CN110408953A - A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide and preparation method thereof - Google Patents
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide and preparation method thereof Download PDFInfo
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Abstract
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide and preparation method thereof, it belongs to electro catalytic electrode material preparation method field.After present invention preparation has the carbon cloth of tungsten oxide seed layer, by sodium tungstate, acetic acid is dissolved in deionized water, solution after being completely dissolved adds concentrated nitric acid, continue stirring to solution to clarify, then ammonium sulfate is added, after mixing evenly, it obtains tungsten oxide nano hydro-thermal reaction solution and is placed in autoclave to carry out hydro-thermal reaction, after mixing by sodium hypophosphite and sulphur powder, it is placed in the upstream of double temperature-area tubular furnaces, the tungsten oxide nanometer linear array of preparation is placed in the downstream of double temperature-area tubular furnaces, in the protection of argon gas, the upstream temperature for controlling tube furnace is 280~300 DEG C, the downstream temperature of tube furnace is 750~850 DEG C, isothermal reaction obtains the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide after a certain period of time.Electrochemical performance of the present invention.
Description
Technical field
The invention belongs to electro catalytic electrode material preparation method fields；More particularly to a kind of phosphorus doping tungsten sulfide@tungsten oxide
Porous core-shell nano line flexible array electrode and preparation method thereof.
Background technique
Renewable green energy resource has become research hotspot in recent years.Hydrogen is considered as that a kind of clean energy resource of environmental protection carries
Body.Electro-chemical water decomposing hydrogen-production is a kind of cleaning, reproducible method instead of fossil fuel.In recent years, water-splitting hydrogen manufacturing is anti-
It answers (HER) hydrogen manufacturing to obtain extensive concern, and is likely to become the main method of hydrogen manufacturing.This depends on efficient elctro-catalyst
Design and synthesis.Currently, platinum base metal and platinum base alloy are most effective catalyst.Unfortunately, the shortage of these noble metals
Their development in terms of electrolysis water are seriously constrained at high price.It is urged therefore, it is necessary to design a kind of low cost and high performance electricity
Agent substitutes noble metal as catalyst.
Transient metal sulfide (TransitionMetalDichalcogenides, TMDs), as molybdenum sulfide, selenizing molybdenum,
Tungsten sulfide, tungsten selenide etc., it is considered to be the catalyst with wide application prospect.Especially TMDs develops reaction with very to hydrogen
Strong edge active and stability.In all TMDs, tungsten sulfide is excellent because of its high surface area and potential a large amount of active sites etc.
It is anisotropic can and be concerned.Currently, people can be carried out a large amount of research to the electrocatalysis for improving tungsten sulfide.In order to increase work
The quantity in property site, enhances the intrinsic activity of active site, and researchers have done a large amount of work, including Heteroatom doping, changes
Become nanostructure, Surface Engineering, interface engineering, nano-sized carbon hydridization etc..However, due to the exposure of active site, electric charge transfer and
The HER activity of the disadvantages of mass transit, tungsten sulfide are not able to satisfy business demand still.The mechanism for improving its catalytic activity is still unclear
Chu.
Tungsten sulfide (WS2) it is used as a kind of transient metal sulfide, there is preferable catalytic, luminescence generated by light and visible light to inhale
Receive etc. performances, be widely used in light emitting diode, solar battery, fluorescent material, lithium ion battery, superconductor, photocatalysis and
The fields such as electrochemical cell.And foreign atom is adulterated in tungsten sulfide can cause electronic perturbation, and then influence its intrinsic catalysis
Performance.
Summary of the invention
It is an object of the present invention to provide a kind of porous core-shell nano line of phosphorus doping tungsten sulfide@tungsten oxide that catalytic performance is high is soft
Property array electrode and preparation method thereof.
The invention is realized by the following technical scheme:
A kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, including it is as follows
Step:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 1~2 time respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, hydrogen peroxide is water-soluble
Liquid is dissolved in deionized water, and the pH for adjusting solution is 1~1.2, and the carbon cloth that step 1 is handled well carries out electro-deposition oxygen in the solution
Change tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved according to certain solid-liquid ratio
In ionized water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, is then added one
Determine the ammonium sulfate of quality, after mixing evenly, obtains tungsten oxide nano hydro-thermal reaction solution, for use；
Step 4 prepares tungsten oxide nanometer linear array: the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained is added
In autoclave, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, after reaction
It takes out, is cleaned with deionized water, dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: according to certain mass
Than the upstream that sodium hypophosphite and sulphur powder after mixing, are placed in double temperature-area tubular furnaces, tungsten oxide nanometer prepared by step 4
Linear array is placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 280~300 DEG C, pipe
The downstream temperature of formula furnace is 750~850 DEG C, and isothermal reaction after a certain period of time, is cooled to room temperature, and obtains phosphorus doping tungsten sulfide@oxygen
Change the porous core-shell nano line flexible array electrode of tungsten.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method is cleaned by ultrasonic 10min in step 1 every time.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, sodium tungstate described in step 2 are Disodium tungstate (Na2WO4) dihydrate, and the concentration of the aqueous hydrogen peroxide solution is 30wt%, described
Sodium tungstate, aqueous hydrogen peroxide solution and deionized water solid-liquid ratio be 0.8~1.0g:0.7~1ml:180~220ml, with height
The pH that chloric acid adjusts solution is 1.2, the method that electro deposition oxidation tungsten uses three electrode constant voltages deposition, the carbon handled well with step 1
Cloth is used as to electrode, silver/silver chlorate as working electrode, platinized platinum as reference electrode, and voltage is set as -0.7V, sedimentation time
It is 400 seconds, high-temperature process temperature is 400~450 DEG C after electro-deposition, handles 60~90min of time.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
The solid-liquid ratio of method, sodium tungstate described in step 2, aqueous hydrogen peroxide solution and deionized water is 0.825g:0.776ml:
200ml, high-temperature process temperature is 400 DEG C after electro-deposition, handles time 60min.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, the sodium tungstate, oxalic acid and
The solid-liquid ratio of deionized water is 4~5g:3~5g:200~280ml, and the volume ratio of the solution and the concentrated nitric acid is
The mass ratio of 1000:1~3, the solution and the ammonium sulfate is 50~60:2~5.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, the sodium tungstate, oxalic acid and
The solid-liquid ratio of deionized water is 4.11g:3.15g:250ml, and the volume ratio of the solution and the concentrated nitric acid is 1000:
1.3, the mass ratio of the solution and the ammonium sulfate is 50:2.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, 180 DEG C of hydrothermal temperature, reaction time 16h in step 4,500 DEG C of high temperature anneal temperature in air, annealing time 8~
10min。
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, the mass ratio of sodium hypophosphite and sulphur powder is 1~3:1~2 in step 5, and the upstream temperature of 80~90min control tube furnace reaches
To 280 DEG C, the downstream temperature of tube furnace reaches 800 DEG C, after 60~70min of isothermal reaction, is cooled in the atmosphere of argon gas
Room temperature obtains the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide tungsten oxide of method preparation, current density 10mAcm-2When
Overpotential be 89mV.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method improves the catalytic activity of transient metal sulfide by doping.Meanwhile the modification of nanostructure and the adjustment of chemical component are
Develop the key of effective base metal evolving hydrogen reaction catalyst.And carbon cloth not only has good as a kind of flexible substrates
Good mechanical performance, it may have excellent electronic conductivity is applied in electro catalytic electrode material and is expected to realize electronics
Quickly conduction and the effect for inhibiting material structure to change, to realize preferable electrocatalysis characteristic.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, phosphorus atoms doping play an important role to the property of tungsten sulfide, and phosphorus atoms doping improves reaction by forming External Defect
Activity and conductivity.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, porous nano linear array not only increases the surface area of material and the active site that exposure is more positive, and induces structure
The bubble that generates of super thin gas meter face quick release electrode surface, thus the matter in the related catalytic process that promotes to develop with gas
Amount transports.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
Method, using carbon cloth as carrier so that specific surface (shell) nanostructure porosity, in terms of all have it is excellent
Catalytic performance and long-time stability.
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
The electrode of method preparation, shows excellent chemical property, current density 10mAcm in HER-2When overpotential be
89mV, Tafel slope 79mVde-1。
A kind of preparation side of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
The electrode of method preparation, has significant long-term durability, and catalytic activity does not decay significantly after 1000 circle CV.
The present invention provides new thinking for the development of advanced electro-catalysis soap-free emulsion polymeization shell core composite material array.
Detailed description of the invention
Fig. 1 is a kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the present invention
The process flow chart of preparation method；
Fig. 2 is 3000 times of SEM photograph of the carbon cloth with tungsten oxide seed layer of one method of specific embodiment preparation；
Fig. 3 is 5000 times of SEM photograph of the carbon cloth with tungsten oxide seed layer of one method of specific embodiment preparation；
Fig. 4 is that 90000 times of SEM of the carbon cloth with tungsten oxide seed layer of one method of specific embodiment preparation shines
Piece；
Fig. 5 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
5000 times of SEM photograph of column electrode；
Fig. 6 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
80000 times of SEM photograph of column electrode；
Fig. 7 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
50000 times of transmission electron microscope photo of column electrode；
Fig. 8 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
400000 times of transmission electron microscope photo of column electrode；
Fig. 9 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
The EDX map of column electrode；
Figure 10 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
The XRD spectra of column electrode；
Figure 11 is the porous core-shell nano line flexibility battle array of phosphorus doping tungsten sulfide@tungsten oxide of one method of specific embodiment preparation
The Raman spectrogram of column electrode；
Figure 12 is a kind of porous core-shell nano line flexible array electricity of phosphorus doping tungsten sulfide@tungsten oxide in specific embodiment two
The linear sweep voltammetry figure of pole；
Figure 13 is one of the specific embodiment two porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide
The Ta Feier electrochemistry spectrogram of electrode；
Figure 14 is one of the specific embodiment two porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide
The electrochemically stable linearity curve of electrode.
Specific embodiment
Specific embodiment 1:
A kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, including it is as follows
Step:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 1~2 time respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, hydrogen peroxide is water-soluble
Liquid is dissolved in deionized water, and the pH for adjusting solution is 1~1.2, and the carbon cloth that step 1 is handled well carries out electro-deposition oxygen in the solution
Change tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved according to certain solid-liquid ratio
In ionized water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, is then added one
Determine the ammonium sulfate of quality, after mixing evenly, obtains tungsten oxide nano hydro-thermal reaction solution, for use；
Step 4 prepares tungsten oxide nanometer linear array: the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained is added
In autoclave, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, after reaction
It takes out, is cleaned with deionized water, dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: according to certain mass
Than the upstream that sodium hypophosphite and sulphur powder after mixing, are placed in double temperature-area tubular furnaces, tungsten oxide nanometer prepared by step 4
Linear array is placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 280~300 DEG C, pipe
The downstream temperature of formula furnace is 750~850 DEG C, and isothermal reaction after a certain period of time, is cooled to room temperature, and obtains phosphorus doping tungsten sulfide@oxygen
Change the porous core-shell nano line flexible array electrode of tungsten.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method is cleaned by ultrasonic 10min in step 1 every time.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate described in step 2 are Disodium tungstate (Na2WO4) dihydrate, and the concentration of the aqueous hydrogen peroxide solution is 30wt%,
The solid-liquid ratio of the sodium tungstate, aqueous hydrogen peroxide solution and deionized water is 0.825g:0.766ml:200ml, uses perchloric acid
The pH for adjusting solution is 1.2, and the method that electro deposition oxidation tungsten uses three electrode constant voltages deposition is made with the carbon cloth that step 1 is handled well
It is used as to electrode, silver/silver chlorate for working electrode, platinized platinum as reference electrode, voltage is set as -0.7V, sedimentation time 400
Second, high-temperature process temperature is 400~450 DEG C after electro-deposition, handles 60~90min of time.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, the sodium tungstate, grass
Acid and the solid-liquid ratio of deionized water are 4.11g:3.15ml:200~280ml, the volume of the solution and the concentrated nitric acid
Than for 1000:1.3, the mass ratio of the solution and the ammonium sulfate is 50:2.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, 180 DEG C of hydrothermal temperature, reaction time 16h in step 4,500 DEG C of high temperature anneal temperature in air, when annealing
Between 10min.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, the mass ratio of sodium hypophosphite and sulphur powder is 1:1 in step 5, and the upstream temperature of 80min control tube furnace reaches 280
DEG C, the downstream temperature of tube furnace reaches 800 DEG C, after isothermal reaction 60min, is cooled to room temperature, obtains in the atmosphere of argon gas
The porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
The stereoscan photograph of Preparation Method, the carbon cloth with tungsten oxide seed layer of preparation is as shown in Figure 2, Figure 3, Figure 4, Cong Tucong Fig. 2
With Fig. 3 it can be seen that tungsten oxide nano is evenly distributed on carbon cloth, the diameter of tungsten oxide nano is about as can be seen from Figure 4
For 70nm.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
The carbon cloth with tungsten oxide seed layer of Preparation Method, preparation has big specific surface area, and active site is more.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, porous core-shell nano line flexible array electrode stereoscan photograph such as Fig. 5 of phosphorus doping tungsten sulfide@tungsten oxide of preparation,
Shown in Fig. 6, compared with Fig. 3 and Fig. 4, the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide maintains original
The size of some nanowire structures, nano wire is essentially identical.Nevertheless, at the same time phosphatization and vulcanization in the case where, it is adjacent
Nano wire can be slightly fused together, or be connected with each other.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, porous core-shell nano line flexible array electrode transmissive electromicroscopic photograph such as Fig. 7 of phosphorus doping tungsten sulfide@tungsten oxide of preparation,
Shown in Fig. 8, it can be seen that nanowire surface has porous structure from Fig. 7, active site exposed amount increases in geometric progression,
Meanwhile transmission electron microscope observing has apparent core-shell structure to nanowire edge.Shown in Fig. 8, internal layer spacing of lattice is about
0.365nm matches with (200) crystal face of tungsten oxide (JCPD Sno.227-1323), and outer layer spacing of lattice is about 0.266nm,
It matches with (101) crystal face of tungsten sulfide (JCPD Sno.08-0237).
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, the porous core-shell nano line flexible array electrode EDS power spectrum of phosphorus doping tungsten sulfide@tungsten oxide of preparation as shown in figure 9,
EDX element mapping graph shows that W, S, P, O element are uniformly distributed in entire material, while EDX further demonstrates described one
The kind porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide has porous structure.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
The porous core-shell nano line flexible array electrode XRD curve of phosphorus doping tungsten sulfide@tungsten oxide of Preparation Method, preparation is as shown in Figure 10,
As seen from Figure 10, the characteristic peak of tungsten oxide is obvious, it was demonstrated that the presence of tungsten oxide, but may due to the diffraction peak of tungsten sulfide
Set it is Chong Die with tungsten oxide, so without the diffraction maximum of apparent tungsten sulfide.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
The porous core-shell nano line flexible array electrode Raman spectrum of phosphorus doping tungsten sulfide@tungsten oxide of Preparation Method, preparation is as shown in figure 11,
The presence of core-shell structure is able to demonstrate that from Figure 11.In spectrum, 353cm-1And 421cm-1The lattice vibration at place is by tungsten sulfide
Caused by the E12g (in face) and A1g (outside face) mode of middle lattice vibration, its presence shows the formation of tungsten sulfide, 700cm-1With
820cm-1The characteristic peak at place derives from WO3Lattice vibration, it was demonstrated that the presence of tungsten oxide.
Specific embodiment 2:
The porous nucleocapsid of a kind of phosphorus doping tungsten sulfide@tungsten oxide prepared according to preparation method described in specific embodiment one
Nano wire flexible array electrode, current density 10mAcm-2When overpotential be 89mV.
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment, into
Row linear sweep voltammetry method of testing, voltage set range are 0 to -1V, and electric current is set as 5mV, and test result is as shown in figure 12, from
It can be seen that the porous core-shell nano line flexible array electrode electro Chemical of a kind of phosphorus doping tungsten sulfide@tungsten oxide in Figure 12
Can be excellent, it is 10mAcm in current density-2When overpotential be 89mV, overpotential represent electrode reaction deviate balance when electrode
The difference of the equilibrium potential of current potential and this electrode reaction, lesser overpotential illustrate that reaction is easier to occur.
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment, into
Row electrochemistry Tafel slope calculates, by converting to linear sweep voltammetry curve, as a result as shown in figure 13, described one
The kind porous core-shell nano line flexible array electrode Tafel slope of phosphorus doping tungsten sulfide@tungsten oxide is 79mVdec-1, Ta Feier is oblique
Rate reduces 88mVdec compared to tungsten sulfide@tungsten oxide-1, this illustrates that the doping of phosphorus atoms improves a kind of phosphorus doping
The electrocatalysis characteristic of the porous core-shell nano line flexible array electrode of tungsten sulfide@tungsten oxide.
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment, into
Row cycle performance test and comparison re-starts linear sweep voltammetry test after carrying out 1000 circle CV tests to electrode material,
Test result is as shown in figure 14, and as can be seen from Figure 14, a kind of porous core-shell nano line of phosphorus doping tungsten sulfide@tungsten oxide is flexible
Compare before and after the circle of array electrode the 1st and the 1000th circle CV, linear sweep voltammetry curve essentially coincides, and shows apparent electrochemistry
Stability.A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide is molten in the sulfuric acid of 0.5M
Outstanding long durability is shown in liquid.
Specific embodiment 3:
A kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, including it is as follows
Step:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 1~2 time respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, hydrogen peroxide is water-soluble
Liquid is dissolved in deionized water, and the pH for adjusting solution is 1~1.2, and the carbon cloth that step 1 is handled well carries out electro-deposition oxygen in the solution
Change tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved according to certain solid-liquid ratio
In ionized water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, is then added one
Determine the ammonium sulfate of quality, after mixing evenly, obtains tungsten oxide nano hydro-thermal reaction solution, for use；
Step 4 prepares tungsten oxide nanometer linear array: the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained is added
In autoclave, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, after reaction
It takes out, is cleaned with deionized water, dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: according to certain mass
Than the upstream that sodium hypophosphite and sulphur powder after mixing, are placed in double temperature-area tubular furnaces, tungsten oxide nanometer prepared by step 4
Linear array is placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 280~300 DEG C, pipe
The downstream temperature of formula furnace is 750~850 DEG C, and isothermal reaction after a certain period of time, is cooled to room temperature, and obtains phosphorus doping tungsten sulfide@oxygen
Change the porous core-shell nano line flexible array electrode of tungsten.
Specific embodiment 4:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode is cleaned by ultrasonic 10min in step 1 every time.
Specific embodiment 5:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode, sodium tungstate described in step 2 are Disodium tungstate (Na2WO4) dihydrate, and the concentration of the aqueous hydrogen peroxide solution is
30wt%, the solid-liquid ratio of the sodium tungstate, aqueous hydrogen peroxide solution and deionized water are 0.8~1.0g:0.7~1ml:180
~220ml, the pH with perchloric acid adjustment solution is 1.2, the method that electro deposition oxidation tungsten uses three electrode constant voltages deposition, with step
1 carbon cloth handled well is used as to electrode, silver/silver chlorate as working electrode, platinized platinum as reference electrode, and voltage is set as-
0.7V, sedimentation time are 400 seconds, and high-temperature process temperature is 400~450 DEG C after electro-deposition, handle 60~90min of time.
Specific embodiment 6:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The solid-liquid ratio of the preparation method of electrode, sodium tungstate described in step 2, aqueous hydrogen peroxide solution and deionized water is 0.825g:
0.776ml:200ml, high-temperature process temperature is 400 DEG C after electro-deposition, handles time 60min.
Specific embodiment 7:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, described
The solid-liquid ratio of sodium tungstate, oxalic acid and deionized water is 4~5g:3~4g:200~280ml, the solution and the dense nitre
The volume ratio of acid is 1000:1~3, and the mass ratio of the solution and the ammonium sulfate is 50~60:2~5.
Specific embodiment 8:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, described
The solid-liquid ratio of sodium tungstate, oxalic acid and deionized water is 4.11g:3.15g:250ml, the body of the solution and the concentrated nitric acid
For product than being 1000:1.3, the mass ratio of the solution and the ammonium sulfate is 50:2.
Specific embodiment 9:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode, 180 DEG C of hydrothermal temperature, reaction time 16h in step 4, high temperature anneal temperature 500 in air
DEG C, 8~10min of annealing time.
Specific embodiment 10:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
The preparation method of electrode, the mass ratio of sodium hypophosphite and sulphur powder is 1~3:1~2 in step 5, and 80~90min controls tube furnace
Upstream temperature reach 280 DEG C, the downstream temperature of tube furnace reaches 800 DEG C, after 60~70min of isothermal reaction, in argon gas
It is cooled to room temperature in atmosphere, obtains the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
Specific embodiment 11:
A kind of porous core-shell nano line flexible array of phosphorus doping tungsten sulfide@tungsten oxide according to specific embodiment three
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of the preparation method preparation of electrode, electric current are close
Degree is 10mAcm-2When overpotential be 89mV.
Specific embodiment 12:
A kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, including it is as follows
Step:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 2 times respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, hydrogen peroxide is water-soluble
Liquid is dissolved in deionized water, and the pH for adjusting solution is 1.2, and the carbon cloth that step 1 is handled well carries out electro deposition oxidation in the solution
Tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved according to certain solid-liquid ratio
In ionized water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, is then added one
Determine the ammonium sulfate of quality, after mixing evenly, obtains tungsten oxide nano hydro-thermal reaction solution, for use；
Step 4 prepares tungsten oxide nanometer linear array: the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained is added
In autoclave, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, after reaction
It takes out, is cleaned with deionized water, dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: according to certain mass
Than the upstream that sodium hypophosphite and sulphur powder after mixing, are placed in double temperature-area tubular furnaces, tungsten oxide nanometer prepared by step 4
Linear array is placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 300 DEG C, tube furnace
Downstream temperature be 850 DEG C, isothermal reaction after a certain period of time, is cooled to room temperature, and obtains the porous core of phosphorus doping tungsten sulfide@tungsten oxide
Shell nano wire flexible array electrode.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method is cleaned by ultrasonic 10min in step 1 every time.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate described in step 2 are Disodium tungstate (Na2WO4) dihydrate, and the concentration of the aqueous hydrogen peroxide solution is 30wt%,
The solid-liquid ratio of the sodium tungstate, aqueous hydrogen peroxide solution and deionized water is 0.8g:0.7ml:200ml, is adjusted with perchloric acid
The pH of solution is 1.2, the method that electro deposition oxidation tungsten uses three electrode constant voltages deposition, using the carbon cloth that step 1 is handled well as work
Make electrode, platinized platinum is used as to electrode, silver/silver chlorate as reference electrode, voltage is set as -0.7V, and sedimentation time is 400 seconds,
High-temperature process temperature is 450 DEG C after electro-deposition, handles time 90min.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, the sodium tungstate, grass
Acid and the solid-liquid ratio of deionized water are 4g:2.5g:250ml, and the volume ratio of the solution and the concentrated nitric acid is 1000:1,
The mass ratio of the solution and the ammonium sulfate is 50:3.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, 180 DEG C of hydrothermal temperature, reaction time 16h in step 4,500 DEG C of high temperature anneal temperature in air, when annealing
Between 10min.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, the mass ratio of sodium hypophosphite and sulphur powder is 1:2 in step 5, and the upstream temperature of 90min control tube furnace reaches 280
DEG C, the downstream temperature of tube furnace reaches 800 DEG C, after isothermal reaction 70min, is cooled to room temperature, obtains in the atmosphere of argon gas
The porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of Preparation Method preparation, porous nano linear array
Not only increase the surface area of material and the active site that exposure is more positive, and the super thin fast quick-release in gas meter face for inducing structure
The bubble that pole surface of discharging generates, the mass transport so that promotion and gas develop in related catalytic process, utilizes carbon fiber
Cloth as carrier so that specific surface (shell) nanostructure porosity, in terms of all have excellent catalytic properties and
Long-time stability, a kind of phosphorus doping tungsten sulfide@tungsten oxide porous core-shell nano line flexible array electrode the 1st circle and the
Compare before and after 1000 circle CV, linear sweep voltammetry curve essentially coincides.
Specific embodiment 13:
A kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, including it is as follows
Step:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 2 times respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, hydrogen peroxide is water-soluble
Liquid is dissolved in deionized water, and the pH for adjusting solution is 1.2, and the carbon cloth that step 1 is handled well carries out electro deposition oxidation in the solution
Tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved according to certain solid-liquid ratio
In ionized water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, is then added one
Determine the ammonium sulfate of quality, after mixing evenly, obtains tungsten oxide nano hydro-thermal reaction solution, for use；
Step 4 prepares tungsten oxide nanometer linear array: the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained is added
In autoclave, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, after reaction
It takes out, is cleaned with deionized water, dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: according to certain mass
Than the upstream that sodium hypophosphite and sulphur powder after mixing, are placed in double temperature-area tubular furnaces, tungsten oxide nanometer prepared by step 4
Linear array is placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 300 DEG C, tube furnace
Downstream temperature be 850 DEG C, isothermal reaction after a certain period of time, is cooled to room temperature, and obtains the porous core of phosphorus doping tungsten sulfide@tungsten oxide
Shell nano wire flexible array electrode.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method is cleaned by ultrasonic 10min in step 1 every time.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate described in step 2 are Disodium tungstate (Na2WO4) dihydrate, and the concentration of the aqueous hydrogen peroxide solution is 30wt%,
The solid-liquid ratio of the sodium tungstate, aqueous hydrogen peroxide solution and deionized water is 1.0g:1.2ml:200ml, is adjusted with perchloric acid
The pH of solution is 1.2, the method that electro deposition oxidation tungsten uses three electrode constant voltages deposition, using the carbon cloth that step 1 is handled well as work
Make electrode, platinized platinum is used as to electrode, silver/silver chlorate as reference electrode, voltage is set as -0.7V, and sedimentation time is 400 seconds,
High-temperature process temperature is 450 DEG C after electro-deposition, handles time 80min.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, the sodium tungstate, grass
Acid and the solid-liquid ratio of deionized water are 5g:5ml:280ml, and the volume ratio of the solution and the concentrated nitric acid is 1000:3,
The mass ratio of the solution and the ammonium sulfate is 60:5.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, 180 DEG C of hydrothermal temperature, reaction time 16h in step 4,500 DEG C of high temperature anneal temperature in air, when annealing
Between 10min.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
Preparation Method, the mass ratio of sodium hypophosphite and sulphur powder is 3:2 in step 5, and the upstream temperature of 90min control tube furnace reaches 280
DEG C, the downstream temperature of tube furnace reaches 800 DEG C, after isothermal reaction 70min, is cooled to room temperature, obtains in the atmosphere of argon gas
The porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
A kind of system of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide described in present embodiment
A kind of porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide of Preparation Method preparation, porous nano linear array
Not only increase the surface area of material and the active site that exposure is more positive, and the super thin fast quick-release in gas meter face for inducing structure
The bubble that pole surface of discharging generates, the mass transport so that promotion and gas develop in related catalytic process, utilizes carbon fiber
Cloth as carrier so that specific surface (shell) nanostructure porosity, in terms of all have excellent catalytic properties and
Long-time stability, a kind of phosphorus doping tungsten sulfide@tungsten oxide porous core-shell nano line flexible array electrode the 1st circle and the
Compare before and after 1000 circle CV, linear sweep voltammetry curve essentially coincides.
Claims (9)
1. a kind of preparation method of the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide, it is characterised in that:
Include the following steps:
Step 1, carbon cloth pretreatment: carbon cloth acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 1~2 time respectively, for use；
Step 2, preparation have the carbon cloth of tungsten oxide seed layer: according to certain solid-liquid ratio that sodium tungstate, aqueous hydrogen peroxide solution is molten
In deionized water, the pH for adjusting solution is 1~1.2, and the carbon cloth that step 1 is handled well carries out electro deposition oxidation in the solution
Tungsten, then after high-temperature process, cleaning obtains the carbon cloth with tungsten oxide seed layer after drying；
Step 3, configuration tungsten oxide nano hydro-thermal reaction solution: sodium tungstate, acetic acid are dissolved in deionization according to certain solid-liquid ratio
In water, the solution after being completely dissolved adds the concentrated nitric acid of certain volume, continues stirring to solution and clarifies, certain matter is then added
The ammonium sulfate of amount obtains tungsten oxide nano hydro-thermal reaction solution, for use after mixing evenly；
Step 4 prepares tungsten oxide nanometer linear array: high pressure is added in the tungsten oxide nano hydro-thermal reaction solution that step 3 is obtained
In reaction kettle, the carbon cloth with tungsten oxide seed layer is placed in autoclave and carries out hydro-thermal reaction, is taken out after reaction,
It is cleaned with deionized water, is dried in Muffle furnace, then high annealing in air, obtain tungsten oxide nanometer linear array；
Step 5 prepares the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide: will according to certain mass ratio
Sodium hypophosphite and sulphur powder after mixing, are placed in the upstream of double temperature-area tubular furnaces, tungsten oxide nanometer linear array prepared by step 4
Column are placed in the downstream of double temperature-area tubular furnaces, and in the protection of argon gas, the upstream temperature for controlling tube furnace is 280~300 DEG C, tube furnace
Downstream temperature be 750~850 DEG C, isothermal reaction after a certain period of time, is cooled to room temperature, and obtains phosphorus doping tungsten sulfide@tungsten oxide
Porous core-shell nano line flexible array electrode.
2. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: be cleaned by ultrasonic 10min in step 1 every time.
3. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: sodium tungstate described in step 2 is Disodium tungstate (Na2WO4) dihydrate, the aqueous hydrogen peroxide solution
Concentration is 30wt%, the solid-liquid ratio of the sodium tungstate, aqueous hydrogen peroxide solution and deionized water be 0.8~1.0g:0.7~
1ml:180~220ml, the pH with perchloric acid adjustment solution is 1.2, and electro deposition oxidation tungsten uses the side of three electrode constant voltages deposition
Method, using the carbon cloth that step 1 is handled well as working electrode, platinized platinum as to electrode, silver/silver chlorate as reference electrode, voltage
It is set as -0.7V, sedimentation time is 400 seconds, and high-temperature process temperature is 400~450 DEG C after electro-deposition, the processing time 60~
90min。
4. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 3
Preparation method, it is characterised in that: the solid-liquid ratio of sodium tungstate described in step 2, aqueous hydrogen peroxide solution and deionized water is
0.825g:0.776ml:200ml, high-temperature process temperature is 400 DEG C after electro-deposition, handles time 60min.
5. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, institute
The solid-liquid ratio of sodium tungstate, oxalic acid and the deionized water stated is 4~5g:3~4g:200~280ml, the solution and described
The volume ratio of concentrated nitric acid is 1000:1~3, and the mass ratio of the solution and the ammonium sulfate is 50~60:2~5.
6. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: sodium tungstate is Disodium tungstate (Na2WO4) dihydrate in step 3, and the acetic acid concentration is 36~38wt%, institute
The solid-liquid ratio of sodium tungstate, oxalic acid and the deionized water stated is 4.11g:3.15ml:250ml, the solution and the dense nitre
The volume ratio of acid is 1000:1.3, and the mass ratio of the solution and the ammonium sulfate is 50:2.
7. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: 180 DEG C of hydrothermal temperature in step 4, reaction time 16h, in air high temperature anneal temperature
500 DEG C, 8~10min of annealing time.
8. the porous core-shell nano line flexible array electrode of a kind of phosphorus doping tungsten sulfide@tungsten oxide according to claim 1
Preparation method, it is characterised in that: the mass ratio of sodium hypophosphite and sulphur powder is 1~3:1~2,80~90min control in step 5
The upstream temperature of tube furnace reaches 280 DEG C, and the downstream temperature of tube furnace reaches 800 DEG C, after 60~70min of isothermal reaction, in argon
It is cooled to room temperature in the atmosphere of gas, obtains the porous core-shell nano line flexible array electrode of phosphorus doping tungsten sulfide@tungsten oxide.
9. a kind of porous nucleocapsid of phosphorus doping tungsten sulfide@tungsten oxide of the preparation of preparation method described in a kind of one of claim 1-8
Nano wire flexible array electrode, it is characterised in that: current density 10mAcm-2When overpotential be 89mV.
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