Background
Organic sewage treatment can be divided into a physical method, a chemical method, a biological method, an electrochemical oxidation method and the like, wherein the electrochemical oxidation method is widely applied due to wide treatment range, flexible application, small secondary pollution, good controllability, low cost and the like compared with other water treatment technologies. Currently, anode materials commonly used in electrochemical oxidation methods are: metal electrodes (Pt, Au, Ir, Ru, alloys, or the like), carbon electrodes (graphite, glassy carbon, or the like), boron-doped diamond thin film (BDD) electrodes, and the like. The boron-doped diamond film electrode has the characteristics of widest electrochemical window, extremely high oxygen evolution potential, extremely low background current, extremely high chemical inertness, pollution and poisoning resistance, extremely low surface adsorption characteristic, high electro-catalytic activity and the like, and has wide application prospect in the field of sewage treatment.
The preparation of the boron-doped diamond film electrode with excellent performance relates to a plurality of technologies such as the selection of base materials, the selection of boron-doped modes, the pretreatment scheme of a base body, the optimization of CVD process parameters, the control of film-base bonding force and the like. In the aspect of substrate pretreatment, in order to increase the deposition area of the boron-doped diamond film, the prior art generally performs the treatments such as polishing, sand blasting, etching, laser cleaning and the like on the surface of the substrate to increase the surface area of the substrate. In terms of selection of a substrate material and control of film-substrate bonding force, titanium and other materials are cheap and are often used as a substrate, however, the materials have poor film-substrate bonding property and are easy to cause shedding of a boron-doped diamond film in the use process of an electrode, and a substrate made of niobium, tantalum and other materials forms a carbide layer on the surface of the substrate when the boron-doped diamond film is deposited, so that the substrate has excellent film-substrate bonding property but is expensive and not suitable for being used as a substrate material.
However, no matter the surface of the substrate is polished, etched, laser cleaned or the transition layer is sputtered on the substrate, the preparation of the boron-doped diamond film electrode is complicated, and in the preparation process of the boron-doped diamond film electrode, a plurality of devices are needed to participate, so that the cost is high. In addition, the surface of the substrate is often cracked by polishing, etching, laser cleaning, and the like. Therefore, how to avoid the generation of cracks, simplify the electrode preparation process, and reduce the tedious substrate surface treatment process is a technical problem that needs to be solved urgently in the field.
Disclosure of Invention
The invention provides a preparation method of a boron-doped diamond film electrode substrate, the boron-doped diamond film electrode substrate, a preparation method of a boron-doped diamond film electrode and the boron-doped diamond film electrode, and aims to solve the problems of complex electrode preparation process, complex surface treatment process of the electrode substrate, cracks caused by the surface treatment process of the electrode substrate and the like in the prior art.
In one aspect, the invention provides a preparation method of a boron-doped diamond film electrode substrate, which comprises the following steps: s1, preparing a first metal raw material, and preparing the lower part of the substrate by using the first metal raw material; s2, preparing a second metal raw material, and printing the upper part of the substrate with a porous structure for depositing the boron-doped diamond film on the upper surface of the lower part of the substrate by using the second metal raw material through a 3D printing technology; wherein the first metal raw material is a corrosion-resistant metal raw material; the second metal raw material is a metal raw material which enables the upper part of the substrate prepared from the second metal raw material to form a carbide layer when the boron-doped diamond film is deposited.
In some embodiments of the invention, the first metal feedstock is selected from 316 stainless steel and/or titanium alloys; the second metal raw material is selected from one or more of niobium, zirconium, molybdenum, tungsten and tantalum. The materials of the first metal raw material and the second metal raw material are not limited to the above materials, and can be reasonably selected by those skilled in the art according to the needs on the premise that the corrosion resistance of the first metal raw material is strong and the second metal raw material can enable the upper part of the substrate to form a carbide layer when the boron-doped diamond film is deposited.
In some embodiments of the invention, the ratio of the thickness of the lower portion of the substrate to the upper portion of the substrate is not less than 5: 1.
In some embodiments of the invention, the lower portion of the substrate is a dense structure.
In some embodiments of the invention, the porous structure of the upper portion of the substrate is comprised of interconnected pores.
In some embodiments of the present invention, the pores in the porous structure of the upper part of the substrate are regularly circular. The shape of the pores in the porous structure of the upper part of the substrate is not limited thereto, and those skilled in the art can design the shape reasonably according to actual needs.
In some embodiments of the invention, the method further comprises: s3, forming a hole penetrating through the upper substrate part and the lower substrate part from the upper surface of the upper substrate part in a direction perpendicular to the upper surface of the upper substrate part, and forming a hole penetrating through the side surface of the lower substrate part from the side surface of the lower substrate part in a direction parallel to the upper surface of the lower substrate part.
On the other hand, the invention also provides a boron-doped diamond film electrode substrate, and the boron-doped diamond film electrode substrate is prepared according to the preparation method of the boron-doped diamond film electrode substrate.
In another aspect, the invention also provides a method for preparing a boron-doped diamond film electrode, which comprises the following steps: s1, preparing the boron-doped diamond film electrode substrate according to the preparation method of the boron-doped diamond film electrode substrate; s2, ultrasonically cleaning the boron-doped diamond film electrode substrate, and drying for later use; s3, placing the boron-doped diamond film electrode substrate processed in the step S2 in a diamond suspension for crystal implantation, then ultrasonically cleaning, and drying for later use; s4, placing the boron-doped diamond film electrode substrate processed in the step S3 in hot wire chemical vapor deposition equipment to deposit the boron-doped diamond film on the upper part of the substrate.
In another aspect, the invention also provides a boron-doped diamond film electrode, which is prepared according to the preparation method of the boron-doped diamond film electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a method for preparing a boron-doped diamond film electrode substrate, which takes two metal materials of a first metal material and a second metal material as raw materials, wherein the second metal material is a metal material which can form a carbide layer on the upper part of the substrate prepared by the second metal material when a boron-doped diamond film is deposited, the upper part of the substrate of the boron-doped diamond film electrode substrate is prepared by utilizing the second metal material, the carbide layer is formed on the upper part of the substrate when the boron-doped diamond film is deposited, and the boron-doped diamond film can be ensured to have good bonding capability with the substrate after being deposited on the upper part of the substrate. The problem of overhigh raw material cost caused by high price of the second metal material (such as tantalum, niobium and the like) is avoided, and the cost is saved.
(2) The preparation method of the boron-doped diamond film electrode substrate utilizes the first metal raw material to prepare the lower part of the substrate, and utilizes the second metal raw material to print the upper part of the substrate with a porous structure on the upper surface of the lower part of the substrate through a 3D printing technology. Compared with the traditional flaky or blocky substrate, the upper part of the electrode substrate prepared by the preparation method disclosed by the invention is of a porous structure, and the treatment such as fussy grinding, etching, laser cleaning and the like is not needed to be carried out on the surface of the substrate, so that the large contact area of the electrode substrate and the boron-doped diamond film can be obtained, the cost is saved, the process is simplified, the equipment use is reduced, meanwhile, cracks caused by the treatment such as grinding, etching, laser cleaning and the like can be avoided, and the problems of weakened strength and shortened service life of the electrode substrate caused by the cracks are further reduced.
(3) The thickness of the lower part of the substrate prepared by the preparation method of the boron-doped diamond film electrode substrate is far larger than that of the upper part of the substrate, the thicker lower part of the substrate provides higher mechanical support for the whole boron-doped diamond film electrode substrate, and the thinner porous upper part of the substrate can ensure that less cost is generated due to less consumption while providing enough deposition area for the deposition of the boron-doped diamond film.
(4) The method for preparing the boron-doped diamond film electrode substrate of the invention makes holes penetrating through the upper part and the lower part of the substrate from the upper surface of the upper part of the substrate along the direction vertical to the upper surface of the upper part of the substrate, and makes holes penetrating through the side surface of the lower part of the substrate from the side surface of the lower part of the substrate along the direction parallel to the upper surface of the lower part of the substrate. After the boron-doped diamond film is deposited, water flow can flow through holes punched in the whole substrate and holes of a porous structure on the upper portion of the substrate, so that the permeability of the substrate is improved, the problem that the boron-doped diamond film cannot be electrolyzed due to the fact that gas generated after electrolysis is attached to the boron-doped diamond film in a bubble form is solved, and the effective electrolysis duration of the boron-doped diamond film electrode is prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of various aspects of the present invention is provided with specific examples, which are only used for illustrating the present invention and do not limit the scope and spirit of the present invention.
Example 1: preparation method of boron-doped diamond film electrode substrate
The preparation method of the boron-doped diamond film electrode substrate comprises the following steps:
s1, preparing a first metal raw material, and preparing the lower part of the substrate with a compact structure by using the first metal raw material, wherein the first metal raw material is a corrosion-resistant metal raw material, and is selected from 316 stainless steel and/or titanium alloy;
s2, preparing a second metal raw material, and printing the upper part of the substrate with a porous structure for depositing the boron-doped diamond film on the upper surface of the lower part of the substrate by using the second metal raw material through a 3D printing technology; the second metal raw material is a metal raw material which can form a carbide layer on the upper part of a substrate prepared from the second metal raw material when the boron-doped diamond film is deposited, the second metal raw material is selected from one or more of niobium, zirconium, molybdenum, tungsten and tantalum, the thickness ratio of the lower part of the substrate to the upper part of the substrate is not less than 5:1, and the porous structure on the upper part of the substrate is formed by mutually communicated holes which are in regular round shapes;
s3, forming a hole penetrating through the upper part of the base and the lower part of the base from the upper surface of the upper part of the base in a direction perpendicular to the upper surface of the upper part of the base, and forming a hole penetrating through the side surface of the lower part of the base from the side surface of the lower part of the base in a direction parallel to the upper surface of the lower part of the base.
The preparation method of the boron-doped diamond film electrode substrate of the embodiment takes two metal materials of a first metal material and a second metal material as raw materials, the second metal material is a metal material which can form a carbide layer on the upper part of the substrate prepared by the second metal material when the boron-doped diamond film is deposited, the upper part of the substrate of the boron-doped diamond film electrode substrate is prepared by the second metal material, the carbide layer is formed on the upper part of the substrate when the boron-doped diamond film is deposited, the good combination capability of the boron-doped diamond film and the substrate can be ensured after the boron-doped diamond film is deposited on the upper part of the substrate, compared with the prior art, on one hand, the excellent combination property of the film substrate can be realized without sputtering a transition layer on the boron-doped diamond film electrode substrate, the process is simplified, on the other hand, the second metal material only occupies a small part of the boron-doped diamond film electrode substrate, the usage amount is very small, the problem of overhigh raw material cost caused by high price of the second metal material (such as tantalum, niobium and the like) is avoided, and the cost is saved.
The second metal raw material selected by the method for preparing the boron-doped diamond film electrode substrate is one or more selected from niobium, zirconium, molybdenum, tungsten and tantalum, and the thermal expansion coefficient of the metal materials is close to that of the boron-doped diamond film, so that the film-substrate binding property of the boron-doped diamond film and the upper part of the substrate can be further ensured, and the boron-doped diamond film is prevented from falling off the substrate.
The method for preparing the boron-doped diamond film electrode substrate in the embodiment utilizes the first metal raw material to prepare the lower part of the substrate, and utilizes the second metal raw material to print the upper part of the substrate with a porous structure on the upper surface of the lower part of the substrate through a 3D printing technology. On one hand, the first metal raw material is a corrosion-resistant material which has strong corrosion resistance and can be used for a long time, so that the service life of the matrix is prolonged; on the other hand, compared with the traditional flaky or blocky substrate, the upper part of the electrode substrate prepared by the preparation method disclosed by the invention is of a porous structure, and the treatment such as fussy polishing, etching, laser cleaning and the like on the surface of the substrate is not needed, so that the large contact area of the electrode substrate and the boron-doped diamond film can be obtained, the cost is saved, the process is simplified, and the equipment use is reduced; the method can avoid cracks caused by polishing, etching, laser cleaning and other treatments, and further reduce the problems of weakened strength and shortened service life of the electrode matrix caused by the cracks. On the other hand, the interconnected holes of the porous structure on the upper part of the substrate prepared by the embodiment are regularly round, so that stress concentration can be reduced, the damage of the substrate caused by the stress concentration can be prevented, and the service life of the substrate can be prolonged; the through holes can ensure the fluid circulation.
The lower portion of the substrate prepared by the method for preparing the boron-doped diamond film electrode substrate is of a compact structure, the thickness ratio of the lower portion of the substrate to the upper portion of the substrate is not less than 5:1, the thickness of the lower portion of the substrate is far greater than that of the upper portion of the substrate, the thicker lower portion of the substrate provides higher mechanical support for the whole boron-doped diamond film electrode substrate, the thinner porous upper portion of the substrate can provide a large enough deposition area for deposition of a boron-doped diamond film, the upper portion of the substrate only occupies a small portion of the boron-doped diamond film electrode substrate, the usage amount of the second metal raw material is small, the problem of high raw material cost caused by high price of the second metal raw material is avoided, and cost is saved.
The method for preparing the boron-doped diamond film electrode substrate of the embodiment creates holes penetrating through the upper part and the lower part of the substrate from the upper surface of the upper part of the substrate along the direction vertical to the upper surface of the upper part of the substrate, and creates holes penetrating through the side surface of the lower part of the substrate from the side surface of the lower part of the substrate along the direction parallel to the upper surface of the lower part of the substrate. After the boron-doped diamond film is deposited, water flow can flow through holes punched in the whole substrate and holes of a porous structure on the upper portion of the substrate, so that the permeability of the substrate is improved, the problem that the boron-doped diamond film cannot be electrolyzed due to the fact that gas generated after electrolysis is attached to the boron-doped diamond film in a bubble form is solved, and the effective electrolysis duration of the boron-doped diamond film electrode is prolonged.
Example 2: boron-doped diamond film electrode substrate
The boron-doped diamond thin film electrode substrate of this example was prepared by the method of preparing the boron-doped diamond thin film electrode substrate of example 1. FIG. 1 is a perspective view of the boron-doped diamond thin film electrode substrate according to the present example. FIG. 2 is a cross-sectional view of the boron-doped diamond thin film electrode substrate of the present example taken along the A-A direction of FIG. 1.
As shown in fig. 1 and 2, the boron-doped diamond film electrode substrate 1 of the present embodiment comprises a substrate upper portion 11 and a substrate lower portion 12, wherein the substrate upper portion 11 and the substrate lower portion 12 are made of two different metal materials, wherein the first metal material for making the substrate lower portion 12 is a corrosion-resistant metal material, which has strong corrosion resistance and can be used for a long time, and the service life of the substrate is prolonged; the second metal raw material for preparing the upper part 11 of the substrate is a metal raw material which can form a carbide layer when the upper part 11 of the substrate prepared from the second metal raw material is deposited with the boron-doped diamond film, and the upper part 11 of the substrate can form the carbide layer when the boron-doped diamond film is deposited, so that the boron-doped diamond film and the upper part 11 of the substrate have good bonding capability.
The upper part 11 of the substrate of the boron-doped diamond film electrode substrate 1 of the embodiment is a porous structure, and the porous structure is composed of through holes 111 which are regularly round. On one hand, the porous structure formed by the through holes 111 can greatly improve the deposition area for the boron-doped diamond film deposition on the substrate, and the large contact area between the electrode substrate and the boron-doped diamond film can be obtained without carrying out fussy polishing, etching, laser cleaning and other treatments on the surface of the substrate, so that the cost is saved, the process is simplified, the equipment use is reduced, meanwhile, cracks caused by polishing, etching, laser cleaning and other treatments can be avoided, and the problems of weakened strength and shortened service life of the electrode substrate caused by the cracks are further reduced. On the other hand, the mutually through holes 111 of the porous structure are regularly round, so that stress concentration can be reduced to the maximum extent, damage to the substrate due to stress concentration is prevented, and the service life of the substrate is prolonged.
The lower substrate part 12 of the boron-doped diamond film electrode substrate 1 of the embodiment is of a compact structure, the thickness ratio of the lower substrate part 12 to the upper substrate part 11 is not less than 5:1, the thickness of the lower substrate part 12 is far greater than that of the upper substrate part 11, the thicker lower substrate part 12 provides higher mechanical support for the whole boron-doped diamond film electrode substrate 1, the thinner upper substrate part 11 can provide a sufficiently large deposition area for deposition of a boron-doped diamond film, and the upper substrate part 11 only occupies a small part of the boron-doped diamond film electrode substrate 1.
The boron-doped diamond thin film electrode substrate 1 of the present example was provided with the hole 112 penetrating the side surface of the substrate lower portion 12 from the side surface of the substrate lower portion 12 in the direction parallel to the upper surface of the substrate lower portion 12, and the substrate 1 was further provided with the hole 112 penetrating the substrate upper portion 11 and the substrate lower portion 12 from the upper surface of the substrate upper portion 11 in the direction perpendicular to the upper surface of the substrate upper portion 11. After the boron-doped diamond film is deposited, water flow can flow through the holes 112 formed in the whole substrate and the mutually communicated holes 111 of the porous structure on the upper part of the substrate, so that the permeability of the substrate is improved, the problem that the boron-doped diamond film cannot be electrolyzed due to the fact that gas generated after electrolysis is attached to the boron-doped diamond film in a bubble form and cannot be contacted with fluid is solved, and the effective electrolysis duration of the boron-doped diamond film electrode is prolonged.
Example 3: preparation method of boron-doped diamond film electrode
The preparation method of the boron-doped diamond film electrode comprises the following steps:
s1, preparing the boron-doped diamond film electrode substrate according to the preparation method of the boron-doped diamond film electrode substrate in the embodiment 1;
s2, ultrasonically cleaning the boron-doped diamond film electrode substrate, and drying for later use;
s3, placing the boron-doped diamond film electrode substrate processed in the step S2 in a diamond suspension for crystal implantation, then ultrasonically cleaning, and drying for later use;
s4, placing the boron-doped diamond film electrode substrate processed in the step S3 in hot wire chemical vapor deposition equipment to deposit the boron-doped diamond film on the upper part of the substrate.
In this example, after the deposition of the boron-doped diamond film on the upper portion of the substrate, the lower portion of the substrate was immersed in an electrically insulating liquid and then dried to form an electrically insulating layer covering the lower portion of the substrate. The electric insulating layer covers all exposed parts of the lower part of the matrix, and when the boron-doped diamond film electrode is used, the lower part of the matrix is isolated from the solution by the electric insulating layer, so that the lower part of the matrix is prevented from participating in electrolytic reaction, and further the influence of the participation of the lower part of the matrix in electrolytic reaction on the electrolytic reaction of the boron-doped diamond film electrode is avoided.
In addition, the method for preparing the boron-doped diamond thin film electrode of the embodiment also has the whole technical effects of the embodiment 1.
Example 4: boron-doped diamond film electrode
The boron-doped diamond thin film electrode of this example was prepared by the method of preparing the boron-doped diamond thin film electrode of example 3. The boron-doped diamond thin film electrode of the present embodiment has all the technical effects of embodiment 2, and in addition, when the boron-doped diamond thin film electrode of the present embodiment is used, the lower portion of the substrate is isolated from the solution by the electrical insulation layer, so as to prevent the lower portion of the substrate from participating in the electrolytic reaction, and further avoid the influence of the participation of the lower portion of the substrate in the electrolytic reaction on the electrolytic reaction of the boron-doped diamond thin film electrode.
The present invention has been described in conjunction with specific embodiments which are intended to be exemplary only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all modifications, variations or alterations that may occur to those skilled in the art without departing from the spirit of the invention. Therefore, various equivalent changes made according to the present invention still fall within the scope covered by the present invention.