3D Printed Metal Substrate Supported Iron Oxide Photoanode

Abstract

This invention discloses a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer integrally formed by 3D printing technology and a metal array structure above it, or a grid-shaped array structure formed by 3D printing technology. The metal array structure has multiple graphic units arranged in an array. The titanium-doped iron oxide layer covers the surface of the 3D-printed metal substrate. By studying the photoelectric properties of 3D-printed metal substrate-supported iron oxide photoanodes formed with different 3D structures and materials, the problems of difficult 3D structure construction of iron oxide photoanodes and low light absorption efficiency of thin-film iron oxide photoanodes are solved. This 3D-printed metal substrate-supported iron oxide photoanode exhibits excellent photoelectric water splitting reaction performance and has high application value in future industries.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new energy materials, and particularly relates to a 3D-printed metal substrate supported iron oxide photoanode. BACKGROUND

[0002] In the field of photoelectrocatalytic water splitting, iron oxide (Fe2O3) photoanode has been widely studied due to its wide light absorption range, good stability, low cost and non-toxicity. However, Fe2O3 has a large light absorption depth but a short hole transport distance, resulting in low light absorption efficiency of thin film Fe2O3 and low photocharge transport efficiency of thick film Fe2O3. A large number of reports show that the use of metal ions (such as Ti) for doping can improve the conductivity and the photocurrent density to some extent. In addition, the construction of 3D structure to increase the light absorption depth or the light reflection path can improve the light absorption efficiency of thin film Fe2O3. However, it is difficult to construct a 3D structure of the photoanode, and therefore, it is urgent to obtain a flexible construction method of the 3D structure of Fe2O3 by using the front-line technology.

[0003] The 3D printing technology controlled by a computer can realize one-step manufacturing of a complex 3D structure with high precision and complexity. However, the 3D printing technology has not been used in the 3D structure design and preparation of Fe2O3 electrode in the prior art. SUMMARY

[0004] The present application aims to overcome the deficiencies in the prior art and provide a 3D-printed metal substrate supported iron oxide photoanode, which solves the problems of difficult 3D structure construction of Fe2O3 and low light absorption efficiency of thin film Fe2O3.

[0005] To achieve the above object, the technical scheme of the present application is as follows.

[0006] A 3D-printed metal substrate supported iron oxide photoanode comprises a 3D-printed metal substrate and a titanium-doped iron oxide layer, wherein the 3D-printed metal substrate comprises a conductive layer and a metal array structure above the conductive layer which are integrally formed by a 3D printing technology, or a grid-shaped array structure formed by a 3D printing technology, a plurality of graphic units arranged in an array are arranged on the metal array structure, and the titanium-doped iron oxide layer is arranged on the surface of the 3D-printed metal substrate.

[0007] Preferably, the metal array structure is arranged on one side surface of the conductive layer, and the distribution area of the metal array structure is at least half of the upper surface area of the conductive layer.

[0008] As preferred, the graphic unit is a conical protrusion, the metal array structure is a conical array, the bottom radius of the conical protrusion is 0.5-0.8 mm, and the height is 1-6 mm.

[0009] As preferred, the graphic unit is a conical protrusion, the metal array structure is a conical array, the bottom radius of the conical protrusion is 0.5-0.8 mm, and the height is 1-6 mm.

[0010] As preferred, the graphic unit is a conical protrusion, the metal array structure is a conical array, the bottom radius of the conical protrusion is 0.5-0.8 mm, and the height is 1-6 mm.

[0011] As preferred, the center distance between two adjacent graphic units in the metal array structure is 1.25 mm.

[0012] As preferred, the grid prism of the grid-shaped array structure is a triangular prism or a cylinder, and the grid spacing is 0.2 mm.

[0013] As preferred, the thickness of the conductive layer is 2 mm.

[0014] As preferred, the 3D printing metal base adopts a titanium alloy.

[0015] As preferred, the 3D printing technology includes a powder sintering technology, a direct metal laser sintering technology, a selective laser melting technology, or an electron beam melting technology.

[0016] Compared with the prior art, the present application has the following beneficial effects:

[0017] (1) The 3D printing metal base supported type iron oxide photoanode has good light absorption properties and photoelectric water splitting reaction performance through the electrode base structure design with certain optical properties, and has high application value in future industry.

[0018] (2) The 3D printing metal base supported type iron oxide photoanode can obtain a 3D printing metal base supported type iron oxide photoanode with high photoelectric current density and good photoelectric performance through the research on the structure and material of the 3D printing metal base.

[0019] (3) The preparation method of the present application has simple process flow, flexible structure design, adjustable parameters, and low cost of experimental drugs and equipment. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings are included to provide a further understanding of embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and, together with the description, serve to explain principles of the application. Other embodiments and many of the intended advantages of the

[0021] Figure 1 Schematic diagram of 3D printed metal substrate with conical array for 3D printed metal substrate supported iron oxide photoanode of embodiments of the present application;

[0022] Figure 2 Finished product diagram for 3D printed metal substrate supported iron oxide photoanode of embodiment 1 of the present application, where a is a side view and top view of 3D printed metal substrate with conical array; b is the prepared 3D printed metal substrate supported iron oxide photoanode;

[0023] Figure 3 Current density-time (J-t) curve for 3D printed metal substrate supported iron oxide photoanode of embodiment 1 of the present application;

[0024] Figure 4 Schematic diagram of 3D printed metal substrate with cylindrical array for 3D printed metal substrate supported iron oxide photoanode of embodiment 7 of the present application;

[0025] Figure 5 Schematic diagram of 3D printed metal substrate with inverted conical array for 3D printed metal substrate supported iron oxide photoanode of embodiment 9 of the present application;

[0026] Figure 6 Schematic diagram of 3D printed metal substrate with grid-shaped array for 3D printed metal substrate supported iron oxide photoanode of embodiment 11 of the present application. DETAILED DESCRIPTION

[0027] The present application will be further described with reference to the drawings and embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not intended to limit the scope of the application. It is further noted that, for the sake of brevity, the figures of the drawings are not necessarily drawn to scale.

[0028] It should be noted that the embodiments and features of the embodiments in the present application can be combined with each other without conflict. The present application will be described in detail below with reference to the drawings and embodiments.

[0029] REFERENCE Figures 1-6This application proposes a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer integrally formed by 3D printing technology and a metal array structure, or a grid-shaped array structure formed by 3D printing technology. The 3D-printed metal substrate is made of titanium alloy. 3D printing technologies include powder sintering, direct metal laser sintering, selective laser melting, or electron beam melting. The metal array structure has multiple patterned units arranged in an array. The metal array structure is located above the conductive layer, exposing a portion of the conductive layer's surface. In a preferred embodiment, the metal array structure is located on one side of the conductive layer, and its distribution area is at least half the area of ​​the upper surface of the conductive layer. The titanium-doped iron oxide layer covers the surface of the 3D-printed metal substrate.

[0030] In one embodiment, the graphic unit is a conical protrusion, the metal array structure is a conical array, and the bottom radius of the conical protrusion is 0.5 to 0.8 mm, and the height is 1 to 6 mm.

[0031] In one embodiment, the graphic unit is an inverted conical recess, the metal array structure is an inverted conical array, the top radius of the inverted conical recess is 0.5 mm, and the height is 1 to 3 mm.

[0032] In one embodiment, the graphic unit is a cylindrical protrusion, the metal array structure is a cylindrical array, the bottom radius of the cylindrical protrusion is 0.5 mm, and the height is 1 to 3 mm.

[0033] In the above embodiments, the thickness of the conductive layer is 2 mm; the center distance between two adjacent patterned units in the metal array structure is 1.25 mm.

[0034] In another embodiment, the grid prisms of the grid array are triangular prisms or cylinders, and the grid spacing is 0.2 mm.

[0035] The following is an illustration through specific examples:

[0036] Example 1

[0037] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it, as shown in the reference. Figure 1 The surface area of ​​the conductive layer on the 3D-printed metal substrate is 1*2cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2The conical array has a bottom radius of 0.5 mm and an array height of 1 mm. Titanium alloy powder is used for 3D printing, resulting in a conical array titanium alloy electrode substrate. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0038] Specifically, ferric chloride hexahydrate (FeCl3·6H2O) was dissolved in water, and a tetrabutyl titanate ethanol solution was added and stirred until dissolved. Then, sodium acetate (CH3COONa) was added, and the solution was stirred until dissolved. The pH was adjusted with 37% concentrated hydrochloric acid, and the mixture was poured into a hydrothermal reactor. A 3D-printed metal substrate with a conical array of titanium alloy was vertically immersed in the mixed solution. The reactor was then placed in an oven for reaction. After the reaction, the electrode was removed, washed, and dried to obtain a 3D β-FeOOH:Ti electrode, i.e., a titanium-doped iron oxide photoanode based on a 3D-printed metal substrate. The obtained β-FeOOH:Ti electrode was then calcined in a muffle furnace to obtain a 3D-printed metal substrate-supported iron oxide photoanode.

[0039] like Figure 2 (a) shows a side view and a top view of a 3D-printed metal substrate with a conical array, obtained through 3D printing technology. 3D printing technology can produce electrode substrates with shapes identical to the designed shapes, such as... Figure 2 (b) is the 3D printed metal substrate supported iron oxide photoanode, in which a titanium-doped iron oxide layer is uniformly attached to the surface of the 3D printed metal substrate.

[0040] The 3D-printed metal-substrate-supported iron oxide photoanode was subjected to current-time curve testing using a Shanghai Chenhua CHI760e electrochemical workstation. The test conditions were as follows: a three-electrode system was used, with the 3D-printed metal-substrate-supported iron oxide photoanode as the working electrode, Hg / HgO as the reference electrode, a Pt mesh as the counter electrode, and 1M NaOH solution as the electrolyte. The bias voltage was set to 1.5V vs. RHE. The illumination instrument was a Beijing PLS-SXE300D xenon lamp with a light intensity of 100mW / cm². 2 The result is as follows Figure 3 As shown, the steady-state photocurrent density of this 3D-printed metal substrate-supported iron oxide photoanode is 0.60 mA / cm² under a bias voltage of 1.5V vs. RHE. 2 .

[0041] Example 2

[0042] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2 The conical array has a bottom radius of 0.5 mm and an array height of 2 mm. Titanium alloy powder was used for 3D printing, resulting in a conical array titanium alloy electrode substrate. A titanium-doped iron oxide layer was attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0043] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.78 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0044] Example 3

[0045] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2 The conical array has a bottom radius of 0.5 mm and an array height of 3 mm. Titanium alloy powder was used for 3D printing, resulting in a conical array titanium alloy electrode substrate. A titanium-doped iron oxide layer was attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0046] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.85 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0047] Example 4

[0048] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2 The conical array has a bottom radius of 0.5 mm and an array height of 6 mm. Titanium alloy powder was used for 3D printing, resulting in a conical array titanium alloy electrode substrate. A titanium-doped iron oxide layer was attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0049] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.93 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0050] Example 5

[0051] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2 The conical array has a bottom radius of 0.5 mm and an array height of 6 mm. Titanium alloy powder was used for 3D printing, resulting in a conical array titanium alloy electrode substrate. A titanium-doped iron oxide layer was attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0052] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 1.03 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0053] Example 6

[0054] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2The bottom radius is 0.8 mm, and the array height is 6 mm. Titanium alloy powder is used for 3D printing, resulting in a conical array of titanium alloy electrode substrates. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0055] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.85 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0056] Example 7

[0057] This embodiment presents a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. (Reference) Figure 4 The 3D-printed metal substrate includes a conductive layer and a metal array structure with a columnar array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2cm². 2 The thickness is 2mm, and the area of ​​the columnar array distribution region on the conductive layer is 1*1cm. 2 The bottom radius is 0.5 mm, and the array height is 1 mm. Titanium alloy powder is used for 3D printing, resulting in a columnar array of titanium alloy electrode substrates. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0058] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.75 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0059] Example 8

[0060] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a columnar array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the columnar array distribution region on the conductive layer is 1*1cm. 2 The bottom radius is 0.5 mm, and the array height is 3 mm. Titanium alloy powder is used for 3D printing, resulting in a columnar array of titanium alloy electrode substrates. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0061] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.89 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0062] Example 9

[0063] This embodiment presents a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. (Reference) Figure 5 The 3D-printed metal substrate includes a conductive layer and a metal array structure with an inverted conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2cm². 2 The total thickness is 3mm, and the area of ​​the inverted conical array distribution region on the conductive layer is 1*1cm. 2 The inverted conical array has several inverted conical recesses, each with a top radius of 0.5 mm and an array height of 1 mm. Titanium alloy powder is used for 3D printing, resulting in a 3D-printed metal substrate with an inverted conical array of titanium alloy electrodes. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0064] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.73 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0065] Example 10

[0066] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with an inverted conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The total thickness is 3mm, and the area of ​​the inverted conical array distribution region on the conductive layer is 1*1cm. 2 The inverted conical array has several inverted conical recesses, each with a top radius of 0.5 mm and an array height of 3 mm. Titanium alloy powder is used for 3D printing, resulting in a 3D-printed metal substrate that is an inverted conical array titanium alloy electrode substrate. Using the same process as in Example 1, a titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate to form a 3D-printed metal substrate-supported iron oxide photoanode.

[0067] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.95 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0068] Example 11

[0069] This embodiment presents a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. (Reference) Figure 6 The 3D-printed metal substrate is a grid array, and the total size of the designed grid array is 1*2cm. 2 The total thickness is 3 mm, the grid prisms are triangular prisms, and the grid spacing is 0.2 mm. Titanium alloy powder is used for 3D printing, resulting in a grid-array titanium alloy electrode substrate. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0070] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.75 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0071] Example 12

[0072] This embodiment proposes a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate is a grid array, and the total size of the designed grid array is 1*2cm. 2 The total thickness is 3 mm, the grid prisms are cylindrical, and the grid spacing is 0.2 mm. Titanium alloy powder is used for 3D printing, resulting in a grid-array titanium alloy electrode substrate. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0073] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.78 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0074] Comparative Example 1

[0075] This comparative example presents a 3D-printed metal substrate-supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a planar metal array structure above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The total thickness is 2 mm. Titanium alloy powder was used for 3D printing, resulting in a planar titanium alloy electrode substrate. A titanium-doped iron oxide layer was attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0076] Under the same test conditions as in Example 1, the steady-state photocurrent density of the planar Fe2O3:Ti electrode under a bias of 1.5V vs. RHE was found to be 0.25 mA / cm². 2 .

[0077] Comparative Example 2

[0078] This embodiment proposes a 3D-printed metal substrate supported iron oxide photoanode, comprising a 3D-printed metal substrate and a titanium-doped iron oxide layer. The 3D-printed metal substrate includes a conductive layer and a metal array structure with a conical array above it. The upper surface area of ​​the conductive layer of the 3D-printed metal substrate is 1*2 cm². 2 The thickness is 2mm, and the area of ​​the metal array structure distribution region on the conductive layer is 1*1cm. 2 The bottom radius is 0.5 mm, and the array height is 1 mm. Stainless steel powder is used for 3D printing, resulting in a conical array of stainless steel electrode substrates. A titanium-doped iron oxide layer is attached to the surface of the 3D-printed metal substrate using the same process as in Example 1, forming a 3D-printed metal substrate-supported iron oxide photoanode.

[0079] Under the same test conditions as in Example 1, the steady-state photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode was 0.22 mA / cm² at a bias voltage of 1.5 V vs. RHE. 2 .

[0080] Therefore, it can be seen that:

[0081] (1) According to Examples 1, 7, 9, 11, 12 and Comparative Example 1, the photocurrent density of the 3D-printed metal substrate-supported iron oxide photoanode is related to the structural design of the 3D-printed metal substrate. The structures of the 3D-printed metal substrate, arranged from largest to smallest photocurrent density, are: conical array, inverted conical array, cylindrical array, grid structure, and planar structure. Compared with planar metal substrates, 3D-printed metal substrates using conical arrays, inverted conical arrays, cylindrical arrays, or grid structures have higher photocurrent densities.

[0082] (2) As can be seen from Examples 1-4 and 7-10, the photocurrent density of the 3D printed metal substrate supported iron oxide photoanode increases with the increase of array height.

[0083] (3) As can be seen from Examples 5 and 6, the photocurrent density of the 3D printed metal substrate supported iron oxide photoanode decreases as the bottom radius of the array increases.

[0084] (4) According to Example 1 and Comparative Example 2, the material of the 3D printed metal substrate significantly affects the photoelectric performance. The photocurrent density of the 3D printed metal substrate supported iron oxide photoanode is related to the material of the 3D printed metal substrate. The materials of the 3D printed metal substrate are arranged from largest to smallest according to the photocurrent density as follows: titanium alloy and stainless steel.

[0085] In summary, this invention, through the rational design of a 3D-printed metal substrate-supported high-performance photoanode with a three-dimensional periodic structure, deterministically increases the ordered light reflection path and constructs a photon incident inclined surface to increase the light absorption depth, thus solving the problem of low light absorption efficiency caused by the random disorder of traditional structures. The embodiments of this application provide a 3D-printed metal substrate-supported iron oxide photoanode that can obtain iron oxide photoanodes based on 3D-printed metal substrates with different structural shapes and materials, exhibiting excellent photoelectric performance. Furthermore, the fabrication process is environmentally friendly and simple, making it highly valuable in practical applications.

[0086] The specific embodiments of this application have been described above, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A 3D printed metal substrate supported type iron oxide photoanode, characterized in that, The application relates to a 3D printing metal base and a titanium-doped iron oxide layer, wherein the 3D printing metal base is made of a titanium alloy, the 3D printing metal base comprises a conductive layer and a metal array structure above the conductive layer which are integrally formed by a 3D printing technology, or a grid-shaped array structure formed by a 3D printing technology, a plurality of graphic units arranged in an array are arranged on the metal array structure, the titanium-doped iron oxide layer is arranged on the surface of the 3D printing metal base, the metal array structure is arranged on one side surface of the conductive layer, and the distribution area of the metal array structure is at least half of the upper surface area of the conductive layer.

2. The 3D-printed metal-based support-type iron oxide photoanode according to claim 1, wherein, The graphic unit is a conical protrusion, the metal array structure is a conical array, the bottom radius of the conical protrusion is 0.5-0.8 mm, and the height is 1-6 mm.

3. The 3D-printed metal-based support-type iron oxide photoanode according to claim 1, wherein, The graphic unit is an inverted conical pit, the metal array structure is an inverted conical array, the top radius of the inverted conical pit is 0.5 mm, and the height is 1-3 mm.

4. The 3D-printed metal-based support-type iron oxide photoanode of claim 1, wherein, The graphic unit is a cylindrical protrusion, the metal array structure is a cylindrical array, the bottom radius of the cylindrical protrusion is 0.5 mm, and the height is 1-3 mm.

5. The 3D-printed metal substrate-supported iron oxide photoanode according to any one of claims 1-4, characterized in that, The center distance between two adjacent graphic units in the metal array structure is 1.25 mm.

6. The 3D-printed metal-based support-type iron oxide photoanode according to claim 1, wherein, The grid prism of the grid-shaped array structure is a triangular prism or a cylindrical shape, and the grid spacing is 0.2 mm.

7. The 3D-printed metal-based supported iron oxide photoanode according to claim 1, wherein, The thickness of the conductive layer is 2 mm.

8. The 3D-printed metal-based support-type iron oxide photoanode according to claim 1, wherein, The 3D printing technology comprises a powder sintering technology, a direct metal laser sintering technology, a selective laser melting technology or an electron beam melting technology.

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