CN108479807A - A kind of preparation method for the stannic disulfide catalyst being used to prepare fuel cell hydrogen - Google Patents
A kind of preparation method for the stannic disulfide catalyst being used to prepare fuel cell hydrogen Download PDFInfo
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- CN108479807A CN108479807A CN201810397128.4A CN201810397128A CN108479807A CN 108479807 A CN108479807 A CN 108479807A CN 201810397128 A CN201810397128 A CN 201810397128A CN 108479807 A CN108479807 A CN 108479807A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The present invention proposes a kind of preparation method for the stannic disulfide catalyst being used to prepare fuel cell hydrogen, using modified porous organosilicon as substrate, molten metal tin and thiocarbamide react for evaporation source, the tin atom of evaporation, which preferentially enters, to be combined in the nanoaperture of organosilicon with modified group, and it is reacted with thiocarbamide and generates stannic disulfide nano particle, there is the organosilicon of stannic disulfide nano particle to immerse hydrofluoric acid load to perform etching, redeposited carbon coating layer, stannic disulfide nano particle is fixed on pore interior, obtain the carbon coating stannic disulfide nanoparticle catalyst of polymolecularity, to reduce its reuniting effect in preparation process, stannic disulfide nanoparticle catalyst is solved to reunite seriously, affect the defect of its catalytic performance.The present invention can inhibit, by organic silicon etching on surface layer, carbon source is uniformly wrapped on stannic disulfide surface at high temperature by hydrofluoric acid electrolyte to the corrosion of stannic disulfide, improve the stability of catalyst in the electrolytic solution.
Description
Technical field
The present invention relates to fuel cell industry water electrolysis hydrogen production technical fields, and in particular to one kind being used to prepare fuel cell
With the preparation method of the stannic disulfide catalyst of hydrogen.
Background technology
In order to reduce the consumption of fossil energy and solve problem of environmental pollution, there is an urgent need to develop clean renewable energies
Source.Although the characteristics of solar energy, wind energy, tide energy and geothermal energy are as clean energy resource large storage capacity, there is intermittence, it is unstable
The shortcomings of determining.It is water, clean environment firendly, and preparation method letter that Hydrogen Energy, which has combustion heat value height, about the 3 of gasoline times, combustion product,
The advantages that single.
Hydrogen powered vehicle refers to the automobile using hydrogen as main energetic as movement.The principle of hydrogen fuel cell is that hydrogen is inputted
In fuel cell, the electronics of hydrogen atom is obstructed by proton exchange membrane, and anode is transmitted to from cathode by external circuit, becomes electric energy drive
Dynamic motor.It is more demanding to hydrogen feedstock due to the particularity of hydrogen fuel cell, currently, water electrolysis hydrogen production substantially meets fuel
The requirement that battery reads hydrogen alcohol.Water electrolysis hydrogen production effectively can convert electric energy more than needed to Hydrogen Energy and store.Electrolysis water
Hydrogen producing technology has purity compared to heat chemistry hydrogen manufacturing, fossil fuel hydrogen manufacturing and the methods of hydrogen generation by biological process and photoelectrocatalysis hydrogen manufacturing
The advantages that high, pollution-free and controllability is strong will be the core technology of the following production hydrogen industry, have very high social benefit and economy
Benefit.
In two electrode system of water electrolysis hydrogen production, after device for preparing hydrogen adds additional power source, under voltage effect, electricity
With current transfer to cathode material, the hydrogen ion in electrolyte obtains electronics in cathode and is reduced into hydrogen the electronics of source cathode
Gas；According to charge balance law, the hydroxide ion in electrolyte is moved to anode material, loses and is electronically generated in electrode surface
Oxygen.In electro-catalysis hydrogen production process, need to improve the activity of catalyst for preparing hydrogen reduce hydrogen on hydrogen electrode generate it is excessively electric
Gesture.If gibbs adsorption free energy of the hydrogen atom on hydrogen electrode is smaller, hydrogen atom will be not easy to be adsorbed on hydrogen electrode, but
It is discharged if adsorption free energy is unfavorable for the hydrogen generated compared with good general.Liberation of hydrogen catalyst must make to reach good dynamic between the two
State balances, could the promotion of maximal efficiency its catalytic activity for hydrogen evolution performance, therefore, when electrolysis the selection of catalyst directly affect
It is electrolysed the main efficiency of aquatic products hydrogen.The noble metals such as Pt, Ru and oxide have high electro catalytic activity to HER and OER, but it is stored up
Measure limited, expensive, the deficiencies of stability is poor hinders its large-scale production and application.Exploitation match in excellence or beauty precious metal catalyst activity and
Sufficiently stable catalyst is particularly important.
Non-precious metal catalyst is mostly nanoscale structures phosphide and sulfide, and the size of structural unit is received between 1
Between -100 nanometer ranges of rice, since its size is already close to the coherence length of electronics, and possess huge surface area, higher
Electrolysis water activity have preferable Research Prospects in water electrolysis hydrogen production field.It includes water that nanoscale sulfide, which prepares synthetic method mainly,
Hot method and infusion process etc..Hydro-thermal method is that reaction raw materials are placed in reaction kettle, using water as reaction dissolvent, by heating, makes reaction
Environment in high temperature and pressure, reaches the condition of synthetic sample, hydro-thermal method have the advantages that it is simple to operation, as Chinese invention is special
Sharp application number 201410058603.7 discloses one step hydro thermal method synthesis nano-sheet tungsten sulfide and its application, and metal is respectively adopted
Tungsten net and thiocarbamide are tungsten source and sulphur source, and by hydro-thermal reaction, even sheet tungsten sulfide is grown on tungsten net surface.Leaching
Stain method logical is often to remove the liquid containing active material to soak all kinds of carriers, when impregnate balance after, remove remaining liq, then carry out with
The processes such as the identical drying of the precipitation method, roasting, activation post-process.Through drying, moisture evaporation is escaped, the salt of active component can be made
Class is retained on the inner surface of carrier, and the salt of these metals and metal oxide is evenly distributed in the pore of carrier, through adding
To get the carried catalyst of high degree of dispersion after thermal decomposition and activation.Such as Chinese invention patent application number 201710791372.4,
A kind of preparation method and application of carbon substrate Supported Co oxidate nano composite material are disclosed, using polymerization-dipping-pyrolysis side
Method prepares carbon substrate Supported Co oxidate nano composite material.
Stannic disulfide crystal belongs to hexagonal crystal system, is a kind of typical group IV-VI n-type semiconductor, direct band gap position
2.1802.44eV having six side CdI of stratiform2The crystal structure of type, with Covalent bonding together between atom, and between layers then
With Van der Waals force in conjunction with and form octahedral structure.Since it has weaker interlaminar action power and wider band gap, from
And it is had wide application prospects in terms of as catalyst.However two sulphur for utilizing common hydro-thermal method, infusion process to prepare
It is serious to change tin nanoparticles catalyst agglomeration, its chemical property of strong influence.It is therefore proposed that one kind being used to prepare fuel
The preparation method of the stannic disulfide catalyst of battery hydrogen, for solving the problems, such as that the reunion of stannic disulfide nano-catalyst particles has
There is highly important practical significance.
Invention content
Reunite for the stannic disulfide nanoparticle catalyst currently with hydro-thermal method, infusion process preparation serious, greatly
Affect the defect of its chemical property, the present invention proposes a kind of stannic disulfide catalyst being used to prepare fuel cell hydrogen
Preparation method greatly improves a nanometer stannic disulfide catalyst to solve the problems, such as that stannic disulfide nano-catalyst particles are reunited
Electrolysis water catalytic activity.
To solve the above problems, the present invention uses following technical scheme：A kind of two sulphur being used to prepare fuel cell hydrogen
The preparation method for changing tin catalyst using modified porous organosilicon as substrate, molten metal tin and thiocarbamide reaction, then passes through hydrogen
Fluoric acid performs etching, redeposited carbon coating layer, obtains the carbon coating stannic disulfide catalyst of polymolecularity, specific preparation process is such as
Under：
（1）Modified porous organic silicon solid material is placed in CVD reaction chambers, heat modification porous organic solid material is extremely
450-500 DEG C, CVD chamber is evacuated to 0.1-10Pa, heating metallic tin to 250-500 DEG C, heating thiocarbamide to 180-200 DEG C,
Evaporated metal tin and thiocarbamide, are passed through argon gas, and argon flow amount control keeps the temperature 1h in 2-50sccm, by chemical vapor deposition 6h, obtains
There is organic silicon composite of stannic disulfide to load；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
For 5-10%, between the temperature of hydrofluoric acid is kept in etching process is 25-40 DEG C, the organic of the stannic disulfide of surface cleaning is obtained
Silicon composite；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is passed through into vacuum drying treatment, then is placed in CVD reactions
In chamber, it is passed through methane and acetylene reaction gas, by 1100-1200 DEG C of high annealing resolution process, cooled to room temperature,
Obtain the carbon coating stannic disulfide catalyst of polymolecularity.
Preferably, the modified porous organosilicon is the cross-linked polymer of polysiloxanes, silicones and silicon rubber, described to change
Property porous organic include amino, polyethers, alcoholic extract hydroxyl group, phenolic group be modified in one kind, aperture 20-100nm, the ratio table of catalyst
Area is 100-1000m2/g。
Preferably, the CVD chamber holding vacuumizes 3-5 hours, leads to argon gas 5-8 hours, and oxygen is discharged, and control gas is dense
Degree is less than 0.001ppm.
Preferably, the heating rate of the heating thiocarbamide is controlled in 5-15 DEG C/min.
Preferably, the evaporation rate of the thiocarbamide is controlled in 1-30mg/h.
Preferably, the stannic disulfide grain diameter is 20-80nm.
Preferably, step（3）Described in vacuum drying treatment be vacuum degree be maintained at 0.5-10kPa, drying temperature is
200-500℃。
Preferably, the gas concentration of the methane and acetylene is respectively 3-8% and 5-10%.
Preferably, the step（3）In the high-temperature process time be 20-50 minutes.
Reunite for the stannic disulfide nanoparticle catalyst prepared currently with the methods of hydro-thermal method, infusion process serious,
Its electro catalytic activity of strong influence, in consideration of it, the present invention proposes a kind of stannic disulfide being used to prepare fuel cell hydrogen
The preparation method of catalyst is loaded into reaction cavity, in 450-500 using molten metal tin and thiocarbamide as evaporation source using argon gas
CVD vacuum depositions are carried out at DEG C, deposition substrate is modified porous organosilicon, keeps the temperature 1h after depositing 6h, load is had stannic disulfide
Organosilicon immerse hydrofluoric acid perform etching, be eventually adding carbon source carry out the high temperature anneal, obtain the carbon coating of polymolecularity
Stannic disulfide catalyst.Being preferentially entered by the tin atom of evaporation in the present invention has in the nanoaperture of organosilicon with modified porous
Modified group combines in machine silicon, and is reacted with thiocarbamide and generate stannic disulfide and be fixed on pore interior, is being prepared to reduce it
Reuniting effect in the process.It is performed etching in addition, thering is the organosilicon of stannic disulfide to immerse hydrofluoric acid load, it will by hydrofluoric acid
Organic silicon etching on surface layer, carbon source are uniformly wrapped on stannic disulfide surface at high temperature, it is suppressed that electrolyte is to stannic disulfide
Corrosion.The present invention solves traditional stannic disulfide nanocatalyst and is unevenly distributed in preparation process, serious problem of reuniting,
And the stability of catalyst in the electrolytic solution is improved, is lived to improve the catalysis of stannic disulfide nanocatalyst electrolysis water
Property.It is well suited for continuing hydrogen supply for fuel cell.
The present invention is subjected to pattern SEM inspections with the stannic disulfide nanoparticle catalyst prepared using hydro-thermal method, infusion process
It surveys, and uses and be tested for the property using three electrode test systems on electrochemical workstation CHI660E, test environment 0.5M
H2SO4Under the conditions of, it is 5mA cm to test Tafel slope and current density-2Overpotential record is as shown in table 1.
Table 1：
The present invention provides a kind of preparation method for the stannic disulfide catalyst being used to prepare fuel cell hydrogen, with prior art phase
Than the feature and excellent effect protruded is：
1, the present invention is reacted as substrate, molten metal tin and thiocarbamide for evaporation source using modified porous organosilicon, the tin of evaporation
Atoms enter in the nanoaperture of organosilicon to be combined with modified group, and is reacted with thiocarbamide and generated stannic disulfide nanometer
Load is had the organosilicon of stannic disulfide nano particle to immerse hydrofluoric acid and performed etching by grain, redeposited carbon coating layer, by curing
Tin nanoparticles are fixed on pore interior, the carbon coating stannic disulfide nanoparticle catalyst of polymolecularity are obtained, to reduce
Its reuniting effect in preparation process improves nano-particle dispersibility, solves common hydro-thermal method, prepared by infusion process
Stannic disulfide nanoparticle catalyst is reunited serious, the strong influence defect of its chemical property.
2, the present invention is by by hydrofluoric acid, by organic silicon etching on surface layer, carbon source is uniformly wrapped on stannic disulfide at high temperature
Surface can inhibit electrolyte to the corrosion of stannic disulfide, improve the stability of catalyst in the electrolytic solution.
3, stannic disulfide nanoparticle catalyst prepared by preparation method of the present invention is reliable and stable, and process is simple, dispersibility
Well, the potentiality with large-scale industrial production, improve stannic disulfide nanoparticle catalyst catalytic activity, are conducive to water
The efficient utilization of resource.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）It is 20nm by aperture, the specific surface area of catalyst is 500m2Amino modified porous organic polysiloxanes, the silicon of/g
The cross-linked polymer solid material of resin and silicon rubber is placed in CVD reaction chambers, heat modification porous organic solid material
To 480 DEG C, CVD chamber is evacuated to 0.1Pa, and the CVD chamber holding vacuumizes 5 hours, leads to argon gas 5 hours, oxygen is discharged,
It controls gas concentration and is less than 0.001ppm, heating metallic tin is to 290 DEG C, and to 200 DEG C, heat temperature raising speed control exists heating thiocarbamide
15 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate control of thiocarbamide are passed through argon gas, argon flow amount control exists in 1mg/h
2sccm keeps the temperature 1h by chemical vapor deposition 6h, obtains load to have grain size being the organosilicon composite wood of the stannic disulfide of 80nm
Material；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
It is 8%, between the temperature of holding hydrofluoric acid is 25-40 DEG C in etching process, the organosilicon for obtaining the stannic disulfide of surface cleaning is multiple
Condensation material；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 0.5kPa, dry temperature by vacuum degree
Degree is 300 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, and it is respectively 6% methane and 9% second to be passed through gas concentration
Alkyne reaction gas, by 1150 DEG C of high annealing resolution process, the high-temperature process time is 35 minutes, and cooled to room temperature obtains
To the carbon coating stannic disulfide catalyst of polymolecularity.
The conductive carbon of the sample and 1mg that take 1mg is dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes it be uniformly mixed, and is formed black
Color suspension pipettes 10 μ L suspensions on glass-carbon electrode, after natural drying, three is used on electrochemical workstation CHI660D
Electrode test system, the glass-carbon electrode of coating test catalyst sample is as working electrode, with 0.5M H2SO4Solution is electrolyte
Solution is saturated Ag/AgCl electrodes as reference electrode, and under the conditions of 0.1M KOH alkaline electrolytes, using saturation calomel
For reference electrode, platinum electrode is used as to electrode, 25 DEG C of water-bath temperature controls, 5mV/s sweep speeds, carries out water electrolysis hydrogen production test,
As shown in table 2.
Embodiment 2
（1）It is 80nm by aperture, the specific surface area of catalyst is 900m2Polyether-modified porous organic polysiloxanes, the silicon of/g
The cross-linked polymer solid material of resin and silicon rubber is placed in CVD reaction chambers, heat modification porous organic solid material
To 500 DEG C, CVD chamber is evacuated to 10Pa, and the CVD chamber holding vacuumizes 3 hours, leads to argon gas 8 hours, oxygen is discharged,
It controls gas concentration and is less than 0.001ppm, heating metallic tin is to 250 DEG C, and to 190 DEG C, heat temperature raising speed control exists heating thiocarbamide
7 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate control of thiocarbamide are passed through argon gas, argon flow amount control exists in 20mg/h
50sccm keeps the temperature 1h by chemical vapor deposition 6h, obtains load to have grain size being the organosilicon composite wood of the stannic disulfide of 20nm
Material；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
It is 5%, between the temperature of holding hydrofluoric acid is 25-40 DEG C in etching process, the organosilicon for obtaining the stannic disulfide of surface cleaning is multiple
Condensation material；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 10kPa, drying temperature by vacuum degree
It for 200 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, it is respectively 3% methane and 10% acetylene to be passed through gas concentration
Reaction gas, by 1200 DEG C of high annealing resolution process, the high-temperature process time is 50 minutes, and cooled to room temperature obtains
The carbon coating stannic disulfide catalyst of polymolecularity.
The conductive carbon of the sample and 1mg that take 1mg is dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes it be uniformly mixed, and is formed black
Color suspension pipettes 10 μ L suspensions on glass-carbon electrode, after natural drying, three is used on electrochemical workstation CHI660D
Electrode test system, the glass-carbon electrode of coating test catalyst sample is as working electrode, with 0.5M H2SO4Solution is electrolyte
Solution is saturated Ag/AgCl electrodes as reference electrode, and under the conditions of 0.1M KOH alkaline electrolytes, using saturation calomel
For reference electrode, platinum electrode is used as to electrode, 25 DEG C of water-bath temperature controls, 5mV/s sweep speeds, carries out water electrolysis hydrogen production test,
As shown in table 2.
Embodiment 3
（1）It is 100nm by aperture, the specific surface area of catalyst is 300m2The modified porous organosilicon polysiloxane of phenolic group, the silicon of/g
The cross-linked polymer solid material of resin and silicon rubber is placed in CVD reaction chambers, heat modification porous organic solid material
To 490 DEG C, CVD chamber is evacuated to 0.1-10Pa, and the CVD chamber holding vacuumizes 3.5 hours, leads to argon gas 7 hours, discharge
Oxygen, control gas concentration are less than 0.001ppm, and heating metallic tin is to 430 DEG C, and heating thiocarbamide is to 200 DEG C, heat temperature raising speed
Control is controlled in 7 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate of thiocarbamide in 25mg/h, is passed through argon gas, argon flow amount control
System keeps the temperature 1h in 2sccm, by chemical vapor deposition 6h, and obtaining load has the organosilicon that grain size is the stannic disulfide of 67nm compound
Material；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
It is 7%, between the temperature of holding hydrofluoric acid is 25-40 DEG C in etching process, the organosilicon for obtaining the stannic disulfide of surface cleaning is multiple
Condensation material；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 4.5kPa, dry temperature by vacuum degree
Degree is 350 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, and it is respectively 8% methane and 6% second to be passed through gas concentration
Alkyne reaction gas, by 1170 DEG C of high annealing resolution process, the high-temperature process time is 50 minutes, and cooled to room temperature obtains
To the carbon coating stannic disulfide catalyst of polymolecularity.
The conductive carbon of the sample and 1mg that take 1mg is dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes it be uniformly mixed, and is formed black
Color suspension pipettes 10 μ L suspensions on glass-carbon electrode, after natural drying, three is used on electrochemical workstation CHI660D
Electrode test system, the glass-carbon electrode of coating test catalyst sample is as working electrode, with 0.5M H2SO4Solution is electrolyte
Solution is saturated Ag/AgCl electrodes as reference electrode, and under the conditions of 0.1M KOH alkaline electrolytes, using saturation calomel
For reference electrode, platinum electrode is used as to electrode, 25 DEG C of water-bath temperature controls, 5mV/s sweep speeds, carries out water electrolysis hydrogen production test,
As shown in table 2.
Embodiment 4
（1）It is 40nm by aperture, the specific surface area of catalyst is 1000m2The modified porous organosilicon polysiloxane of alcoholic extract hydroxyl group of/g,
The cross-linked polymer solid material of silicones and silicon rubber is placed in CVD reaction chambers, heat modification porous organic solid material
For material to 500 DEG C, CVD chamber is evacuated to 0.1Pa, and the CVD chamber holding vacuumizes 5 hours, leads to argon gas 8 hours, oxygen is discharged
Gas, control gas concentration are less than 0.001ppm, and heating metallic tin is to 250 DEG C, and heating thiocarbamide is to 190 DEG C, heat temperature raising speed control
System is controlled in 12 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate of thiocarbamide in 25mg/h, is passed through argon gas, argon flow amount control
System keeps the temperature 1h in 45sccm, by chemical vapor deposition 6h, and obtaining load has the organosilicon that grain size is the stannic disulfide of 65nm multiple
Condensation material；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
It is 9.5%, between the temperature of holding hydrofluoric acid is 35 DEG C in etching process, the organosilicon for obtaining the stannic disulfide of surface cleaning is multiple
Condensation material；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 9.5kPa, dry temperature by vacuum degree
Degree is 350 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, and it is respectively 3% methane and 5% second to be passed through gas concentration
Alkyne reaction gas, by 1120 DEG C of high annealing resolution process, the high-temperature process time is 24 minutes, and cooled to room temperature obtains
To the carbon coating stannic disulfide catalyst of polymolecularity.
The conductive carbon of the sample and 1mg that take 1mg is dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes it be uniformly mixed, and is formed black
Color suspension pipettes 10 μ L suspensions on glass-carbon electrode, after natural drying, three is used on electrochemical workstation CHI660D
Electrode test system, the glass-carbon electrode of coating test catalyst sample is as working electrode, with 0.5M H2SO4Solution is electrolyte
Solution is saturated Ag/AgCl electrodes as reference electrode, and under the conditions of 0.1M KOH alkaline electrolytes, using saturation calomel
For reference electrode, platinum electrode is used as to electrode, 25 DEG C of water-bath temperature controls, 5mV/s sweep speeds, carries out water electrolysis hydrogen production test,
As shown in table 2.
Embodiment 5
（1）It is 60nm by aperture, the specific surface area of catalyst is 100~1000m2Amino, polyethers, alcoholic extract hydroxyl group, the phenolic group of/g changes
The cross-linked polymer solid material of the modified porous organosilicon polysiloxane of property, silicones and silicon rubber is placed in CVD reaction chambers,
For heat modification porous organic solid material to 490 DEG C, CVD chamber is evacuated to 10Pa, and the CVD chamber holding vacuumizes
4.5 hours, lead to argon gas 8 hours, oxygen is discharged, control gas concentration is less than 0.001ppm, and heating metallic tin is to 360 DEG C, heating
To 200 DEG C, heat temperature raising speed control controls thiocarbamide in 12.5 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate of thiocarbamide
In 12mg/h, it is passed through argon gas, argon flow amount control keeps the temperature 1h in 30sccm, by chemical vapor deposition 6h, and obtaining load has grain
Diameter is organic silicon composite of the stannic disulfide of 75nm；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
It is 6.5%, between the temperature of holding hydrofluoric acid is 25-40 DEG C in etching process, obtains the organosilicon of the stannic disulfide of surface cleaning
Composite material；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 8kPa, drying temperature by vacuum degree
It for 250 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, it is respectively 7% methane and 8% acetylene to be passed through gas concentration
Reaction gas, by 1180 DEG C of high annealing resolution process, the high-temperature process time is 50 minutes, and cooled to room temperature obtains
The carbon coating stannic disulfide catalyst of polymolecularity.
The conductive carbon of the sample and 1mg that take 1mg is dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes it be uniformly mixed, and is formed black
Color suspension pipettes 10 μ L suspensions on glass-carbon electrode, after natural drying, three is used on electrochemical workstation CHI660D
Electrode test system, the glass-carbon electrode of coating test catalyst sample is as working electrode, with 0.5M H2SO4Solution is electrolyte
Solution is saturated Ag/AgCl electrodes as reference electrode, and under the conditions of 0.1M KOH alkaline electrolytes, using saturation calomel
For reference electrode, platinum electrode is used as to electrode, 25 DEG C of water-bath temperature controls, 5mV/s sweep speeds, carries out water electrolysis hydrogen production test,
As shown in table 2.
Comparative example 1
Same amount hydro-thermal method is prepared into nanometer stannic disulfide and carries out water electrolysis hydrogen production test, test condition is identical as embodiment 1-5, surveys
Performance is tried as shown in table 2.
Comparative example 2
（1）It is 20nm by aperture, the specific surface area of catalyst is 500m2Amino modified porous organic polysiloxanes, the silicon of/g
The cross-linked polymer solid material of resin and silicon rubber is placed in CVD reaction chambers, heat modification porous organic solid material
To 480 DEG C, CVD chamber is evacuated to 0.1Pa, and the CVD chamber holding vacuumizes 5 hours, leads to argon gas 5 hours, oxygen is discharged,
It controls gas concentration and is less than 0.001ppm, heating metallic tin is to 290 DEG C, and to 200 DEG C, heat temperature raising speed control exists heating thiocarbamide
15 DEG C/min, evaporated metal tin and thiocarbamide, the evaporation rate control of thiocarbamide are passed through argon gas, argon flow amount control exists in 1mg/h
2sccm keeps the temperature 1h by chemical vapor deposition 6h, obtains load to have grain size being the organosilicon composite wood of the stannic disulfide of 80nm
Material;
（2）Organic silicon composite of the stannic disulfide of the surface cleaning is maintained at 0.5kPa, dry temperature by vacuum degree
Degree is 300 DEG C of vacuum drying treatments, then is placed in CVD reaction chambers, and it is respectively 6% methane and 9% second to be passed through gas concentration
Alkyne reaction gas, by 1150 DEG C of high annealing resolution process, the high-temperature process time is 35 minutes, and cooled to room temperature obtains
To carbon coating stannic disulfide nanocatalyst.
The carbon coating stannic disulfide nanocatalyst prepared in comparative example 2 is subjected to water electrolysis hydrogen production test, test condition
Identical as embodiment 1-5, test performance is as shown in table 2.
Table 2
It can be obtained by above-mentioned comparison, the carbon coating stannic disulfide nano-catalytic provided by the invention in acid or alkaline system
Agent has overpotential more lower than non-modified catalyst（Current density is 5.0 mA/cm2）, and with without hf etching
The catalyst of the organosilicon on surface layer is compared, and higher catalytic stability is shown.
Claims (9)
1. a kind of preparation method for the stannic disulfide catalyst being used to prepare fuel cell hydrogen, which is characterized in that using modification
Porous organic is as substrate, molten metal tin and thiocarbamide reaction, then is performed etching by hydrofluoric acid, redeposited carbon coating layer,
The carbon coating stannic disulfide catalyst of polymolecularity is obtained, specific preparation process is as follows：
（1）Modified porous organic silicon solid material is placed in CVD reaction chambers, heat modification porous organic solid material is extremely
450-500 DEG C, CVD chamber is evacuated to 0.1-10Pa, heating metallic tin to 250-500 DEG C, heating thiocarbamide to 180-200 DEG C,
Evaporated metal tin and thiocarbamide, are passed through argon gas, and argon flow amount control keeps the temperature 1h in 2-50sccm, by chemical vapor deposition 6h, obtains
There is organic silicon composite of stannic disulfide to load；
（2）It will be performed etching in the organic silicon composite immersion hydrofluoric acid for loading and have stannic disulfide, the concentration of hydrofluoric acid
For 5-10%, between the temperature of hydrofluoric acid is kept in etching process is 25-40 DEG C, the organic of the stannic disulfide of surface cleaning is obtained
Silicon composite；
（3）Organic silicon composite of the stannic disulfide of the surface cleaning is passed through into vacuum drying treatment, then is placed in CVD reactions
In chamber, it is passed through methane and acetylene reaction gas, by 1100-1200 DEG C of high annealing resolution process, cooled to room temperature,
Obtain the carbon coating stannic disulfide catalyst of polymolecularity.
2. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the modified porous organosilicon is the cross-linked polymer of polysiloxanes, silicones and silicon rubber, the modification is more
Hole organosilicon includes one kind in amino, polyethers, alcoholic extract hydroxyl group, phenolic group modification, aperture 20-100nm, the specific surface area of catalyst
For 100-1000m2/g。
3. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the CVD chamber holding vacuumizes 3-5 hours, lead to argon gas 5-8 hours, oxygen is discharged, control gas concentration is small
In 0.001ppm.
4. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the heating rate of the heating thiocarbamide is controlled in 5-15 DEG C/min.
5. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the evaporation rate of the thiocarbamide is controlled in 1-30mg/h.
6. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the stannic disulfide grain diameter is 20-80nm.
7. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, step（3）Described in vacuum drying treatment be vacuum degree be maintained at 0.5-10kPa, drying temperature 200-500
℃。
8. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the gas concentration of the methane and acetylene is respectively 3-8% and 5-10%.
9. a kind of preparation method of stannic disulfide catalyst being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that, the step（3）In the high-temperature process time be 20-50 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289874A (en) * | 2018-11-16 | 2019-02-01 | 安徽师范大学 | A kind of cobalt doped stannic disulphide nano slice array material and its preparation method and application |
| CN110918132A (en) * | 2019-12-02 | 2020-03-27 | 厦门大学 | Water electrolysis material with self-supporting double-carbon sandwich structure and preparation method thereof |
| CN111939934A (en) * | 2020-08-18 | 2020-11-17 | 合肥工业大学 | SnS2/C/Si ternary nano array photoelectric catalyst and preparation method thereof |
-
2018
- 2018-04-28 CN CN201810397128.4A patent/CN108479807A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289874A (en) * | 2018-11-16 | 2019-02-01 | 安徽师范大学 | A kind of cobalt doped stannic disulphide nano slice array material and its preparation method and application |
| CN109289874B (en) * | 2018-11-16 | 2021-03-16 | 安徽师范大学 | Cobalt-doped tin disulfide nanosheet array material and preparation method and application thereof |
| CN110918132A (en) * | 2019-12-02 | 2020-03-27 | 厦门大学 | Water electrolysis material with self-supporting double-carbon sandwich structure and preparation method thereof |
| CN111939934A (en) * | 2020-08-18 | 2020-11-17 | 合肥工业大学 | SnS2/C/Si ternary nano array photoelectric catalyst and preparation method thereof |
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