[0070] As shown in Figure 3 , Figure 4As shown in the scanning electron microscope, the front and back images of the three-dimensional highly ordered hollow cuprous oxide nanometer array can be seen, and the slits between the hollow nanowires can well allow light to enter the material inside and at the same time can be used as a rapid ion transmission channel, thereby improving the responsivity and response speed of the material.

[0071] When the three-dimensional highly ordered hollow cuprous oxide nanometer array of Example 2 is subjected to X-ray detection, as shown in Figure 5 , the X-ray diffraction pattern of the three-dimensional highly ordered hollow cuprous oxide nanometer array is obtained, which is consistent with the cuprous oxide standard card (Cu2O PDF #01-077-0199), indicating that the main component of the material is Cu2O, and the content of CuO is low, which has no negative effect on photoelectric detection.

[0072] When the three-dimensional highly ordered hollow cuprous oxide nanometer array of Example 2 is subjected to X-ray detection, as shown in Figure 6 and Figure 7 , the X-ray photoelectron spectrum of Cu2p orbit and the Cu LMM Auger electron spectrum of the three-dimensional highly ordered hollow cuprous oxide nanometer array are obtained, respectively, from which it can be seen that the valence state of Cu in the material is mainly Cu + and a small amount of Cu 2+ .

[0073] When the three-dimensional highly ordered hollow cuprous oxide nanometer array of Example 2 is subjected to X-ray detection, as shown in Figure 8 , the UV-visible absorption spectrum and the corresponding Tacu curve of the three-dimensional highly ordered hollow cuprous oxide nanometer array are shown, and in the range of 850-350nm light, the absorption of the material to light is mainly concentrated in the near ultraviolet light band, i.e. about 365nm, and according to the Tacu curve, the band gap is about 2.88eV.

[0074] When the three-dimensional highly ordered hollow cuprous oxide nanometer array of Example 3 is applied to photoelectric detector for detection, as shown in Figure 9 , under the 365nm pulsed light with a power intensity of 0.7mW / cm 2 , the photocurrent curve of the three-dimensional highly ordered hollow cuprous oxide nanometer array is obtained, the photoelectrochemical type photoelectric detector is immersed in 0.1M Na2SO4 electrolyte, the reference electrode is Ag / AgCl reference electrode, and the counter electrode is platinum wire, a-0.4V bias is applied to the reference electrode, and at the same time, 365nm wavelength pulsed light is used for irradiation, the power is controlled to be 0.7mW / cm 2 , the pulsed light is adjusted to be on and off every 10s, the photocurrent is about 2.4µA / cm 2 , and the responsivity is 3.43mA / W, which proves that the photoelectrochemical type photoelectric detector has very high responsivity in deep sea detection.

[0075] The three-dimensional highly-ordered hollow cuprous oxide nanometer array of embodiment three is applied to a photoelectric detector for detection, and under the same test condition, the influence of different bias of the three-dimensional highly-ordered hollow cuprous oxide nanometer array on photocurrent is shown in the following table 1 when the power intensity is 0.7 mW / cm 2 Figure 9 2 Figure 10 The response time curve of the three-dimensional highly-ordered hollow cuprous oxide nanometer array is shown in the following table 2 when the power intensity is 0.7 mW / cm 2

[0076] The three-dimensional highly-ordered hollow cuprous oxide nanometer array of embodiment three is applied to a photoelectric detector for detection, and under the same test condition, the influence of different bias of the three-dimensional highly-ordered hollow cuprous oxide nanometer array on photocurrent is shown in the following table 1 when the power intensity is 0.7 mW / cm 2 Figure 9 2 Figure 11 The response time curve of the three-dimensional highly-ordered hollow cuprous oxide nanometer array is shown in the following table 2 when the power intensity is 0.7 mW / cm 2

[0077] The above embodiments are only used to illustrate the technical method of the present application and are not limited. Although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical method of the present application can be modified or replaced equivalently without departing from the spirit and scope of the technical method of the present application.​​

Claims

1. A method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray, characterized in that: include: S1. Electrochemically anodic oxidation is performed on the impure aluminum to obtain an alumina template having a plurality of vertical holes with a plurality of transverse holes on the inner wall, and the vertical holes are not connected to each other. After the hole expansion treatment, the plurality of vertical holes are connected to each other by transverse holes to obtain a three-dimensional porous alumina template with back aluminum; S2, using the three-dimensional porous alumina template as the cathode and graphite as the anode, constant current electrodeposition is performed in a Cu electrodeposition solution to obtain a three-dimensional porous alumina template with back aluminum loaded with copper nanowires; S3, removing the three-dimensional porous alumina template with back aluminum using an alkaline solution to obtain a three-dimensional interconnected self-supporting copper nanowire array; S4. Annealing the three-dimensional interconnected self-supporting copper nanowire array at 180-220° C. in a local oxygen-deficient environment and then naturally cooling the array to obtain a three-dimensional highly ordered hollow cuprous oxide nanowire array.

2. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 1, wherein: In S1, the conditions for electrochemical anodization of the impurity aluminum are as follows: the impurity aluminum is placed in a phosphoric acid electrolyte for anodization, the electrolyte is a 0.25-0.35M phosphoric acid solution, and the solvent of the phosphoric acid solution is a mixture of anhydrous ethanol and water; the anodization voltage is 190-200V, the temperature is 4-6°C, and the oxidation time is 18-22h.

3. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 2, wherein: In S1, the impurity in the impurity aluminum is copper, and the impurity content is 1%; The conditions for electrochemical anodization of impure aluminum are as follows: the impure aluminum is placed in a phosphoric acid electrolyte for anodization, the electrolyte is a 0.3M phosphoric acid solution, and the solvent of the phosphoric acid solution is anhydrous ethanol: pure water mixed in a volume ratio of 1:9; the anodization voltage is 195V, the temperature is 5°C, and the oxidation time is 20h.

4. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 1, 2 or 3, wherein: In S1, the hole expansion processing method is: The alumina template obtained after electrochemical anodization is dried and immersed in a 4-6wt% phosphoric acid solution at 38-45°C for 30-50 minutes to expand the pores, and the unconnected vertical pores inside the alumina template are expanded and connected through the transverse holes; after washing with pure water, a three-dimensional porous alumina template with back aluminum is obtained, and the pure water is stored for future use.

5. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 1, wherein: In S2, the Cu electrodeposition solution contains 90-100 g / L of CuSO4 and 40-50 g / L of H2SO4.

6. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 1, wherein: In S3, the alkaline solution is a 3-5 M NaOH solution; After multiple pure water rinses and drying, a three-dimensional interconnected self-supporting copper nanowire array was obtained.

7. The method for preparing a three-dimensional ordered hollow cuprous oxide nanoarray according to claim 1, wherein: In S4, the three-dimensional interconnected self-supporting copper nanowire array prepared in S3 is placed between two flat pieces of foam copper to obtain a local oxygen-deficient environment. The three-dimensional interconnected self-supporting copper nanowire array and the foam copper are placed in a furnace as a whole. After being kept in an air atmosphere of 200°C for 15 hours, the temperature is naturally lowered to obtain a three-dimensional ordered hollow cuprous oxide nanoarray.

8. A three-dimensional ordered hollow cuprous oxide nanoarray, characterized in that: The method is prepared according to any one of claims 1 to 7.

9. A self-powered photoelectrochemical photodetector, characterized in that: The invention comprises FTO conductive glass and the three-dimensional ordered hollow cuprous oxide nanoarray according to claim 8; the three-dimensional ordered hollow cuprous oxide nanoarray is combined with the surface of the FTO conductive glass.

10. Use of the three-dimensional ordered hollow cuprous oxide nanoarray according to claim 8 in the preparation of a photodetector.

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