CN110496616B - Photoelectrocatalysis metal-loaded boron-doped diamond, preparation method and application - Google Patents
Photoelectrocatalysis metal-loaded boron-doped diamond, preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention provides a photoelectrocatalysis metal-loaded boron-doped diamond, which comprises a substrate, a boron-doped diamond layer arranged on any side of the substrate, and a metal nanoparticle catalyst uniformly loaded at the tip of the conical structure layer, wherein the boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer. The photoelectrocatalysis metal-loaded boron-doped diamond has high catalytic activity, high stability and high selectivity in a chemical process, and the selectivity and the efficiency of the catalytic process are greatly improved.
Description
Technical Field
The invention relates to the field of photoelectrochemical catalytic electrodes, in particular to photoelectrocatalysis metal-loaded boron-doped diamond and a preparation method and application thereof.
Background
With the increasing global population, the depletion of fossil fuels and the global environmental problems become more serious, and the search for new fuels that can replace the traditional fossil fuels and reduce the environmental burden and realize the sustainable utilization of energy is urgent. The ammonia gas is mainly used for producing chemical fertilizers in chemical engineering processes, plays an important role in solving global grain problems, is also a green energy carrier and is a potential energy transmission fuel.
The ammonia gas generated by nitrogen reduction mainly plays a role in chemical production, and the synthetic ammonia has great significance for solving the global grain problem for the growth of crops. At present, the main method for preparing ammonia gas by nitrogen reduction in industrial production is to use the Haber-Boschtt method, the process conditions required by the Haber-Boschtt method are harsh, the reaction temperature needs to be kept within the range of 500 ℃ of 300-. The reaction for reducing the nitrogen by adopting the photoelectrochemistry catalytic reaction or the electrochemical catalytic reaction has the following advantages compared with the traditional Harper-Borster method in which the photoelectrochemistry catalytic reduction of the nitrogen to generate the ammonia gas: (1) the reduction technology has mild conditions; (2) a large amount of energy is not consumed, and the carbon footprint is reduced; (3) the equipment is simple, and the complex reaction equipment is prevented from being built in a factory
Whether the reaction of reducing nitrogen into ammonia gas by photoelectrocatalysis or electrocatalysis can be carried out efficiently depends on the design of a catalytic electrode. The traditional electrode material has poor adsorption capacity and low stability on nitrogen, so that the reaction rate is slow and the catalytic capability is weak. Meanwhile, the intermediates participating in the reaction have high energy, so that the reaction is difficult to continue, the reduction yield is low, and the use of the intermediate is limited.
Disclosure of Invention
The invention aims to provide a photoelectrocatalysis metal-loaded boron-doped diamond and a preparation method and application thereof, and aims to solve the problems of poor stability and weak catalytic capability of an electrode material for photoelectrocatalysis reaction in the prior art.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the utility model provides a photoelectrocatalysis's boron doping diamond of load metal, load metal's boron doping diamond includes the basement, sets up the boron doping diamond layer of basement arbitrary side, boron doping diamond layer is including leveling the bottom and perpendicular to level the conical structure layer of bottom, and evenly load the metal nanoparticle catalyst at the tip of conical structure layer.
And a preparation method of the photoelectrocatalytic metal-loaded boron-doped diamond, which comprises the following steps:
providing boron-doped diamond as a carrier, wherein the boron-doped diamond comprises a substrate and boron-doped diamond layers arranged on any side of the substrate;
etching the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer;
and providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering mode to obtain the photoelectrocatalysis metal-loaded boron-doped diamond.
And a photoelectrocatalysis reduction reaction electrode, wherein the material of the reduction reaction electrode is the photoelectrocatalysis metal-loaded boron-doped diamond or the photoelectrocatalysis metal-loaded boron-doped diamond prepared by the method.
And the application of the photoelectrocatalytic metal-loaded boron-doped diamond or the photoelectrocatalytic metal-loaded boron-doped diamond electrode prepared by the method in photoelectrocatalytic reduction reaction.
Compared with the prior art, the invention provides a photoelectrocatalysis metal-loaded boron-doped diamond, which comprises a substrate and a boron-doped diamond layer arranged on any side of the substrate, wherein the boron-doped diamond layer comprises a flat bottom layer, a conical structure layer vertical to the flat bottom layer and metal nano particles uniformly loaded at the tip of the conical structure layer. The boron-doped diamond layer is used as a carrier, the diamond is a wide bandgap semiconductor material, the high-concentration boron-doped diamond can obtain excellent conductivity, semimetal or even metal conductivity can be realized, the resistivity is low, the stability is high, electrons are provided for the reaction, the reaction is accelerated, and the reaction rate is improved; the boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer, and the conical structure layer is formed, so that the boron-doped diamond layer has a larger specific surface area, can be beneficial to loading of more metal catalysts, and can enhance the catalytic activity; the metal nanoparticle catalyst is uniformly loaded at the tip position of the conical structure layer, the metal nanoparticles and the boron-doped diamond carrier interact, and the interaction enables metal atoms to have low coordination and maximum atom utilization efficiency, so that the prepared photoelectrocatalysis metal-loaded boron-doped diamond has high catalytic activity, stability and selectivity of a chemical process, and the selectivity and efficiency of the catalytic process are greatly improved.
The preparation method of the photoelectrocatalysis metal-loaded boron-doped diamond comprises the steps of firstly providing a boron-doped diamond carrier, and etching the surface of a boron-doped diamond layer on any side of a substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer; providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering mode to obtain the metal-loaded boron-doped diamond; the adopted magnetron sputtering method is simple, convenient, rapid and easy to control, and simultaneously, the magnetron sputtering method can ensure the larger adhesive force of the metal nano particles and the boron-doped diamond carrier, has good material stability, improves the catalytic efficiency and is beneficial to industrial application.
According to the photoelectrocatalysis reduction reaction electrode provided by the invention, the material of the photoelectrocatalysis reduction reaction electrode is the photoelectrocatalysis metal-loaded boron-doped diamond or the photoelectrocatalysis metal-loaded boron-doped diamond prepared by the method, and in the process of carrying out photoelectrocatalysis reduction reaction by taking the metal-loaded boron-doped diamond as the material of the working electrode, the reduction reaction has high catalytic activity, and the catalytic rate of the electrode reaches a high level.
The application of the photoelectrocatalytic metal-loaded boron-doped diamond electrode or the photoelectrocatalytic metal-loaded boron-doped diamond electrode prepared by the method in photoelectrocatalytic reduction reactions comprises chemical reactions such as photoelectrocatalytic nitrogen reduction.
Drawings
Fig. 1 is a schematic diagram of a photoelectrocatalytic gold nanoparticle-supported boron-doped diamond electrode provided in example 1 of the present invention.
Fig. 2 is a schematic view of a gold nanoparticle-supported boron-doped diamond electrode provided in comparative example 1 of the present invention.
Fig. 3 is a schematic view of a boron-doped diamond electrode provided in comparative example 3 of the present invention.
FIG. 4 is a schematic diagram of the photoelectrocatalytic nitrogen reduction reaction performed in example 2, comparative example 2, and comparative example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a photoelectrocatalysis metal-loaded boron-doped diamond, which comprises a substrate and a boron-doped diamond layer arranged on any side of the substrate, wherein the boron-doped diamond layer comprises a flat bottom layer, a conical structure layer vertical to the flat bottom layer and a metal nanoparticle catalyst uniformly loaded at the tip of the conical structure layer.
Specifically, the metal-loaded boron-doped diamond comprises a substrate, and preferably, the substrate is made of any one material selected from a silicon wafer, a chromium sheet, a titanium mesh, carbon cloth and a molybdenum mesh. In a preferred embodiment of the invention, a chromium plate is selected as the substrate for subsequent processing.
Specifically, the boron-doped diamond layer is arranged on any one side of the substrate and comprises a flat bottom layer and a conical structure layer perpendicular to the flat bottom layer. The boron-doped diamond layer can be used as a carrier for subsequent treatment, the boron-doped diamond layer is used as the carrier, the diamond is a wide bandgap semiconductor material, the high-concentration boron-doped diamond can obtain excellent conductivity, semimetal and even metal conductivity can be realized, the resistivity is low, the stability is high, electrons are provided for reaction, the reaction is accelerated, and the reaction rate is improved. Furthermore, the boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer, and the conical structure layer is formed, so that the conical structure layer has a larger specific surface area, is beneficial to loading of more metal catalysts, and enhances the catalytic activity. Preferably, the thickness of the boron doped diamond layer is 500nm to 10 μm. If the thickness of the obtained boron-doped diamond layer is too thin, the stability of the diamond film is poor and the deposition is not uniform; if the thickness of the obtained boron-doped diamond layer is too thick, the boron-doped diamond layer is easy to fall off, and the subsequent use is influenced. In a preferred embodiment of the invention, the thickness of the boron doped diamond layer is 10 μm.
Preferably, the thickness of the flat bottom layer is 500 nm-5 μm; the height of the conical structure layer is 500 nm-2 mu m. More preferably, in the tapered structure layer, the diameter of the bottom of the tapered structure is 100 μm to 1 μm; the radius of curvature of the tip of the tapered structure does not exceed 20 nm.
Specifically, the metal nanoparticle catalyst is uniformly loaded at the tip of the conical structure layer, the catalyst is uniformly loaded at the tip of the conical structure layer, most of the catalytic particles are exposed, and the catalytic characteristic can be realized, and the metal nanoparticles and the boron-doped diamond layer interact with each other, so that metal atoms have low coordination and maximum atom utilization efficiency, the prepared boron-doped diamond loaded by the metal nanoparticles has high catalytic activity, stability and selectivity in an electrochemical process, and the selectivity and efficiency in the catalytic process are greatly improved. Preferably, the metal nanoparticles are any one of gold, silver, platinum, ruthenium, palladium, iridium, niobium and molybdenum, and the metal nanoparticles are noble metals, and the noble metals have good catalytic activity and stability, can prolong the service life of the electrode, can strongly adsorb nitrogen molecules, enable the catalytic reaction to smoothly proceed on the surface of the electrode, and improve the reaction rate.
Preferably, the particle size of the metal nanoparticle catalyst is 0.1nm to 20 nm. Among them, the size of the catalyst is an important factor affecting the catalytic activity. When the catalysts are present in the form of blocks, their catalytic performance depends on their exposed surface, and the catalytic effect is poor; when the particle size is reduced to the nanometer size range, non-metallic properties, including some new reaction properties and higher catalytic properties, are created. Preferably, the particle size of the catalyst is 0.1nm to 20 nm. If the particle size of the catalytic particles is too small, a large amount of aggregation is easily caused, and the catalytic effect is poor; if the particle diameter of the catalytic particles is too large, the catalytic effect is not exerted.
Preferably, the ratio of the supported area of the metal nanoparticle catalyst to the area of the boron-doped diamond layer is 10% to 20%. If the catalyst loading area is too large, the metal nanoparticles are too large, and excessive accumulation is caused at the tip of the boron-doped diamond conical structure, so that the catalytic effect is poor; if the loading area of the catalyst is too small, the metal nanoparticles are too small, the catalytic efficiency is not high enough, and the catalytic effect is poor.
The invention provides a photoelectrocatalysis metal-loaded boron-doped diamond, which comprises a substrate and a boron-doped diamond layer arranged on any side of the substrate, wherein the boron-doped diamond layer comprises a flat bottom layer, a conical structure layer vertical to the flat bottom layer and a metal catalyst uniformly loaded at the tip of the conical structure layer. The boron-doped diamond layer is used as a carrier, the diamond is a wide bandgap semiconductor material, the high-concentration boron-doped diamond can obtain excellent conductivity, semimetal or even metal conductivity can be realized, the resistivity is low, the stability is high, electrons are provided for the reaction, the reaction is accelerated, and the reaction rate is improved; the boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer, and the conical structure layer is formed, so that the conical structure layer has a larger specific surface area, is beneficial to loading of more metal catalysts, and enhances the catalytic activity; the metal nanoparticle catalyst is uniformly loaded at the tip position of the conical structure layer, and the metal nanoparticles and the boron-doped diamond carrier interact with each other, so that metal atoms have low coordination and maximum atom utilization efficiency, the prepared photoelectrocatalysis metal-loaded boron-doped diamond has high catalytic activity, stability and selectivity in a chemical process, and the selectivity and efficiency in the catalytic process are greatly improved.
Accordingly, the photoelectrocatalytic metal-loaded boron-doped diamond is prepared by the following method.
The embodiment of the invention provides a preparation method of a photoelectrocatalysis metal-loaded boron-doped diamond, which comprises the following steps:
s01, providing a boron-doped diamond as a carrier, wherein the boron-doped diamond comprises a substrate and a boron-doped diamond layer arranged on any side of the substrate;
s02, etching the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer;
and S03, providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering mode to obtain the photoelectrocatalysis metal-loaded boron-doped diamond.
Specifically, in step S01, a substrate is provided, and preferably, the substrate is made of any one material selected from a silicon wafer, a chromium sheet, a titanium mesh, a carbon cloth, and a molybdenum mesh. In a preferred embodiment of the invention, said radicalThe bottom material is chromium sheet. Preferably, the area of the substrate material is 4 multiplied by 4 to 10 multiplied by 10cm2The thickness is 0.5 mm.
Preferably, the substrate is subjected to pretreatment, wherein the pretreatment is ultrasonic treatment by respectively adopting an acid solution and an organic solvent, and then the substrate is placed in a nano diamond powder suspension for ultrasonic treatment for 1-3 hours. Further preferably, the substrate is subjected to ultrasonic treatment by using an acid solution, so as to clean impurities on the surface of the substrate, and simultaneously form defects on the surface of the substrate, thereby facilitating subsequent deposition treatment. In a preferred embodiment of the invention, a mixed solution of hydrogen peroxide and concentrated sulfuric acid is selected for acid washing treatment, wherein the volume ratio of the hydrogen peroxide solution to the concentrated sulfuric acid solution is 10: 1. Preferably, the time for ultrasonic treatment by adding the acid solution is 30-40 minutes.
Further preferably, in the step of performing ultrasonic treatment on the substrate by using an organic solvent, the substrate is firstly cleaned by using acetone, and then is treated by using acetone, so that organic impurities on the surface of the substrate material can be dissolved and cleaned due to the fact that acetone has good fat solubility and water solubility. Preferably, the addition amount of the acetone is 50mL, and the ultrasonic cleaning time is 10-20 minutes.
After the acetone is ultrasonically cleaned, the acetone is ultrasonically cleaned by ethanol, and impurities which are not cleaned and residual acetone solution can be removed by further cleaning by the ethanol, so that the surface of the substrate material is ensured to be free of impurities, and meanwhile, a rugged micro surface structure is formed on the substrate material; the rugged microscopic surface structure is a crystal planting site which is a stable adsorption position of the diamond seed crystal. Facilitating subsequent processing of the substrate material. Preferably, the addition amount of the ethanol is 50mL, and the ultrasonic cleaning time is 10-20 minutes.
Further preferably, the substrate is subjected to ultrasonic treatment by using an organic solvent, and then is placed in the nano-diamond powder suspension for ultrasonic treatment for 1-3 hours, and preferably, the preparation method of the nano-diamond powder suspension comprises the following steps: providing 1-5mL of purchased diamond solution, and adding 100-400mL of deionized water. The particle size of the prepared nano diamond powder suspension is 1-100 nm. The solution is added to ensure that the substrate material is immersed. And implanting diamond seed crystals on the surface of the substrate material to prepare for subsequent deposition treatment. If the ultrasonic treatment time is too short, the nano-diamond cannot be uniformly implanted into the surface of the substrate material, and if the ultrasonic treatment time is too long, the diamond seed crystals on the surface fall off, thereby affecting the subsequent deposition treatment.
Preferably, the substrate is placed in the nano-diamond powder suspension for ultrasonic treatment for 1-3 hours, and then dried in inert gas flow at room temperature, so that impurities cannot exist in the subsequent deposition treatment process. In a preferred embodiment of the invention, the inert gas stream is selected from a nitrogen stream and treated in a nitrogen stream to avoid introducing other impurities during the preparation process.
Preferably, a layer of boron doped diamond is prepared on either side of the substrate using a hot wire vapour phase chemical deposition process. Preferably, the specific operation method of the hot wire vapor phase chemical deposition method is as follows:
s11, placing the pretreated chromium sheet substrate on a base station of a hot wire vapor deposition device, and keeping the chromium sheet in the middle of a hot wire and parallel to the hot wire; the distance between the hot wire and the surface of the chromium sheet is 20 mm.
S12, pumping the pressure in the furnace to be below 0.1Pa, and then introducing reaction gas to carry out a deposition reaction.
In step S11, preferably, the hot wires are tantalum wires with a diameter of 0.5 to 0.6mm, and the number of the hot wires is 9 to 10 hot wires. Further preferably, the chromium sheet is kept in the middle of the hot wire and parallel to the hot wire, wherein the distance between the hot wire and the surface of the chromium sheet is 6-25 mm, the temperature of the hot wire is 2000-2400 ℃, the power of the hot wire is 5000-7000W, and the temperature of the chromium sheet substrate is 500-850 ℃. In the preferred embodiment of the invention, 9 tantalum wires with the diameter of 0.5mm are selected as the hot wires, and the distance between the hot wires and the surface of the chromium sheet is kept to be 20 mm; the temperature of the hot wire is kept at 2000 ℃, the power of the hot wire is 6900W, and the temperature of the chromium film substrate is 500 ℃.
In the step S12, it is preferable that the total gas pressure of the introduced reaction gas is 1000-5000Pa, and the total gas flow rateIs 500 sccm. More preferably, the reaction gas is an inert gas or CH4、H2And Trimethylborane (TMB), wherein CH4As a carbon source for diamond deposition, CH4The concentration is 1.5-5%; the trimethylborane is used as a boron doping source for BDD deposition and is a mixed gas of the trimethylborane and hydrogen, and the concentration of the trimethylborane in the mixed gas is 0.1-1%. H2The function is to etch the non-diamond carbon; the function of the inert gas is to keep the total gas flow constant, and in a preferred embodiment of the invention, the inert gas is argon. In a preferred embodiment of the invention, the reaction gas is Ar or CH4、H2And Trimethylborane (TMB). In one embodiment of the present invention, the total gas flow rate is set to 500sccm, wherein the reactive gas ensures each gas CH4、H2The flow rates of Ar and TMB are 10sccm, 100sccm, 370sccm and 20 sccm.
Preferably, after the gas is introduced, the deposition pressure is adjusted to 1500 Pa; preferably, in the step of preparing the boron-doped diamond layer on any one side of the substrate by using a hot wire vapor-phase chemical deposition method, the deposition time of the hot wire vapor-phase chemical deposition method is 8-10 hours, so that the diamond film starts to nucleate and grow to prepare the boron-doped diamond layer. In the preferred embodiment of the invention, after the gas is introduced, the deposition pressure is adjusted to be 1500Pa, and the deposition time is set to be 10 hours to obtain the boron-doped diamond layer with the thickness of about 10 mu m, namely the boron-doped diamond carrier.
Specifically, in step S02, etching is performed on the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, where the processed boron-doped diamond layer includes a flat bottom layer and a tapered structure layer perpendicular to the flat bottom layer. The boron-doped diamond carrier is etched to obtain a flat bottom layer and a conical structure layer perpendicular to the flat bottom layer, the conical structure layer can increase the specific surface area of the boron-doped diamond carrier, so that the load can be increased in the subsequent treatment processThe amount of the particles is changed, and the catalytic effect can be further improved. Preferably, the etching treatment method comprises: after the deposition process is finished, the distance between the substrate and the tantalum wire is reduced to 5cm, CH4The gas flow rate of (2) is adjusted to 10sccm, H2The gas flow rate of (2) was adjusted to 490sccm, and etching was performed without changing other conditions. The etching time was 4 hours. If the etching time is too long, the nano structure can be damaged, and the subsequent further processing treatment is influenced; if the etching time is too short, a tapered structure layer cannot be obtained, which is not beneficial to improving the catalytic effect.
Specifically, in step S03, a metal target is provided, and metal sputtering is performed on the surface of the boron-doped diamond carrier in a magnetron sputtering manner, so as to obtain the photoelectrocatalysis metal-loaded boron-doped diamond.
Preferably, the metal target is selected from any one of a gold target, a silver target, a platinum target, a ruthenium target, a niobium target, a palladium target, a molybdenum target and an iridium target. In the embodiment of the invention, a gold target material is selected for reaction.
Preferably, in the step of keeping the surface of the boron-doped diamond carrier parallel to and facing the metal target, the distance between the boron-doped diamond carrier and the metal target is 5-15 cm. If the distance between the boron-doped diamond carrier and the metal target is adjusted, if the distance is too long, the loaded metal nanoparticles are too few; if the distance is too short, the amount of the metal nanoparticles in charge is excessive, and the metal nanoparticles are likely to agglomerate, which is not favorable for the catalytic action.
Specifically, metal sputtering treatment is carried out on the surface of the boron-doped diamond carrier in a magnetron sputtering mode, so as to obtain the metal-loaded boron-doped diamond. Preferably, a magnetron sputtering apparatus is provided, and the prepared diamond film is placed in the magnetron sputtering apparatus, and the surface of the boron-doped diamond carrier is kept parallel and opposite to the gold target material, so that the metal nanoparticles obtained by magnetron sputtering can be supported on the boron-doped diamond carrier.
Preferably, during the sputtering process, the pressure and time are adjusted, and sputtering is carried outAnd after the end, closing the mechanical pump, opening the air release valve, taking out the sample, and closing the air release valve. Further preferably, the pressure intensity in the cavity of the equipment is adjusted to be 1-2 multiplied by 10-3Pa. Further preferably, the time of the sputtering treatment is 2 to 4 minutes. If the sputtering time is too short, the loading capacity of the metal nanoparticles is not enough, which is not beneficial to the catalytic reaction; if the sputtering time is too long, the metal nanoparticles are excessively loaded, and the excessive metal nanoparticles are easily agglomerated and cannot exert a catalytic effect.
The preparation method of the photoelectrocatalysis metal-loaded boron-doped diamond comprises the steps of firstly providing a boron-doped diamond carrier, and etching the surface of a boron-doped diamond layer on any side of a substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer; providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering mode to obtain the metal-loaded boron-doped diamond; the adopted magnetron sputtering method is simple, convenient, rapid and easy to control, and simultaneously, the magnetron sputtering method can ensure the larger adhesive force of the metal nano particles and the boron-doped diamond carrier, has good material stability, improves the catalytic efficiency and is beneficial to industrial application.
Correspondingly, the embodiment of the invention also provides a photoelectrocatalysis reduction reaction electrode, and the reduction reaction electrode is made of the photoelectrocatalysis metal-loaded boron-doped diamond or the photoelectrocatalysis metal-loaded boron-doped diamond prepared by the method. Preferably, the photoelectrocatalytic reduction reaction comprises a photoelectrocatalytic reduction reaction of nitrogen into ammonia.
In a preferred embodiment of the invention, the prepared metal-loaded boron-doped diamond is used as a working electrode for carrying out photoelectrocatalytic reduction on nitrogen. The specific operation is as follows: a sealed double-cell reactor is provided, with the working electrode compartment and the counter electrode compartment separated by glass sheets to allow electrons to pass through but prevent mixing of the solutions. The prepared boron-doped diamond carrying metalAs a working electrode, a Pt sheet electrode was used as a counter electrode, and the distance between the working electrode and the counter electrode was 2 cm. Deionized water solution is added into the working electrode chamber, and equal volume of 0.1M KI solution is added into the electrode chamber. N is pre-introduced into the working electrode chamber for 0.5h before the reaction starts2Then continuously introducing N2. Photoelectrocatalysis reduction of N using irradiation of working electrode by electro Hg/Xe arc lamp2And (4) reacting.
The metal-loaded boron-doped diamond is used as a material of the working electrode for photoelectrocatalysis reduction reaction, and in the process of carrying out photoelectrocatalysis reaction by using the metal-loaded diamond as the material of the working electrode, the photoelectrocatalysis reduction reaction has higher catalytic activity, and the catalytic rate of the electrode reaches a higher level.
Correspondingly, the photoelectrocatalytic metal-loaded boron-doped diamond or the photoelectrocatalytic metal-loaded boron-doped diamond electrode prepared by the method is applied to photoelectrocatalytic reduction reaction in the embodiment of the invention.
The application of the photoelectrocatalytic metal-loaded boron-doped diamond electrode or the photoelectrocatalytic metal-loaded boron-doped diamond electrode prepared by the method in photoelectrocatalytic reduction reaction comprises chemical reactions such as reduction of photoelectrocatalytic nitrogen into ammonia gas.
The invention will now be described in further detail by taking the photoelectrocatalytic metal-loaded boron-doped diamond as an example, as well as a preparation method and application thereof.
Example 1
The preparation method of the photoelectrocatalysis gold-loaded boron-doped diamond comprises the following steps:
the method comprises the following steps: providing a boron doped diamond carrier comprising a substrate and boron doped diamond layers disposed on either side of the substrate;
firstly, providing a substrate made of chromium sheet materials, and pretreating the substrate: placing the substrate in a beaker, adding 100mL of hydrogen peroxide solution and 10mL of concentrated sulfuric acid, and carrying out ultrasonic treatment for 30 min; cleaning with water after ultrasonic treatment, adding 50mL of acetone, and performing ultrasonic treatment for 10 min; and then, replacing the acetone with ethanol, carrying out ultrasonic treatment for 10min, removing impurities on the surface of the substrate chromium sheet through two ultrasonic steps, and simultaneously forming a certain defect on the surface to form a crystal implantation site. Then taking out the chromium sheet, and placing the chromium sheet in deionized water for ultrasonic cleaning for 10 min. Finally, the cleaned substrate is placed in the nano diamond powder suspension for ultrasonic treatment for 1 hour, and diamond seed crystals are implanted on the surface of the substrate. After the sonication was completed, the substrate chromium plate was dried in a nitrogen stream at room temperature.
Secondly, preparing a boron-doped diamond layer on any side of the substrate by adopting a hot wire vapor chemical deposition method, which comprises the following specific operations: and (3) placing the pretreated chromium sheet substrate on a base station, keeping the chromium sheet in the middle of the hot wire and parallel to the hot wire, and keeping the distance between the hot wire and the surface of the chromium sheet to be 20 mm. The internal pressure of the furnace is forcibly pumped to be below 0.1Pa, and then reaction mixed gas CH is introduced4As a carbon source for diamond deposition, TMB was used as a boron doping source for boron doped diamond layer deposition. The TMB used is a mixed gas of TMB and hydrogen, and the concentration of TMB in the mixed gas is 0.1%. And adjusting the deposition pressure to start the nucleation and growth of the diamond film. The specific parameters are as follows: 9 tantalum wires with the diameter of 0.5mm are taken as hot wires, the distance between the hot wires and the surface of the chromium sheet is 20mm, and CH4/H2The flow rate of/Ar/TMB is 10sccm/100sccm/350sccm/30sccm/, the total gas flow rate is 500sccm, the deposition pressure is 1500Pa, the power of the hot wire: 6900W, carbon cloth substrate temperature: 500 ℃, deposition time: a boron doped diamond layer with a thickness of about 10 μm was obtained for 10 hours.
Step two: etching the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer; the method comprises the following specific operation steps: after the deposition is finished, adjusting the test parameters, reducing the distance between the substrate and the tantalum wire to 5cm, and controlling the gas flow CH4/H2The etching time was changed to 10sccm/490sccm and 4 h.
Step three: providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering manner to obtain a photoelectrocatalysis loadMetallic boron doped diamond. The specific operation is as follows: and placing the prepared diamond film in a magnetron sputtering device, keeping the diamond film parallel to and facing the gold target material, and keeping the distance between the target material and the surface of the substrate to be 5-15 cm. Opening the mechanical pump to pump the pressure in the cavity to 1-2 × 10-3Pa, setting sputtering time for 2-4 min, starting sputtering, after sputtering is finished, closing the mechanical pump, opening the air release valve, taking out the sample, and closing the air release valve to obtain the photoelectrocatalysis metal-loaded boron-doped diamond.
The structure of the prepared photoelectrocatalytic metal-loaded boron-doped diamond electrode is shown in fig. 1, the metal-loaded boron-doped diamond electrode comprises a substrate, a boron-doped diamond layer arranged on any side of the substrate, and the boron-doped diamond layer comprises a flat bottom layer, a conical structure layer perpendicular to the flat bottom layer, and a metal nanoparticle catalyst uniformly loaded at the tip of the conical structure layer.
Example 2
The photoelectrocatalytic gold-loaded boron-doped diamond prepared in example 1 is used as an electrode to carry out photoelectrocatalytic nitrogen reduction reaction, as shown in fig. 4, and the method specifically comprises the following steps:
a sealed double-cell reactor is adopted, and a working electrode chamber and a counter electrode chamber are separated by glass sheets, so that electrons can pass through but the solution is prevented from mixing. The prepared diamond film electrode is used as a working electrode, the Pt sheet electrode is used as a counter electrode, and the distance between the working electrode and the counter electrode is 2 cm. Deionized water solution is added into the working electrode chamber, and 0.1M KI solution with the same volume is added into the electrode chamber. N is pre-introduced into the working electrode chamber for 0.5h before the reaction starts2Then continuously introducing N2. The working electrode was irradiated with Hg/Xe arc lamp for treatment, followed by testing of the reduction performance, and finally the amount of ammonia generated by nitrogen reduction was determined by the indophenol blue method.
Comparative example 1
A preparation method of gold-loaded boron-doped diamond comprises the following steps:
the method comprises the following steps: providing a boron doped diamond carrier comprising a substrate and a boron doped diamond layer disposed on either side of the substrate;
firstly, providing a substrate made of chromium sheet materials, and pretreating the substrate: placing the substrate in a beaker, adding 100mL of hydrogen peroxide solution and 10mL of concentrated sulfuric acid, and carrying out ultrasonic treatment for 30 min; cleaning with water after ultrasonic treatment, adding 50mL of acetone, and performing ultrasonic treatment for 10 min; and then, replacing the acetone with ethanol, carrying out ultrasonic treatment for 10min, removing impurities on the surface of the substrate chromium sheet through two ultrasonic steps, and simultaneously forming a certain defect on the surface to form a crystal implantation site. Then taking out the chromium sheet, and placing the chromium sheet in deionized water for ultrasonic cleaning for 10 min. Finally, the cleaned substrate is placed in the nano-diamond powder suspension for ultrasonic treatment for 1 hour, and diamond seed crystals are implanted on the surface of the substrate. After the sonication was completed, the substrate chromium plate was dried in a nitrogen stream at room temperature.
Secondly, preparing a boron-doped diamond layer on any one side of the substrate by adopting a hot wire vapor chemical deposition method, which specifically comprises the following steps: and (3) placing the pretreated chromium sheet substrate on a base station, keeping the chromium sheet in the middle of the hot wire and parallel to the hot wire, and keeping the distance between the hot wire and the surface of the chromium sheet to be 20 mm. The internal pressure of the furnace is forcibly pumped to be below 0.1Pa, and then reaction mixed gas CH is introduced4As a carbon source for diamond deposition, TMB was used as a boron doping source for boron doped diamond layer deposition. The TMB used is a mixed gas of TMB and hydrogen, and the concentration of TMB in the mixed gas is 0.1%. And adjusting the deposition pressure to start the nucleation and growth of the diamond film. The specific parameters are as follows: 9 tantalum wires with the diameter of 0.5mm are taken as hot wires, the distance between the hot wires and the surface of the chromium sheet is 20mm, and CH4/H2The flow rate of/Ar/TMB is 10sccm/100sccm/350sccm/30sccm/, the total gas flow rate is 500sccm, the deposition pressure is 1500Pa, the power of the hot wire: 6900W, carbon cloth substrate temperature: 500 ℃, deposition time: a boron doped diamond layer with a thickness of about 10 μm was obtained for 10 hours.
Step two: and providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering mode to obtain the metal-loaded boron-doped diamond. The specific operation is as follows: and (3) suspending the prepared diamond film in a magnetron sputtering device, keeping the diamond film parallel to and facing the gold target material, and keeping the distance between the target material and the surface of the substrate to be 5-15 cm. And opening the mechanical pump, forcibly pumping the internal pressure of the cavity to 1-2 x 10 < -3 > Pa, setting the sputtering time to be 2-4 min, starting sputtering, closing the mechanical pump after the sputtering is finished, opening a gas release valve, taking out the sample, and closing the gas release valve to obtain the metal-loaded boron-doped diamond.
The prepared gold-loaded boron-doped diamond electrode structure is shown in fig. 2, and comprises a substrate, a boron-doped diamond layer arranged on any side of the substrate, and a metal nanoparticle catalyst uniformly loaded on the surface of the boron-doped diamond layer.
Comparative example 2
The gold-loaded boron-doped diamond prepared in comparative example 1 is used as an electrode to perform a photoelectrocatalytic nitrogen reduction reaction as shown in fig. 4, and the method comprises the following specific steps:
a sealed double-cell reactor is adopted, and a working electrode chamber and a counter electrode chamber are separated by glass sheets, so that electrons can pass through but the solution is prevented from mixing. The prepared diamond film electrode is used as a working electrode, the Pt sheet electrode is used as a counter electrode, and the distance between the working electrode and the counter electrode is 2 cm. Deionized water solution is added into the working electrode chamber, and 0.1M KI solution with the same volume is added into the electrode chamber. N is pre-introduced into the working electrode chamber for 0.5h before the reaction starts2Then continuously introducing N2. The working electrode was irradiated with Hg/Xe arc lamps for treatment, followed by a test for reducing properties, and finally the amount of ammonia generated by nitrogen reduction was determined by the indophenol blue method.
Comparative example 3
The preparation method of the boron-doped diamond comprises the following steps:
the method comprises the following steps: providing a boron doped diamond carrier comprising a substrate and a boron doped diamond layer disposed on either side of the substrate;
firstly, providing a substrate of chromium sheet materials, and pretreating the substrate: placing the substrate in a beaker, adding 100mL of hydrogen peroxide solution and 10mL of concentrated sulfuric acid, and carrying out ultrasonic treatment for 30 min; cleaning with water after ultrasonic treatment, adding 50mL of acetone, and performing ultrasonic treatment for 10 min; and then, replacing the acetone with ethanol, carrying out ultrasonic treatment for 10min, removing impurities on the surface of the substrate chromium sheet through two ultrasonic steps, and simultaneously forming a certain defect on the surface to form a crystal implantation site. Then taking out the chromium sheet, and placing the chromium sheet in deionized water for ultrasonic cleaning for 10 min. Finally, the cleaned substrate is placed in the nano diamond powder suspension for ultrasonic treatment for 1 hour, and diamond seed crystals are implanted on the surface of the substrate. After the sonication was completed, the substrate chromium plate was dried in a nitrogen stream at room temperature.
Secondly, preparing a boron-doped diamond layer on any side of the substrate by adopting a hot wire vapor chemical deposition method, which comprises the following specific operations: and (3) placing the pretreated chromium sheet substrate on a base station, keeping the chromium sheet in the middle of the hot wire and parallel to the hot wire, and keeping the distance between the hot wire and the surface of the chromium sheet to be 20 mm. The internal pressure of the furnace is forcibly pumped to be below 0.1Pa, and then reaction mixed gas CH is introduced4As a carbon source for diamond deposition, TMB was used as a boron doping source for boron doped diamond layer deposition. Wherein the TMB is a mixed gas of TMB and hydrogen, and the concentration of TMB in the mixed gas is 0.1%. And adjusting the deposition pressure to start the nucleation and growth of the diamond film. The specific parameters are as follows: 9 tantalum wires with the diameter of 0.5mm are taken as hot wires, the distance between the hot wires and the surface of the chromium sheet is 20mm, and CH4/H2The flow rate of/Ar/TMB is 10sccm/100sccm/350sccm/30sccm/, the total gas flow rate is 500sccm, the deposition pressure is 1500Pa, the power of the hot wire: 6900W, carbon cloth substrate temperature: 500 ℃, deposition time: a boron doped diamond layer with a thickness of about 10 μm was obtained for 10 hours.
Step two: etching the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer; the specific operation steps are as follows: after the deposition is finished, adjusting test parameters, reducing the distance between the substrate and the tantalum wire to 5cm, and controlling the gas flow CH4/H2The etching time was changed to 10sccm/490sccm and 4 h.
The prepared boron-doped diamond electrode structure is shown in fig. 3, and the boron-doped diamond electrode comprises a substrate and boron-doped diamond layers arranged on any side of the substrate, wherein each boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer.
Comparative example 4
The boron-doped diamond prepared in the comparative example 3 is used as an electrode to carry out a photoelectrocatalytic nitrogen reduction reaction as shown in fig. 4, and the method comprises the following specific steps:
a sealed double-cell reactor is adopted, and a working electrode chamber and a counter electrode chamber are separated by glass sheets, so that electrons can pass through but the solution is prevented from mixing. The prepared diamond film electrode is used as a working electrode, the Pt sheet electrode is used as a counter electrode, and the distance between the working electrode and the counter electrode is 2 cm. Deionized water solution is added into the working electrode chamber, and 0.1M KI solution with the same volume is added into the electrode chamber. N is pre-introduced into the working electrode chamber for 0.5h before the reaction starts2Then continuously introducing N2. The working electrode was irradiated with Hg/Xe arc lamp for treatment, followed by testing of the reduction performance, and finally the amount of ammonia generated by nitrogen reduction was determined by the indophenol blue method.
The results of the photoelectrocatalytic nitrogen reduction reactions described in the above example 2, comparative example 2, and comparative example 4 were analyzed, and the results were as follows:
for example 2, the catalytic rate and also the faradaic efficiency of the electrode were highest under irradiation by an Hg/Xe arc lamp, with an ammonia production rate of 5 μ g h-1cm-2The Faraday efficiency reaches 20%.
For comparative example 2, the catalytic rate and also the faradaic efficiency of the electrode were improved under irradiation with an Hg/Xe arc lamp, with an ammonia production rate of 2 μ g h-1cm-2The Faraday efficiency reaches 10%.
For comparative example 4, the catalytic rate and also the faradaic efficiency of the electrode were improved under irradiation with an Hg/Xe arc lamp, with an ammonia production rate of 1 μ g h-1cm-2The Faraday efficiency reaches 5 percent.
Experiments prove that the prepared photoelectrocatalysis metal-loaded boron-doped diamond electrode comprises a substrate and a boron-doped diamond layer arranged on any side of the substrate, wherein the boron-doped diamond layer comprises a flat bottom layer, a conical structure layer perpendicular to the flat bottom layer and a metal nanoparticle catalyst uniformly loaded at the tip of the conical structure layer, and the photoelectrocatalysis metal-loaded boron-doped diamond electrode has higher catalytic activity in the experimental process of photoelectrocatalysis nitrogen reduction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The utility model provides a photoelectrocatalysis's boron doping diamond of load metal, its characterized in that, load metal's boron doping diamond includes the base, sets up in the boron doping diamond layer of any side of base, boron doping diamond layer is including leveling the bottom and perpendicular to level the conical structure layer of bottom to and the even load is in the metal nanoparticle catalyst of the tip of conical structure layer, make metal nanoparticle and boron doping diamond carrier interact, make metal atom have low coordination and the biggest atom utilization efficiency.
2. The photoelectrocatalytic metal-loaded boron-doped diamond of claim 1, wherein the flat underlayer has a thickness of 500nm to 5 μ ι η; and/or the presence of a gas in the gas,
the height of the conical structure layer is 500 nm-2 mu m.
3. The photoelectrocatalytic metal-loaded boron-doped diamond according to claim 1, wherein in the tapered structure layer, a bottom diameter of the tapered structure is 100nm to 1 μ ι η; and/or the presence of a gas in the gas,
the radius of curvature of the tip of the tapered structure does not exceed 20 nm.
4. The photoelectrocatalytic metal-loaded boron-doped diamond according to any one of claims 1 to 3, wherein the metal nanoparticle catalyst has a particle size of 0.1nm to 20 nm.
5. The photoelectrocatalytic metal-loaded boron-doped diamond of any one of claims 1 to 3, wherein the proportion of the loading area of the metal nanoparticle catalyst in the area of the boron-doped diamond layer is 10% to 20%.
6. A preparation method of photoelectrocatalysis metal-loaded boron-doped diamond is characterized by comprising the following steps:
providing boron-doped diamond as a carrier, wherein the boron-doped diamond comprises a substrate and boron-doped diamond layers arranged on any side of the substrate;
etching the surface of the boron-doped diamond layer on any side of the substrate to obtain a processed boron-doped diamond layer, wherein the processed boron-doped diamond layer comprises a flat bottom layer and a conical structure layer vertical to the flat bottom layer;
and providing a metal target, and performing metal sputtering treatment on the surface of the boron-doped diamond carrier in a magnetron sputtering manner to obtain the photoelectrocatalysis metal-loaded boron-doped diamond.
7. The method for preparing a metal-loaded boron-doped diamond according to claim 6, wherein the metal target is selected from any one of a gold target, a silver target, a platinum target, a ruthenium target, a palladium target, an iridium target, a niobium target, and a molybdenum target.
8. The method for preparing a photoelectrocatalytic metal-loaded boron-doped diamond according to any one of claims 6 to 7, wherein the sputtering treatment time is 2 to 4 minutes; and/or the presence of a gas in the gas,
the distance between the conical structural layer and the metal target is 5-15 cm.
9. A photoelectrocatalysis reduction reaction electrode, which is characterized in that the material of the reduction reaction electrode is the photoelectrocatalysis metal-loaded boron-doped diamond of any one of the claims 1 to 5 or the photoelectrocatalysis metal-loaded boron-doped diamond prepared by the method of any one of the claims 6 to 8.
10. Use of a photoelectrocatalytic metal-loaded boron-doped diamond comprising a photoelectrocatalytic diamond according to any one of claims 1 to 5 or an electrode of a photoelectrocatalytic metal-loaded boron-doped diamond prepared by a method according to any one of claims 6 to 8 in a photoelectrocatalytic reduction reaction.
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