CN110408953B - Phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode and preparation method thereof - Google Patents

Phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode and preparation method thereof Download PDF

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CN110408953B
CN110408953B CN201910744440.0A CN201910744440A CN110408953B CN 110408953 B CN110408953 B CN 110408953B CN 201910744440 A CN201910744440 A CN 201910744440A CN 110408953 B CN110408953 B CN 110408953B
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tungsten oxide
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porous core
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CN110408953A (en
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陈明华
王凡
陈庆国
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Harbin University of Science and Technology
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Abstract

A phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode and a preparation method thereof belong to the field of preparation methods of electrocatalytic electrode materials. After preparing carbon cloth with a tungsten oxide seed layer, dissolving sodium tungstate and acetic acid in deionized water, adding concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, then adding ammonium sulfate, uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution, placing the tungsten oxide nanowire hydrothermal reaction solution into a high-pressure reaction kettle for hydrothermal reaction, uniformly mixing sodium hypophosphite and sulfur powder, placing the mixture at the upstream of a double-temperature-zone tubular furnace, placing the prepared tungsten oxide nanowire array at the downstream of the double-temperature-zone tubular furnace, controlling the upstream temperature of the tubular furnace to be 280-300 ℃ under the protection of argon gas, controlling the downstream temperature of the tubular furnace to be 750-850 ℃, and reacting at constant temperature for a certain time to obtain the phosphorus-doped tungsten sulfide porous tungsten oxide core-shell flexible array electrode. The invention has excellent electrochemical performance.

Description

Phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode and preparation method thereof
Technical Field
The invention belongs to the field of preparation methods of electrocatalytic electrode materials; in particular to a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode and a preparation method thereof.
Background
Renewable green energy has become a research hotspot in recent years. Hydrogen is considered to be an environmentally friendly clean energy carrier. The electrochemical water decomposition hydrogen production replaces fossil fuel, and is a clean and reproducible method. In recent years, hydrogen production by the water splitting hydrogen production reaction (HER) has received wide attention and is likely to be the primary method of hydrogen production. Depending on the design and synthesis of the high efficiency electrocatalyst. Currently, platinum-based metals and platinum-based alloys are the most effective catalysts. Unfortunately, the shortage and high price of these precious metals severely limits their development in the electrolysis of water. Therefore, there is a need to design a low-cost, high-performance electrocatalyst to replace the noble metal as a catalyst.
Transition Metal Sulfides (TMDs), such as molybdenum sulfide, molybdenum selenide, tungsten sulfide, tungsten selenide, and the like, are considered as catalysts having a wide range of application prospects. Particularly TMDs have strong edge activity and stability to hydrogen evolution reaction. Among all TMDs, tungsten sulfide is of great interest because of its superior properties of high surface area and potentially large number of active sites. At present, a great deal of research is being conducted on improving the electrocatalytic properties of tungsten sulfide. In order to increase the number of active sites and enhance the intrinsic activity of the active sites, researchers have done a great deal of work including heteroatom doping, nanostructure modification, surface engineering, interface engineering, nanocarbon hybridization, and the like. However, the HER activity of tungsten sulfide still fails to meet commercial requirements due to drawbacks such as active site exposure, charge transfer and mass transport. The mechanism for improving the catalytic activity is not clear.
Tungsten sulfide (WS)2) As a transition metal sulfide, the transition metal sulfide has better performances of catalysis, photoluminescence, visible light absorption and the like, and is widely used in the fields of light emitting diodes, solar cells, fluorescent materials, lithium ion batteries, superconductors, photocatalysis, electrochemical cells and the like. Doping tungsten sulfide with foreign atoms can cause electronic perturbation and further affect the intrinsic catalytic performance of the tungsten sulfide.
Disclosure of Invention
The invention aims to provide a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode with high catalytic performance and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth for 1-2 times by using acetone, ethanol and deionized water respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1-1.2, performing electrodeposition tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning, and drying to obtain the carbon cloth with the tungsten oxide seed layer;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: and (2) uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tube furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tube furnace, controlling the upstream temperature of the tube furnace to be 280-300 ℃ and the downstream temperature of the tube furnace to be 750-850 ℃ under the protection of argon gas, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
The preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the step 1 of ultrasonic cleaning for 10min each time.
The invention relates to a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, which is characterized in that sodium tungstate in step 2 is sodium tungstate dihydrate, the concentration of an aqueous hydrogen peroxide solution is 30 wt%, and the material-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to deionized water is 0.8-1.0 g: 0.7-1 ml: 180-220 ml, adjusting the pH value of the solution to 1.2 by using perchloric acid, electrodepositing tungsten oxide by adopting a three-electrode constant-pressure deposition method, setting the voltage to be-0.7V by taking the carbon cloth processed in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, setting the deposition time to be 400 seconds, setting the high-temperature treatment temperature after electrodeposition to be 400-450 ℃ and setting the treatment time to be 60-90 min.
The invention relates to a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, wherein the feed-liquid ratio of sodium tungstate, aqueous hydrogen peroxide and deionized water in step 2 is 0.825 g: 0.776 ml: 200ml, the high-temperature treatment temperature after electrodeposition is 400 ℃, and the treatment time is 60 min.
The invention relates to a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, which is characterized in that sodium tungstate is sodium tungstate dihydrate in step 3, the concentration of acetic acid is 36-38 wt%, and the material-liquid ratio of sodium tungstate to oxalic acid to deionized water is 4-5 g: 3-5 g: 200-280 ml, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 1-3, wherein the mass ratio of the solution to the ammonium sulfate is 50-60: 2 to 5.
The invention relates to a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, which is characterized in that sodium tungstate is sodium tungstate dihydrate in step 3, the concentration of acetic acid is 36-38 wt%, and the material-liquid ratio of sodium tungstate to oxalic acid to deionized water is 4.11 g: 3.15 g: 250ml, and the volume ratio of the solution to the concentrated nitric acid is 1000: 1.3, the mass ratio of the solution to the ammonium sulfate is 50: 2.
the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps of carrying out hydrothermal reaction at 180 ℃ for 16h, carrying out high-temperature annealing in air at 500 ℃ for 8-10 min.
The invention relates to a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, wherein in the step 5, the mass ratio of sodium hypophosphite to sulfur powder is 1-3: and (3) controlling the upstream temperature of the tubular furnace to reach 280 ℃ and the downstream temperature of the tubular furnace to reach 800 ℃ in 80-90 min, reacting at a constant temperature for 60-70 min, and cooling to room temperature in an argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
The phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the preparation methodThe heterogeneous tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode has the current density of 10mAcm-2The overpotential in this case was 89 mV.
According to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, the catalytic activity of transition metal sulfide is improved by doping. Meanwhile, modification of the nanostructure and adjustment of chemical components are the key to the development of an effective non-noble metal hydrogen evolution reaction catalyst. The carbon fiber cloth serving as a flexible substrate has good mechanical properties and excellent electronic conductivity, and is expected to realize the rapid conduction of electrons and the effect of inhibiting the structural change of the material when being applied to an electrocatalytic electrode material, so that the good electrocatalytic performance is realized.
According to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, phosphorus atom doping plays an important role in the property of tungsten sulfide, and the phosphorus atom doping improves the reaction activity and the conductivity by forming external defects.
According to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, the porous nanowire array not only increases the surface area of the material and exposes more active sites, but also enables the structure-induced super-hydrophobic surface to quickly release bubbles generated on the surface of the electrode, so that the mass transport in a catalytic process related to gas evolution is promoted.
According to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, carbon fiber cloth is used as a carrier, so that a specific surface (shell) nanostructure has excellent catalytic performance and long-term stability in the aspects of porosity, surface area and the like.
The electrode prepared by the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode shows excellent electrochemical performance in HER, and the current density is 10mAcm-2The overpotential of time is 89mV, and the Tafel slope is 79mVde-1。
The electrode prepared by the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode has remarkable long-term durability, and the catalytic activity of the electrode is not obviously attenuated after 1000 CV cycles.
The invention provides a new idea for the development of an advanced electrocatalytic unbonded shell-core composite material array.
Drawings
FIG. 1 is a process flow diagram of a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the invention;
FIG. 2 is an SEM photograph at 3000 times of a carbon cloth with a tungsten oxide seed layer prepared by a method according to an embodiment;
FIG. 3 is a SEM photograph of carbon cloth with a tungsten oxide seed layer taken at a magnification of 5000 times as prepared by one embodiment of the present invention;
FIG. 4 is an SEM photograph of a carbon cloth with a tungsten oxide seed layer taken at 90000 times magnification prepared by a method according to one embodiment;
FIG. 5 is a SEM photograph of the phosphorus doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the method of the embodiment at a magnification of 5000 times;
FIG. 6 is an SEM photograph of the phosphorus doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode at a magnification of 80000 times;
FIG. 7 is a transmission electron microscope photograph of 50000 times of the flexible array electrode of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire prepared by the method of the first embodiment;
FIG. 8 is a 400000 times transmission electron microscope photograph of a flexible array electrode of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire prepared by a method according to an embodiment;
FIG. 9 is an EDX spectrum of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the method of the first embodiment;
FIG. 10 is an XRD spectrum of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the method of the first embodiment;
FIG. 11 is a Raman spectrum of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the method of the embodiment;
FIG. 12 is a linear scanning voltammogram of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the second embodiment;
fig. 13 is a tafel electrochemical spectrum of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the second embodiment;
fig. 14 is an electrochemical stability curve of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the second embodiment.
Detailed Description
The first embodiment is as follows:
a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth for 1-2 times by using acetone, ethanol and deionized water respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1-1.2, performing electrodeposition tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning, and drying to obtain the carbon cloth with the tungsten oxide seed layer;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: and (2) uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tube furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tube furnace, controlling the upstream temperature of the tube furnace to be 280-300 ℃ and the downstream temperature of the tube furnace to be 750-850 ℃ under the protection of argon gas, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, ultrasonic cleaning is performed for 10min each time in step 1.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in step 2, the sodium tungstate is sodium tungstate dihydrate, the concentration of the aqueous hydrogen peroxide solution is 30 wt%, and the material-to-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to deionized water is 0.825 g: 0.766 ml: 200ml, adjusting the pH of the solution to 1.2 by using perchloric acid, electrodepositing tungsten oxide by adopting a three-electrode constant-pressure deposition method, setting the voltage to be minus 0.7V by taking the carbon cloth processed in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, wherein the deposition time is 400 seconds, the high-temperature treatment temperature after electrodeposition is 400-450 ℃, and the treatment time is 60-90 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, in step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the material-to-liquid ratio of sodium tungstate, oxalic acid and deionized water is 4.11 g: 3.15 ml: 200-280 ml, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 1.3, the mass ratio of the solution to the ammonium sulfate is 50: 2.
according to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, in the step 4, hydrothermal reaction temperature is 180 ℃, reaction time is 16h, high-temperature annealing temperature in air is 500 ℃, and annealing time is 10 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in the step 5, the mass ratio of sodium hypophosphite to sulfur powder is 1: controlling the upstream temperature of the tubular furnace to reach 280 ℃ in 1, 80min, controlling the downstream temperature of the tubular furnace to reach 800 ℃, carrying out constant temperature reaction for 60min, and cooling to room temperature in the argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, scanning electron micrographs of the prepared carbon cloth with the tungsten oxide seed layer are shown in fig. 2, fig. 3 and fig. 4, it can be seen from fig. 2 and fig. 3 that the tungsten oxide nanowires are uniformly distributed on the carbon cloth, and it can be seen from fig. 4 that the diameter of the tungsten oxide nanowires is about 70 nm.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, the prepared carbon cloth with the tungsten oxide seed layer has a large specific surface area and many active sites.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, scanning electron micrographs of the prepared phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode are shown in fig. 5 and 6, and compared with fig. 3 and 4, the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode maintains the original nanowire structure, and the nanowires have basically the same size. Nevertheless, in the case of simultaneous phosphating and sulfurization, adjacent nanowires slightly fuse together or are connected to each other.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, transmission electron microscope photographs of the prepared phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode are shown in fig. 7 and 8, and it can be seen from fig. 7 that the surface of the nanowire has a porous structure, the exposure of active sites is increased in geometric progression, and meanwhile, the edge of the nanowire has an obvious core-shell structure as observed by a transmission electron microscope. As shown in FIG. 8, the lattice spacing of the inner layer is about 0.365nm and coincides with the (200) plane of tungsten oxide (JCPD Sno.227-1323), and the lattice spacing of the outer layer is about 0.266nm and coincides with the (101) plane of tungsten sulfide (JCPD Sno.08-0237).
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, an EDS energy spectrum of the prepared phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is shown in fig. 9, an EDX element mapping chart shows that W, S, P, O elements are uniformly distributed in the whole material, and the EDX further proves that the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode has a porous structure.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, an XRD curve of the prepared phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is shown in fig. 10, and as seen from fig. 10, a characteristic peak of tungsten oxide is obvious, which proves the existence of tungsten oxide, but a diffraction peak of tungsten sulfide may not be obvious because the diffraction peak position of tungsten sulfide overlaps with tungsten oxide.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, a raman spectrum of the prepared phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is shown in fig. 11, and the existence of a core-shell structure can be proved from fig. 11. In the spectrum, 353cm-1And 421cm-1The lattice vibration of (A) is caused by E12g (in-plane) and A1g (out-of-plane) modes of lattice vibration in tungsten sulfide, the presence of which indicates the formation of tungsten sulfide, 700cm-1And 820cm-1The characteristic peak is derived from WO3The presence of tungsten oxide was confirmed by the lattice vibration of (2).
The second embodiment is as follows:
the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the preparation method according to the specific embodimentCurrent density of 10mAcm-2The overpotential in this case was 89 mV.
In the flexible array electrode of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire, a linear sweep voltammetry test method is performed, the voltage setting range is 0 to-1V, the current is set to 5mV, and the test result is shown in fig. 12, and it can be seen from fig. 12 that the flexible array electrode of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire has excellent electrochemical performance and the current density is 10mAcm-2The overpotential at that time was 89mV, which represents the difference between the electrode potential at which the electrode reaction deviated from equilibrium and the equilibrium potential of this electrode reaction, with a smaller overpotential indicating that the reaction is more likely to occur.
In the flexible array electrode of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire, electrochemical tafel slope calculation is performed, and the result obtained by converting a linear scanning voltammetry curve is shown in fig. 13, where the tafel slope of the flexible array electrode of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire is 79 mddec-1The Tafel slope is reduced by 88mVdec compared with tungsten sulfide @ tungsten oxide-1The electro-catalysis performance of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is improved by doping phosphorus atoms.
The phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment is compared with a cycle performance test, 1000 cycles of CV test are performed on an electrode material, a linear scanning voltammetry test is performed again, and the test result is shown in FIG. 14, as can be seen from FIG. 14, the 1 st cycle of CV and the 1000 th cycle of CV of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode are compared with each other, the linear scanning voltammetry curves are basically overlapped, and obvious electrochemical stability is displayed. The phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode shows excellent long-term durability in a 0.5M sulfuric acid solution.
The third concrete implementation mode:
a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth for 1-2 times by using acetone, ethanol and deionized water respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1-1.2, performing electrodeposition tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning, and drying to obtain the carbon cloth with the tungsten oxide seed layer;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: and (2) uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tube furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tube furnace, controlling the upstream temperature of the tube furnace to be 280-300 ℃ and the downstream temperature of the tube furnace to be 750-850 ℃ under the protection of argon gas, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
The fourth concrete implementation mode:
according to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode described in the third specific embodiment, in the step 1, ultrasonic cleaning is performed for 10min each time.
The fifth concrete implementation mode:
according to a third specific embodiment, in the step 2, the sodium tungstate is sodium tungstate dihydrate, the concentration of the aqueous hydrogen peroxide solution is 30 wt%, and the material-to-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to the deionized water is 0.8-1.0 g: 0.7-1 ml: 180-220 ml, adjusting the pH value of the solution to 1.2 by using perchloric acid, electrodepositing tungsten oxide by adopting a three-electrode constant-pressure deposition method, setting the voltage to be-0.7V by taking the carbon cloth processed in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, setting the deposition time to be 400 seconds, setting the high-temperature treatment temperature after electrodeposition to be 400-450 ℃ and setting the treatment time to be 60-90 min.
The sixth specific implementation mode:
according to a third specific embodiment, in the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, the feed-to-liquid ratio of sodium tungstate, aqueous hydrogen peroxide and deionized water in the step 2 is 0.825 g: 0.776 ml: 200ml, the high-temperature treatment temperature after electrodeposition is 400 ℃, and the treatment time is 60 min.
The seventh embodiment:
according to a third specific embodiment, in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the ratio of sodium tungstate to oxalic acid to deionized water is 4-5 g: 3-4 g: 200-280 ml, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 1-3, wherein the mass ratio of the solution to the ammonium sulfate is 50-60: 2 to 5.
The specific implementation mode is eight:
according to a third specific embodiment, in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the ratio of sodium tungstate to oxalic acid to deionized water is 4.11 g: 3.15 g: 250ml, and the volume ratio of the solution to the concentrated nitric acid is 1000: 1.3, the mass ratio of the solution to the ammonium sulfate is 50: 2.
the specific implementation method nine:
according to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, in the step 4, the hydrothermal reaction temperature is 180 ℃, the reaction time is 16 hours, the high-temperature annealing temperature in air is 500 ℃, and the annealing time is 8-10 min.
The detailed implementation mode is ten:
according to the third specific embodiment, in the step 5, the mass ratio of sodium hypophosphite to sulfur powder is 1-3: and (3) controlling the upstream temperature of the tubular furnace to reach 280 ℃ and the downstream temperature of the tubular furnace to reach 800 ℃ in 80-90 min, reacting at a constant temperature for 60-70 min, and cooling to room temperature in an argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
The concrete implementation mode eleven:
according to the third specific embodiment, the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is prepared by the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, and the current density is 10mAcm-2The overpotential in this case was 89 mV.
The specific implementation mode twelve:
a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth with acetone, ethanol and deionized water for 2 times respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1.2, performing electrodeposition of tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning and drying to obtain the carbon cloth with the tungsten oxide seed layer;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: and (2) uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tubular furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tubular furnace, controlling the upstream temperature of the tubular furnace to be 300 ℃ and the downstream temperature of the tubular furnace to be 850 ℃ under the protection of argon, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, ultrasonic cleaning is performed for 10min each time in step 1.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in step 2, the sodium tungstate is sodium tungstate dihydrate, the concentration of the aqueous hydrogen peroxide solution is 30 wt%, and the material-to-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to deionized water is 0.8 g: 0.7 ml: 200ml, adjusting the pH value of the solution to 1.2 by perchloric acid, adopting a three-electrode constant-pressure deposition method for electrodepositing tungsten oxide, taking the carbon cloth processed in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, setting the voltage to be-0.7V, setting the deposition time to be 400 seconds, setting the high-temperature treatment temperature after electrodeposition to be 450 ℃ and setting the treatment time to be 90 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the material-to-liquid ratio of sodium tungstate, oxalic acid and deionized water is 4 g: 2.5 g: 250ml, and the volume ratio of the solution to the concentrated nitric acid is 1000: 1, the mass ratio of the solution to the ammonium sulfate is 50: 3.
according to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, in the step 4, hydrothermal reaction temperature is 180 ℃, reaction time is 16h, high-temperature annealing temperature in air is 500 ℃, and annealing time is 10 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in the step 5, the mass ratio of sodium hypophosphite to sulfur powder is 1: and 2, controlling the upstream temperature of the tubular furnace to reach 280 ℃ in 90min, controlling the downstream temperature of the tubular furnace to reach 800 ℃, carrying out constant temperature reaction for 70min, and cooling to room temperature in the argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
According to the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, the porous nanowire array not only increases the surface area of a material and exposes more active sites, but also enables the structure-induced super-hydrophobic surface to quickly release bubbles generated on the surface of the electrode, so that the mass transport in the catalysis process related to gas evolution is promoted, and the carbon fiber cloth is used as a carrier, so that the specific surface (shell) nanostructure has excellent catalytic performance and long-term stability in the aspects of porosity, surface area and the like.
The specific implementation mode is thirteen:
a preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth with acetone, ethanol and deionized water for 2 times respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1.2, performing electrodeposition of tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning and drying to obtain the carbon cloth with the tungsten oxide seed layer;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: and (2) uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tubular furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tubular furnace, controlling the upstream temperature of the tubular furnace to be 300 ℃ and the downstream temperature of the tubular furnace to be 850 ℃ under the protection of argon, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, ultrasonic cleaning is performed for 10min each time in step 1.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in step 2, the sodium tungstate is sodium tungstate dihydrate, the concentration of the aqueous hydrogen peroxide solution is 30 wt%, and the material-to-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to deionized water is 1.0 g: 1.2 ml: 200ml, adjusting the pH value of the solution to 1.2 by perchloric acid, adopting a three-electrode constant-pressure deposition method for tungsten oxide electrodeposition, taking the carbon cloth treated in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, setting the voltage to be-0.7V, setting the deposition time to be 400 seconds, setting the high-temperature treatment temperature after electrodeposition to be 450 ℃ and setting the treatment time to be 80 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode in the embodiment, in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the ratio of sodium tungstate to oxalic acid to deionized water is 5 g: 5 ml: 280ml, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 3, the mass ratio of the solution to the ammonium sulfate is 60: 5.
according to the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, in the step 4, hydrothermal reaction temperature is 180 ℃, reaction time is 16h, high-temperature annealing temperature in air is 500 ℃, and annealing time is 10 min.
In the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to the embodiment, in the step 5, the mass ratio of sodium hypophosphite to sulfur powder is 3: and 2, controlling the upstream temperature of the tubular furnace to reach 280 ℃ in 90min, controlling the downstream temperature of the tubular furnace to reach 800 ℃, carrying out constant temperature reaction for 70min, and cooling to room temperature in the argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
According to the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode, the porous nanowire array not only increases the surface area of a material and exposes more active sites, but also enables the structure-induced super-hydrophobic surface to quickly release bubbles generated on the surface of the electrode, so that the mass transport in the catalysis process related to gas evolution is promoted, and the carbon fiber cloth is used as a carrier, so that the specific surface (shell) nanostructure has excellent catalytic performance and long-term stability in the aspects of porosity, surface area and the like.

Claims (6)

1. A preparation method of a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode is characterized by comprising the following steps: the method comprises the following steps:
step 1, pretreatment of carbon cloth: ultrasonically cleaning the carbon cloth for 1-2 times by using acetone, ethanol and deionized water respectively for later use;
step 2, preparing the carbon cloth with the tungsten oxide seed layer: dissolving sodium tungstate and aqueous hydrogen peroxide in deionized water according to a certain feed-liquid ratio, adjusting the pH of the solution to 1-1.2, performing electrodeposition tungsten oxide on the carbon cloth treated in the step 1 in the solution, performing high-temperature treatment, cleaning, and drying to obtain the carbon cloth with the tungsten oxide seed layer;
in the step 2, the sodium tungstate is sodium tungstate dihydrate, the concentration of the aqueous hydrogen peroxide solution is 30 wt%, and the feed-liquid ratio of the sodium tungstate to the aqueous hydrogen peroxide solution to the deionized water is 0.8-1.0 g: 0.7-1 mL: 180-220 mL, adjusting the pH value of the solution to 1.2 by using perchloric acid, adopting a three-electrode constant-pressure deposition method for the electro-deposition of tungsten oxide, setting the voltage to be-0.7V by taking the carbon cloth treated in the step 1 as a working electrode, a platinum sheet as a counter electrode and silver/silver chloride as a reference electrode, setting the deposition time to be 400 seconds, setting the high-temperature treatment temperature to be 400-450 ℃ after electro-deposition, and setting the treatment time to be 60-90 min;
step 3, preparing a tungsten oxide nanowire hydrothermal reaction solution: dissolving sodium tungstate and acetic acid in deionized water according to a certain feed-liquid ratio, adding a certain volume of concentrated nitric acid into the completely dissolved solution, continuously stirring until the solution is clear, adding a certain mass of ammonium sulfate, and uniformly stirring to obtain a tungsten oxide nanowire hydrothermal reaction solution for later use;
in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the feed-liquid ratio of sodium tungstate to oxalic acid to deionized water is 4-5 g: 3-4 g: 200-280 mL, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 1-3, wherein the mass ratio of the solution to the ammonium sulfate is 50-60: 2-5;
step 4, preparing the tungsten oxide nanowire array: adding the tungsten oxide nanowire hydrothermal reaction solution obtained in the step (3) into a high-pressure reaction kettle, placing the carbon cloth with the tungsten oxide seed layer into the high-pressure reaction kettle for hydrothermal reaction, taking out the carbon cloth after the reaction is finished, cleaning the carbon cloth with deionized water, drying the carbon cloth in a muffle furnace, and then annealing the carbon cloth at a high temperature in the air to obtain a tungsten oxide nanowire array;
in the step 4, annealing at a high temperature of 500 ℃ in air for 8-10 min;
the hydrothermal reaction temperature in the step 4 is 180 ℃, and the reaction time is 16 h;
step 5, preparing the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode: uniformly mixing sodium hypophosphite and sulfur powder according to a certain mass ratio, placing the mixture at the upstream of a double-temperature-zone tube furnace, placing the tungsten oxide nanowire array prepared in the step (4) at the downstream of the double-temperature-zone tube furnace, controlling the upstream temperature of the tube furnace to be 280-300 ℃ and the downstream temperature of the tube furnace to be 750-850 ℃ under the protection of argon gas, carrying out constant-temperature reaction for a certain time, and cooling to room temperature to obtain a phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode;
in the step 5, the mass ratio of the sodium hypophosphite to the sulfur powder is 1-3: 1 to 2.
2. The preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to claim 1, characterized in that: in the step 1, ultrasonic cleaning is carried out for 10min each time.
3. The preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to claim 1, characterized in that: the feed-liquid ratio of the sodium tungstate, the aqueous hydrogen peroxide solution and the deionized water in the step 2 is 0.825 g: 0.776 mL: 200mL, the high-temperature treatment temperature after electrodeposition is 400 ℃, and the treatment time is 60 min.
4. The preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to claim 1, characterized in that: in the step 3, sodium tungstate is sodium tungstate dihydrate, the concentration of acetic acid is 36-38 wt%, and the feed-liquid ratio of sodium tungstate to oxalic acid to deionized water is 4.11 g: 3.15 mL: 250mL, wherein the volume ratio of the solution to the concentrated nitric acid is 1000: 1.3, the mass ratio of the solution to the ammonium sulfate is 50: 2.
5. the preparation method of the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode according to claim 1, characterized in that: and (5) controlling the upstream temperature of the tubular furnace to reach 280 ℃ in 80-90 min, controlling the downstream temperature of the tubular furnace to reach 800 ℃, carrying out constant temperature reaction for 60-70 min, and cooling to room temperature in the argon gas atmosphere to obtain the phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode.
6. A phosphorus-doped tungsten sulfide @ tungsten oxide porous core-shell nanowire flexible array electrode prepared by the preparation method of any one of claims 1 to 5 is characterized in that: the current density is 10mA cm-2The overpotential in this case was 89 mV.
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