CN114457376B - Preparation method of boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction - Google Patents
Preparation method of boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction Download PDFInfo
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Abstract
A preparation method of boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction belongs to the technical field of electrocatalysis. Firstly preparing a boron-doped titanium dioxide nanotube structure by using an anodic oxidation method as a magnetron sputtering matrix material; sputtering molybdenum disulfide onto the boron-doped titanium dioxide nanotube array by utilizing the radio frequency sputtering function of magnetron sputtering to form a molybdenum disulfide film with a certain shape structure; cutting and packaging the structure to obtain a test electrode; the electrocatalytic nitrogen reduction performance of the electrodes was tested in 0.1mol/L hydrochloric acid under sealed conditions using an H-shaped cell with a reaction chamber capacity of 50 ml. The catalytic effect and the cycle performance are relatively good.
Description
Technical Field
A preparation method of boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction belongs to the technical field of electrocatalysis.
Background
Titanium dioxide (TiO) 2 ) The nano material is an important multifunctional semiconductor material, and has great application prospect in the fields of catalysis, energy sources and the like. Wherein, tiO 2 The nanotube array has the advantages of unique photoelectrochemical property, ordered tubular structure with large specific surface area, stable physicochemical property and the like, and especially can be used for constructing proper structures such as oxygen vacancies, doping and the like on the surface of the nanotube array through proper process adjustment, thereby having great significance for subsequent modification for application in different fields.
Electrochemical nitrogen reduction is an emerging research direction, which is of great importance in terms of environmental protection. The current industrial nitrogen reduction technology needs a large amount of energy to maintain a severe nitrogen reduction condition, and the electrochemical nitrogen reduction technology can realize the selective catalysis of nitrogen molecules at active sites through structural design under the environmental condition, and the current fast-developed green energy technology is combined, so that a green and energy-saving nitrogen reduction process is realized in the future.
Disclosure of Invention
The preparation method of the boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction comprises the steps of firstly preparing a boron-doped titanium dioxide nanotube structure serving as a magnetron sputtering matrix material by an anodic oxidation method; sputtering molybdenum disulfide onto the boron-doped titanium dioxide nanotube array by utilizing the radio frequency sputtering function of magnetron sputtering to form a molybdenum disulfide film with a certain shape structure; cutting and packaging the structure to obtain a test electrode; the electrocatalytic nitrogen reduction performance of the electrodes was tested in 0.1mol/L hydrochloric acid under sealed conditions using an H-shaped cell with a reaction chamber capacity of 50 ml. The working potential of the electrode prepared by immobilizing molybdenum disulfide on the nanotube array under the conditions of the radio frequency parameter of 200W, 200 ℃ and 45s is-0.15V and-0.2V vs. RHEThe first catalytic rate and Faraday efficiency during the catalytic process can reach 2.455 mug/(h cm) 2 ) And 44.6%, and 60% of the primary catalysis can still be achieved after five experiments. The method shows that the battery cathode material prepared by the titanium dioxide nanotube array immobilized molybdenum disulfide is very feasible.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
(1) Pretreatment of titanium sheets: firstly, removing dirt on the surface of a titanium sheet by a physical and chemical method, and drying for later use;
the method comprises the following steps: washing cut titanium sheet (44 x 100 mm) with detergent and tap water, respectively ultrasonic treating with deionized water and ethanol for 10min, ultrasonic washing with HF and HNO acid solution 3 、H 2 The mixed liquid of O is subjected to ultrasonic treatment in deionized water for 10min after pickling, so that dirt on the surface of a titanium sheet can be removed, and the titanium sheet is dried for later use;
(2) Constant pressure boration: at 0.5wt% NH 4 BF 4 Performing electrochemical anodic boration treatment in 5wt% deionized water and an organic solution which takes ethylene glycol as a solution; the method comprises the steps of carrying out a first treatment on the surface of the
The method comprises the following steps: constant pressure treatment is carried out for 240min under the potential of 60V, then a sample is taken out, and the sample is washed with a small amount of ethanol and then air-dried for standby;
(3) Constant pressure anodic oxidation: anodizing in an organic solution containing fluoride ions;
the method comprises the following steps: performing constant pressure treatment at 60V for 30min, taking out the sample, washing with a small amount of ethanol, and air drying;
(4) And (3) heat treatment: carrying out heat treatment on the oxidized sample in a resistance furnace at 200-450 ℃, preserving heat for 2 hours, and then cooling to room temperature along with the furnace;
(5) Preparing an electrocatalytic nitrogen reduction structure by magnetron sputtering: taking the boron doped titanium oxide nano array after the heat treatment in the step (4) as a matrix, and cooling to 45 ℃ for taking out after vacuumizing, heating, pre-sputtering and sputtering, wherein the sputtering step comprises the following steps: sputtering a molybdenum disulfide target material by using a radio frequency power supply, wherein the magnetron sputtering parameters are 200W, 200 ℃ and 45s, and then turning off the radio frequency power supply; heating the substrate during sputtering, cooling to 45deg.C, and taking out the sampleOf these, the back vacuum degree is preferably 8×10 -4 Pa, the pre-sputtering time was 180s, and the argon pressure was 1.5Pa.
Preparation of working electrode: cutting the structure obtained in the step (5) to 1cm 2 The cut sample is linked with 8cm long end part peeling copper wire by adhesive tape, then the joint surface is sealed by sealing glue after rosin and paraffin are mixed and melted, and the test is carried out after the joint surface is air-dried and stabilized.
Compared with the prior art, the invention has the beneficial effects that:
preparing a boron-doped titanium oxide nanotube structure by using an anodic oxidation method as a matrix material for inducing molybdenum disulfide to be formed; sputtering molybdenum disulfide onto a boron-doped titanium dioxide nanotube array by using a radio frequency power supply to form a uniformly distributed B-Mo binary site structure, wherein the structure can transport electrons to a reverse bond orbit of a nitrogen molecule under a given working potential so as to crack a nitrogen-nitrogen triple bond; meanwhile, the structures of the same molybdenum and boron with different less than d orbitals and different p orbitals are used to ensure that the two elements have different capability of predominating electrons on two nitrogen atoms in a nitrogen molecule, so that the dinitrogen molecule is catalyzed on the site and simultaneously generates intramolecular polarization to generate an additional triple bond decomposition effect, and the morphology is shown in figure 1. The first catalytic rate and Faraday efficiency of the structure formed under the conditions of the magnetron sputtering parameters of 200W, 200 ℃ and 45s can reach 2.455 mug/(H cm) respectively when the structure is catalyzed in 0.1mol/L hydrochloric acid under the working potential of-0.15V and-0.2V vs. RHE under the sealing condition by using an H-shaped electrolytic cell with the reaction chamber capacity of 50ml 2 ) And 44.6%, and 60% of the primary catalysis can still be achieved after five experiments, which shows that the battery anode material prepared by the boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide is feasible.
Drawings
Fig. 1: moS after magnetron sputtering 2 /B-TiO 2 SEM image of structure;
fig. 2: moS after magnetron sputtering 2 /B-TiO 2 EDX map of structure;
fig. 3:1cm 2 Example 1 catalytic rate and faraday efficiency plot for an electrode;
fig. 4:1cm 2 Example 1 original electricity of electrodeFlow-time curve and uv-vis spectroscopic data;
fig. 5:1cm 2 Example 2 catalytic rate and faraday efficiency plot for an electrode;
fig. 6:1cm 2 Example 3 catalytic rate and faraday efficiency plot for an electrode.
Detailed Description
The following illustrates a specific embodiment of a method for preparing the boron-doped titania nanotube array-supported molybdenum disulfide for electrochemical nitrogen reduction according to the present invention, but the present invention is not limited to the following examples.
The process parameters of the boride treatment and anodic oxidation after pretreatment of the metallic titanium sheet in the following examples: the boration treatment voltage is 60V for 240min, then the sample is oxidized for 30min under 60V, and the sample is taken out, washed with a small amount of ethanol and dried; the organic solution containing fluorine ions is 5gNH 4 HF. A mixed solution of 1L of ethylene glycol and 10ml of water.
Cutting and packaging the structure to obtain a test negative electrode; the electrocatalytic nitrogen reduction performance (nitrogen gas inlet rate: 20 ml/min) of an electrode is tested in 0.1mol/L hydrochloric acid under a sealed condition by using an H-shaped electrolytic cell with the reaction chamber capacity of 50ml, and ammonia gas is generated by reduction; the constant voltage operating potential is-0.05V-0.4V, preferably-0.15V-0.2V.
Example 1
Cleaning, ultrasonic and acid washing a metal titanium sheet, performing boronization in an organic solution containing boron ions for 4 hours, performing constant-pressure anodic oxidation in the organic solution containing fluorine ions for 30 minutes, performing heat treatment at 450 ℃, performing ultrasonic treatment in ethanol, and drying; the boron doped titanium oxide nanotube array sheet after heat treatment is put into a magnetron sputtering system, the parameters of the radio frequency power supply for sputtering molybdenum disulfide comprise sputtering power of 200W, sputtering time of 45s, sputtering temperature of 200 ℃, wherein the vacuum degree of the back bottom is 8 multiplied by 10 -4 Pa, pre-sputtering time is 180s, impurities and oxides are removed, and argon pressure is 1.5Pa; vacuum-pumping, heating, pre-sputtering, cooling to 45deg.C, and taking out to obtain 1cm 2 The electrode of (2) is subjected to electrochemical nitrogen reduction performance test.
Example 2
Cleaning, ultrasonic and acid washing a metal titanium sheet, performing boronization in an organic solution containing boron ions for 4 hours, performing constant-pressure anodic oxidation in the organic solution containing fluorine ions for 30 minutes, performing heat treatment at 450 ℃, performing ultrasonic treatment in ethanol, and drying; the boron doped titanium oxide nanotube array sheet after heat treatment is put into a magnetron sputtering system, the parameters of the radio frequency power supply for sputtering molybdenum disulfide comprise sputtering power of 200W, sputtering time of 30s, sputtering temperature of 200 ℃, wherein the vacuum degree of the back bottom is 8 multiplied by 10 -4 Pa, pre-sputtering time is 180s, impurities and oxides are removed, and argon pressure is 1.5Pa; vacuum-pumping, heating, pre-sputtering, cooling to 45deg.C, and taking out to obtain 1cm 2 The electrode of (2) is subjected to electrochemical nitrogen reduction performance test.
Example 3
Cleaning, ultrasonic and acid washing a metal titanium sheet, performing boronization in an organic solution containing boron ions for 4 hours, performing constant-pressure anodic oxidation in the organic solution containing fluorine ions for 30 minutes, performing heat treatment at 450 ℃, performing ultrasonic treatment in ethanol, and drying; the boron doped titanium oxide nanotube array sheet after heat treatment is put into a magnetron sputtering system, the parameters of the radio frequency power supply for sputtering molybdenum disulfide comprise sputtering power of 200W, sputtering time of 60s, sputtering temperature of 200 ℃, wherein the vacuum degree of the back bottom is 8 multiplied by 10 -4 Pa, pre-sputtering time is 180s, impurities and oxides are removed, and argon pressure is 1.5Pa; vacuum-pumping, heating, pre-sputtering, cooling to 45deg.C, and taking out to obtain 1cm 2 The electrode of (2) is subjected to electrochemical nitrogen reduction performance test.
The above embodiment has good repeatability and similar technical effects are obtained.
Table 1 summary of experimental parameters
TABLE 2 data on catalytic Rate and Faraday efficiency of samples with RF parameters of 200W, 45s, 200℃at different operating potentials
。
Claims (4)
1. The preparation method of the boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction is characterized by comprising the following steps of:
(1) Pretreatment of titanium sheets: firstly, removing dirt on the surface of a titanium sheet by a physical and chemical method, and drying for later use;
(2) Constant pressure boration: at 0.5wt% NH 4 BF 4 Performing electrochemical anodic boration treatment in 5wt% deionized water and an organic solution with ethylene glycol as a solvent;
the method comprises the following steps: constant pressure treatment is carried out for 240min under the potential of 60V, then a sample is taken out, and the sample is washed with a small amount of ethanol and then air-dried for standby;
(3) Constant pressure anodic oxidation: anodizing in an organic solution containing fluoride ions;
the method comprises the following steps: performing constant pressure treatment at 60V for 30min, taking out the sample, washing with a small amount of ethanol, and air drying;
(4) And (3) heat treatment: carrying out heat treatment on the oxidized sample in a resistance furnace at 200-450 ℃, preserving heat for 2 hours, and then cooling to room temperature along with the furnace;
(5) Preparing an electrocatalytic nitrogen reduction structure by magnetron sputtering: taking the boron doped titanium oxide nano array after the heat treatment in the step (4) as a matrix, cooling to 45 ℃ and taking out after vacuumizing, heating, pre-sputtering and sputtering, wherein sputtering: and sputtering a molybdenum disulfide target material by using a radio frequency power supply.
2. The method for preparing the boron-doped titanium dioxide nanotube array immobilized molybdenum disulfide for electrochemical nitrogen reduction according to claim 1, wherein the magnetron sputtering parameters in the step (5) are 200W, 200 ℃ and 45s, and then the radio frequency power supply is turned offThe method comprises the steps of carrying out a first treatment on the surface of the Heating the substrate during sputtering, cooling to 45deg.C, and taking out sample, wherein the vacuum degree of the back substrate is 8X10 -4 Pa, the pre-sputtering time was 180s, and the argon pressure was 1.5Pa.
3. The boron doped titanium dioxide nanotube array prepared according to any one of claims 1-2 carries molybdenum disulfide.
4. The use of the boron doped titania nanotube array immobilized molybdenum disulfide prepared according to any one of claims 1-2 as a cathode for electrochemical catalytic nitrogen reduction to produce ammonia.
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| Mechanism on reduction and nitridation of micrometer‐sized titania with ammonia gas;Yongjie Liu 等;Journal of the American Ceramic Society;第103卷(第6期);3905-3916 * |
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| 玻璃基底TiO_2纳米管阵列的制备及其光电性能研究;郭宏;白晶;李金花;周保学;蔡伟民;;材料科学与工艺(05);666-670 * |
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