CN106637273B - Carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole and preparation and application - Google Patents
Carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole and preparation and application Download PDFInfo
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Abstract
The present invention relates to carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole and preparation and application, belong to optoelectronic pole Material Field.Chromium strontium titanate doping nano cubic block with visible light characteristic is uniformly modified into periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtain chromium strontium titanate doping/titanium dioxide nanotube composite electrode, the method coated again by carbon source, by inert gas calcination processing, carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole is prepared.And using this heterojunction structure optoelectronic pole as optical anode material during photoelectrocatalysis, the glycoxidative hydrogen production process of grape is catalyzed for efficient photoelectricity treater.Compared with prior art, photoelectrocatalysis hydrogen production process of the present invention is simple and easy, and easy to operate and applicable elements are mild.In addition, carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole oxidizing glucose promotion hydrogen output is 23.97 times of hydrogen production by water decomposition amount, and it shows excellent photoelectrocatalysis stability.
Description
Technical field
The present invention relates to a kind of optoelectronic pole materials, coat chromium strontium titanate doping/titanium dioxide more particularly, to a kind of carbon-coating
Nanotube optoelectronic pole and preparation and application.
Background technique
Hydrogen Energy is mainly largely extensive in the form of molecular water as ideal pollution-free green high-capacity new energy
It is distributed in nature, reports that protium occupies 75% or more earth component according to statistics.It has the following characteristics that as the energy
(1) energy is high, 3 times higher than gasoline quantity of heat production；(2) it is used convenient for storage and transport；(3) only have when nontoxic and burning aquatic
At will not be polluted to ambient enviroment.It is developed so far, the main method of industrial hydrogen production are as follows: fossil energy hydrogen manufacturing, electrolysis water system
Hydrogen, biological hydrogen production and photoelectrocatalysis hydrogen production by water decomposition etc..Wherein, photoelectrocatalysis hydrogen production by water decomposition is a kind of not only economical but also green
Hydrogen manufacturing ideal method.
The key of photoelectrocatalysis hydrogen production by water decomposition technology is that the overpotential and exploitation in reduction reaction process have excellent performance light
Electrocatalyst materials.It is well known that thermodynamics electromotive force required for water decomposition hydrogen manufacturing is 1.23V.However it is electric when applying electrode
When on electrode, water decomposition hydrogen production reaction is practical to be difficult to occur gesture 1.23V, should need to apply high overpotential driving water decomposition
Reaction occurs.According to thermodynamic principles, external world's driving energy consumption required for oxidation of the biomass derivatives oxidation compared to water is lower.
Therefore, it is aoxidized using biomass derivatives substitution pure water, promoting light induced electron to be transferred to efficient hydrogen manufacturing at Pt cathode has
Potential development prospect.Up to the present, many semiconductor photoelectrocatalysielectrode agent materials are widely used in photoelectrocatalysis hydrogen manufacturing,
But the respective defect of semiconductor is to limit its practical application, such as wide band gap semiconducter (such as TiO2) catalyst is only to ultraviolet light
It is able to carry out strong absorption, but ultraviolet spectra only accounts for about the 5% of solar spectrum gross energy, causes wide band gap semiconducter to the sun
The utilization of luminous energy and conversion ratio are lower.And although narrow gap semiconductor catalyst can effectively absorb visible luminous energy, this
There is stronger photoetch in based semiconductor such as CdS etc., and stability is poor, to significantly reduce its photoelectric catalytically active.
In order to solve above-mentioned problem, scientists have carried out a large amount of scientific research and have attempted.
Summary of the invention
The object of the invention is in order to overcome above-mentioned existing photoelectrocatalysis hydrogen producing technology existing defects, and provide a kind of carbon
Layer cladding chromium strontium titanate doping/titania nanotube optoelectronic pole and preparation and application.
The present invention is by chromium strontium titanate doping and carbon-coating with excellent visible light absorption and good conductive characteristic
As co-catalyst, they are supported in periodically ordered titania nanotube basal electrode, constructs to obtain carbon-coating cladding chromium
Strontium titanate doping/titania nanotube optoelectronic pole, the photoelectricity extremely heterojunction structure, while carbon-coating is coated into chromium doped titanic acid
Strontium/titania nanotube optoelectronic pole combines realization rapidly and efficiently photoelectrocatalysis biomass derived with photoelectrocatalysis hydrogen producing technology
Object aoxidizes hydrogen manufacturing.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole, the chromium with visible light characteristic is mixed
Miscellaneous strontium titanates nano cubic block uniformly modifies periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtains chromium doping
Strontium titanates/titanium dioxide nanotube composite electrode, then the method coated by carbon source pass through inert gas calcination processing, preparation
Obtain carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole.
Carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole preparation method, comprising the following steps:
(1) preparation of periodically ordered Nano tube array of titanium dioxide basal electrode:
Using platinized platinum and titanium plate as cathode and an anode, in electrolyte solution, additional tank voltage is 20~80V, into
Row multistep Anodic after anodization, is ultrasonically treated 0.1~2min of anodization product with secondary distilled water, then calcine knot
Periodically ordered Nano tube array of titanium dioxide basal electrode is prepared in crystallization anodization product；
Preferably, in this step, pre-process to titanium plate: titanium plate is successively polishing to its surface with 100~800# sand paper
It is smooth；Again with 5~10min of ultrasonic cleaning is carried out to it respectively in secondary distilled water and ethanol solution, then blown with nitrogen
Do its surface.
Preferably, in this step, the electrolyte solution is to contain 0.1~1.0wt%NH4F and 1.0~3.0vol%
H2The ethylene glycol solution of O.
Preferably, in this step, distance is 0.5~2cm between two electrodes.
Preferably, in this step, the temperature of the calcining is 400~600 DEG C, and when calcining heats up or the rate of cooling is
1~5 DEG C/min, calcining is carried out under air atmosphere.
(2) chromium strontium titanate doping/titanium dioxide nanotube composite electrode preparation:
The periodically ordered Nano tube array of titanium dioxide basal electrode that step (1) is prepared be placed in containing barium source with
In the mixed solution of chromium source, then mixed solution and basal electrode are transferred in polytetrafluoroethyllining lining reaction kettle, carried out molten
Agent thermal response, after cooling, with secondary distilled water cleaning sample electrode surface, drying and processing, be prepared chromium strontium titanate doping/
Titanium dioxide nanotube composite electrode；
Preferably, in this step, the barium source includes Sr (OH)2·8H2O or Sr (NO3)2, the chromium source includes Cr
(NO3)2·9H2O or Cr (OH)2, in the mixed solution containing barium source and chromium source, the concentration of Sr is 0.0001~0.0005mol/
The concentration of L, Cr are 0.001~0.005mol/L, further include concentration in the mixed solution containing barium source and chromium source are 1~5mol/L
NaOH.
Preferably, in this step, the temperature for carrying out solvent thermal reaction is 50~200 DEG C, and the time is 10~60min.
Preferably, in this step, the condition of drying are as follows: 0.5~3h drying and processing in 50~100 DEG C of vacuum drying ovens.
(3) carbon-coating coats the preparation of chromium strontium titanate doping/titania nanotube optoelectronic pole:
Chromium strontium titanate doping/titanium dioxide nanotube composite electrode that step (2) obtains is soaked in carbon source and carries out carbon
Source cladding, is cleaned after taking-up with secondary distilled water, drying and processing；Using calcination processing under inert atmosphere, carbon-coating is prepared
Coat chromium strontium titanate doping/titania nanotube optoelectronic pole.
Preferably, in this step, the carbon source is glucose solution, and concentration is 0.5~10mg/mL.
Preferably, in this step, the condition of drying are as follows: 0.5~3h drying and processing in 50~100 DEG C of vacuum drying ovens.
Preferably, in this step, the temperature of the calcining is 400~600 DEG C, and when calcining heats up or the rate of cooling is
1~5 DEG C/min, calcining is carried out under nitrogen or argon atmosphere.
The present invention constructs and the carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole photoelectricity being prepared is urged
Metaplasia substance and its derivative oxidation promote hydrogen manufacturing.Specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel in sealing gas circulating system, chromium is coated with the carbon-coating
Strontium titanate doping/titania nanotube optoelectronic pole is as light anode, and platinized platinum is as cathode, saturated calomel electrode (SCE) conduct
Reference electrode.
(2) the KOH electrolyte solution containing biomass and its derivative is prepared, it is preferable that the KOH electrolyte solution
Concentration be 0.1~1mol/L, the concentration of the biomass and its derivative in KOH electrolyte solution be 0.05~
0.3mol/L。
(3) 300W short arc Xe lamp is equipped with visible filter as visible light source, and application -0.3V (vs.SCE) is biased in
At cathode, thermal conductivity sensor (TCD) is equipped with finally by online gas-chromatography (GC) and carries out qualitative and quantitative survey to gas is collected
It is fixed.
Preferably, the biomass and its derivative are glucose.
In the present invention first by multistep Anodic method, preparation grows vertical growth week in titanium plate substrate
The orderly Nano tube array of titanium dioxide of phase property is as optical substrate electrode material, since titania nanotube has excellent light
The advantages that electrochemical stability, big specific surface area and compatible good biological, becomes structure and has excellent performance desired light
Electrochemical material.Narrow-band semiconductor material is modified in titania nanotube surface, the suction to visible light can be significantly increased
Receipts and transformation efficiency, and it is effectively improved the characteristics such as sample electrode photostability.By being modified solvent-thermal method for chromium strontium titanate doping
Nano cubic block is uniformly modified in titania nanotube basal electrode surface；Solvent cladding and calcination processing method are recycled, it will
Carbon-coating is coated at chromium strontium titanate doping/titania nanotube photoanode surface, and carbon-coating cladding chromium doped titanic acid is prepared
Strontium/titania nanotube optical anode material.Photoelectrochemical behaviour test shows that carbon-coating coats chromium strontium titanate doping/titanium dioxide
Nanotube shows excellent visible light absorption and photoelectrochemical behaviour, and photoelectricity density value is up to 0.44mA/cm2.Knot
Fruit further demonstrates that the preparation-obtained sample electrode of the present invention has the glycoxidative promotion system of the photoelectrocatalysis grape significantly increased
Hydrogen characteristic.In addition, heterojunction structure optoelectronic pole prepared by the present invention shows repeatability, that is, pass through the visible light in 5 periods
After loop test, the density of photocurrent value of heterojunction structure light anode still maintains 0.44mA/cm2.As a result this is further demonstrated that
Invention heterojunction structure optical anode material has the glycoxidative hydrogen production activity of photoelectrocatalysis grape of superelevation.
Compared with prior art, the invention has the following advantages that
(1) present invention selects biomass derivatives glucose to substitute water oxygen hydrogen manufacturing as oxide species, can derived from it
Photoelectrocatalysis is effectively reduced and aoxidizes overpotential in the process, to effectively reduce energy consumption；And it can efficiently turn photoelectron
Move to hydrogen production by water decomposition at Pt cathode.
(2) present invention is by the modification of chromium strontium titanate doping nano cubic block in periodically ordered titania nanotube substrate electricity
Pole.Since chromium strontium titanate doping has excellent visible light absorption, so as to significantly increase chromium strontium titanate doping/dioxy
Change absorption and transformation efficiency of the titanium nanotube sample electrode to visible light, further increases the PhotoelectrocatalytiPerformance Performance of sample electrode.
(3) carbon-coating is coated on chromium strontium titanate doping/titania nanotube sample electrode surface by the present invention, is prepared
Carbon-coating coats chromium strontium titanate doping/titania nanotube heterojunction structure light anode.Since carbon-coating has excellent electronic conduction
Property and optical absorption characteristics, so as to significantly increase carbon-coating coat chromium strontium titanate doping/titania nanotube hetero-junctions
Structure light anode photoelectrochemical behaviour and photoelectrocatalysis Equilibrium in Hydrogen Preparation from Glucose characteristic.
(4) present invention will coat chromium strontium titanate doping/titania nanotube heterojunction structure as photoelectricity aurora using carbon-coating
The glycoxidative hydrogen manufacturing of electro-catalysis grape, hydrogen output are up to 193.03 μm of ol/cm2, hydrogen output is the 23.97 of photolysis water hydrogen amount
Times.
Detailed description of the invention
Fig. 1 is that carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole shape appearance figure.
Fig. 2 is that carbon-coating coats chromium strontium titanate doping/glycoxidative promotion of titania nanotube optoelectronic pole photoelectrocatalysis grape
Hydrogen manufacturing chromatogram.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Carbon-coating coats chromium strontium titanate doping/titania nanotube heterojunction structure optoelectronic pole preparation method, including following
Step:
(1) titanium plate successively uses 100#, 300# and 800# sand paper to be polishing to its surface smooth；Again with secondary distilled water and
Ultrasonic cleaning 10min is carried out to it respectively in ethanol solution, then with being dried with nitrogen its surface.At room temperature, tradition two
In electrode system, using platinized platinum and titanium plate as cathode and an anode, electrode spacing 1cm；Outside plus tank voltage be 60V when into
Row multistep Anodic.Anodic electrolyte solution are as follows: 0.3wt%NH4F and 2.0vol%H2The ethylene glycol of O is molten
Liquid.After anodization, it is ultrasonically treated anodization product 1min with secondary distilled water, then 500 DEG C of calcined crystallineization sun under air atmosphere
Polarized products, are prepared periodically ordered titania nanotube basal electrode, and heating and rate of temperature fall are 2 DEG C/min.
(2) basal electrode will be prepared in step (1) to be placed in containing 0.0024mol/L Sr (OH)2·8H2O、0.0013mol/
L Cr(NO3)2·9H2The 40mL H of O and 3.125mol/L NaOH2In O；Above-mentioned mixed solution and basal electrode material are turned
It moves in polytetrafluoroethyllining lining；Solvent-thermal method is recycled, reacts 40min under 150 DEG C of constant temperatures；After cooling, with two
Secondary distilled water cleaning sample electrode surface is placed in 1h drying and processing in 60 DEG C of vacuum drying ovens, chromium strontium titanate doping/bis- is prepared
Titanium oxide nanotubes composite sample electrode.
(3) composite sample in step (2) is soaked in 15min in the glucose solution of various concentration (2mg/mL), taken out
Cleaned afterwards with secondary distilled water, be placed in 2h drying and processing in 60 DEG C of vacuum drying ovens, be prepared carbon-coating cladding chromium strontium titanate doping/
Titania nanotube heterojunction structure optoelectronic pole.As shown in Figure 1, the chromium strontium titanate doping nano cubic that a large amount of side lengths are about 80nm
Block deposition modification is in the surface TNTAs, and by after carbon coating, not to nano cubic block in process of the present invention and nanotube-shaped
Structure impacts.
Embodiment 2
At room temperature, optical electro-chemistry is carried out on CHI660c electrochemical workstation using traditional three-electrode system
It can test, the carbon-coating prepared using embodiment 1 coats chromium strontium titanate doping/titania nanotube heterojunction structure optoelectronic pole as light
Anode, saturated calomel electrode (SCE) and Pt piece are respectively as reference electrode and to electrode.With 0.1mol/L glucose
0.5mol/LKOH solution is as electrolyte.Ampere i-t curve test is the result shows that carbon-coating coats chromium strontium titanate doping/titanium dioxide
Titanium nano tube hetero-junction structure optoelectronic pole density of photocurrent value is up to 0.44mA/cm2.At its surface compared to pure water oxidation
Aoxidize density of photocurrent value 0.28mA/cm2, as a result further demonstrate that biomass derivatives glucose is easier at photoelectricity pole surface
Oxidation reaction occurs, increases the density of photocurrent value of sample electrode.
Embodiment 3
It is equipped in three electrode reactors of self-control and vacuum air-channel in sealing gas circulating system, is prepared with embodiment 1
Carbon-coating coats chromium strontium titanate doping/titania nanotube heterojunction structure optoelectronic pole as light anode, and platinized platinum is as cathode and satisfies
Reference electrode, electrolyte solution are used as with calomel electrode (SCE) are as follows: the 0.5mol/LKOH electrolysis containing 0.1mol/L glucose
Matter solution.300W short arc Xe lamp is equipped with visible filter as visible light source and application -0.3V (vs.SCE) is biased in Pt yin
At pole.Thermal conductivity sensor (TCD), which is equipped with, finally by online gas-chromatography (GC) carries out qualitative and quantitative determination to gas is collected.
(in Fig. 2, curve is respectively 1h, 2h, 3h, 4h, 5h, 6h from bottom to top) as shown in Figure 2, the yield of hydrogen is with anti-at Pt cathode
Incremental between seasonable shows the trend being gradually increased.Carbon-coating coats chromium strontium titanate doping/titania nanotube heterojunction structure
The glycoxidative hydrogen manufacturing amount of optoelectronic pole photoelectrocatalysis grape is up to 193.03 μm of ol/cm2, it is 23.97 times of photolysis water hydrogen amount.
Embodiment 4
A kind of carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole, the chromium with visible light characteristic is mixed
Miscellaneous strontium titanates nano cubic block uniformly modifies periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtains chromium doping
Strontium titanates/titanium dioxide nanotube composite electrode, then the method coated by carbon source pass through inert gas calcination processing, preparation
Obtain carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole.Specific method the following steps are included:
(1) preparation of periodically ordered Nano tube array of titanium dioxide basal electrode:
Pre-process to titanium plate: it is smooth that titanium plate is successively polishing to its surface with 100#, 300#, 800# sand paper；Again
With ultrasonic cleaning 5min is carried out to it respectively in secondary distilled water and ethanol solution, then with its surface is dried with nitrogen, with platinized platinum
With titanium plate respectively as cathode and an anode, distance is 0.5cm between two electrodes, (contains 0.1wt%NH in electrolyte solution4F
And 1.0vol%H2The ethylene glycol solution of O) in, additional tank voltage is 20V, carries out multistep Anodic, after anodization, is used
Secondary distilled water is ultrasonically treated anodization product 0.1min, then the calcined crystalline anodization product under air atmosphere, calcining
Temperature is 400 DEG C, heats up when calcining or the rate of cooling is 1 DEG C/min, periodically ordered titania nanotube is prepared
Array substrate electrode；
(2) chromium strontium titanate doping/titanium dioxide nanotube composite electrode preparation:
The periodically ordered Nano tube array of titanium dioxide basal electrode that step (1) is prepared be placed in containing barium source with
In the mixed solution of chromium source, barium source includes Sr (OH)2·8H2O or Sr (NO3)2, chromium source includes Cr (NO3)2·9H2O or Cr
(OH)2, in the mixed solution containing barium source and chromium source, the concentration of Sr is 0.0001mol/L, and the concentration of Cr is 0.001mol/L,
It further include the NaOH that concentration is 1mol/L in mixed solution containing barium source and chromium source.Then mixed solution and basal electrode are turned
It moves in polytetrafluoroethyllining lining reaction kettle, solvent thermal reaction 60min is carried out at 50 DEG C, it is after cooling, clear with secondary distilled water
Sample electrode surface is washed, it is multiple that chromium strontium titanate doping/titania nanotube is prepared in 3h drying and processing in 50 DEG C of vacuum drying ovens
Composite electrode；
(3) carbon-coating coats the preparation of chromium strontium titanate doping/titania nanotube optoelectronic pole:
It is 0.5mg/ that chromium strontium titanate doping/titanium dioxide nanotube composite electrode that step (2) obtains, which is soaked in concentration,
Carbon source cladding is carried out in the glucose solution of mL, is cleaned after taking-up with secondary distilled water, 3h drying and processing in 50 DEG C of vacuum drying ovens；
Using calcination processing under inert atmosphere (nitrogen or argon gas), the temperature of calcining is 400 DEG C, and when calcining heats up or the rate of cooling
For 1 DEG C/min, carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole is prepared.
Carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole photoelectricity that the present embodiment is constructed and is prepared
It is catalyzed the glycoxidative promotion hydrogen manufacturing of grape.Specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel in sealing gas circulating system, chromium Doped with Titanium is coated with carbon-coating
Sour strontium/titania nanotube optoelectronic pole is as light anode, and platinized platinum is as cathode, and saturated calomel electrode (SCE) is as reference electricity
Pole.
(2) the KOH electrolyte solution containing glucose is prepared, it is preferable that KOH concentration of electrolyte solutions is 0.1mol/L,
Concentration of the glucose in KOH electrolyte solution is 0.05mol/L.
(3) 300W short arc Xe lamp is equipped with visible filter as visible light source, and application -0.3V (vs.SCE) is biased in
At cathode, thermal conductivity sensor (TCD) is equipped with finally by online gas-chromatography (GC) and carries out qualitative and quantitative survey to gas is collected
It is fixed.
Embodiment 5
A kind of carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole, the chromium with visible light characteristic is mixed
Miscellaneous strontium titanates nano cubic block uniformly modifies periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtains chromium doping
Strontium titanates/titanium dioxide nanotube composite electrode, then the method coated by carbon source pass through inert gas calcination processing, preparation
Obtain carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole.Specific method the following steps are included:
(1) preparation of periodically ordered Nano tube array of titanium dioxide basal electrode:
Pre-process to titanium plate: it is smooth that titanium plate is successively polishing to its surface with 100#, 400#, 800# sand paper；Again
With ultrasonic cleaning 8min is carried out to it respectively in secondary distilled water and ethanol solution, then with its surface is dried with nitrogen, with platinized platinum
With titanium plate respectively as cathode and an anode, distance is 1cm between two electrodes, (contains 0.5wt%NH in electrolyte solution4F and
2.0vol%H2The ethylene glycol solution of O) in, additional tank voltage is 50V, multistep Anodic is carried out, after anodization, with two
Secondary distilled water is ultrasonically treated anodization product 1min, then the calcined crystalline anodization product under air atmosphere, the temperature of calcining
It is 500 DEG C, heats up when calcining or the rate of cooling is 3 DEG C/min, periodically ordered Nano tube array of titanium dioxide is prepared
Basal electrode；
(2) chromium strontium titanate doping/titanium dioxide nanotube composite electrode preparation:
The periodically ordered Nano tube array of titanium dioxide basal electrode that step (1) is prepared be placed in containing barium source with
In the mixed solution of chromium source, barium source includes Sr (OH)2·8H2O or Sr (NO3)2, chromium source includes Cr (NO3)2·9H2O or Cr
(OH)2, in the mixed solution containing barium source and chromium source, the concentration of Sr is 0.0003mol/L, and the concentration of Cr is 0.003mol/L,
It further include the NaOH that concentration is 3mol/L in mixed solution containing barium source and chromium source.Then mixed solution and basal electrode are turned
It moves in polytetrafluoroethyllining lining reaction kettle, solvent thermal reaction 40min is carried out at 100 DEG C, it is after cooling, clear with secondary distilled water
Sample electrode surface is washed, chromium strontium titanate doping/titania nanotube is prepared in 1.5h drying and processing in 80 DEG C of vacuum drying ovens
Combination electrode；
(3) carbon-coating coats the preparation of chromium strontium titanate doping/titania nanotube optoelectronic pole:
It is 5.0mg/ that chromium strontium titanate doping/titanium dioxide nanotube composite electrode that step (2) obtains, which is soaked in concentration,
Carbon source cladding is carried out in the glucose solution of mL, is cleaned after taking-up with secondary distilled water, 2h drying and processing in 70 DEG C of vacuum drying ovens；
Using calcination processing under inert atmosphere (nitrogen or argon gas), the temperature of calcining is 500 DEG C, and when calcining heats up or the rate of cooling
For 3 DEG C/min, carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole is prepared.
Carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole photoelectricity that the present embodiment is constructed and is prepared
It is catalyzed the glycoxidative promotion hydrogen manufacturing of grape.Specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel in sealing gas circulating system, chromium Doped with Titanium is coated with carbon-coating
Sour strontium/titania nanotube optoelectronic pole is as light anode, and platinized platinum is as cathode, and saturated calomel electrode (SCE) is as reference electricity
Pole.
(2) the KOH electrolyte solution containing glucose is prepared, it is preferable that KOH concentration of electrolyte solutions is 0.5mol/L,
Concentration of the glucose in KOH electrolyte solution is 0.15mol/L.
(3) 300W short arc Xe lamp is equipped with visible filter as visible light source, and application -0.3V (vs.SCE) is biased in
At cathode, thermal conductivity sensor (TCD) is equipped with finally by online gas-chromatography (GC) and carries out qualitative and quantitative survey to gas is collected
It is fixed.
Embodiment 6
A kind of carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole, the chromium with visible light characteristic is mixed
Miscellaneous strontium titanates nano cubic block uniformly modifies periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtains chromium doping
Strontium titanates/titanium dioxide nanotube composite electrode, then the method coated by carbon source pass through inert gas calcination processing, preparation
Obtain carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole.Specific method the following steps are included:
(1) preparation of periodically ordered Nano tube array of titanium dioxide basal electrode:
Pre-process to titanium plate: it is smooth flat that titanium plate is successively polishing to its surface with 100#, 300#, 500#, 800# sand paper
It is whole；Again with carrying out ultrasonic cleaning 10min to it respectively in secondary distilled water and ethanol solution, then with being dried with nitrogen its surface,
Using platinized platinum and titanium plate as cathode and an anode, distance is 2cm between two electrodes, (contains 1.0wt% in electrolyte solution
NH4F and 3.0vol%H2The ethylene glycol solution of O) in, additional tank voltage is 80V, carries out multistep Anodic, anodization
Afterwards, anodization product 2min, then the calcined crystalline anodization product under air atmosphere, calcining are ultrasonically treated with secondary distilled water
Temperature be 600 DEG C, heat up when calcining or the rate of cooling be 5 DEG C/min, periodically ordered nano titania is prepared
Pipe array substrate electrode；
(2) chromium strontium titanate doping/titanium dioxide nanotube composite electrode preparation:
The periodically ordered Nano tube array of titanium dioxide basal electrode that step (1) is prepared be placed in containing barium source with
In the mixed solution of chromium source, barium source includes Sr (OH)2·8H2O or Sr (NO3)2, chromium source includes Cr (NO3)2·9H2O or Cr
(OH)2, in the mixed solution containing barium source and chromium source, the concentration of Sr is 0.0005mol/L, and the concentration of Cr is 0.005mol/L,
It further include the NaOH that concentration is 5mol/L in mixed solution containing barium source and chromium source.Then mixed solution and basal electrode are turned
It moves in polytetrafluoroethyllining lining reaction kettle, solvent thermal reaction 10min is carried out at 200 DEG C, it is after cooling, clear with secondary distilled water
Sample electrode surface is washed, chromium strontium titanate doping/nano titania is prepared in 0.5h drying and processing in 100 DEG C of vacuum drying ovens
Pipe combination electrode；
(3) carbon-coating coats the preparation of chromium strontium titanate doping/titania nanotube optoelectronic pole:
It is 10mg/mL that chromium strontium titanate doping/titanium dioxide nanotube composite electrode that step (2) obtains, which is soaked in concentration,
Glucose solution in carry out carbon source cladding, cleaned after taking-up with secondary distilled water, in 100 DEG C of vacuum drying ovens at 0.5h drying
Reason；Using calcination processing under inert atmosphere (nitrogen or argon gas), the temperature of calcining is 600 DEG C, and when calcining heats up or cooling
Rate is 5 DEG C/min, and carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole is prepared.
Carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole photoelectricity that the present embodiment is constructed and is prepared
It is catalyzed the glycoxidative promotion hydrogen manufacturing of grape.Specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel in sealing gas circulating system, chromium Doped with Titanium is coated with carbon-coating
Sour strontium/titania nanotube optoelectronic pole is as light anode, and platinized platinum is as cathode, and saturated calomel electrode (SCE) is as reference electricity
Pole.
(2) the KOH electrolyte solution containing glucose is prepared, it is preferable that KOH concentration of electrolyte solutions is 1mol/L, Portugal
Concentration of the grape sugar in KOH electrolyte solution is 0.3mol/L.
(3) 300W short arc Xe lamp is equipped with visible filter as visible light source, and application -0.3V (vs.SCE) is biased in
At cathode, thermal conductivity sensor (TCD) is equipped with finally by online gas-chromatography (GC) and carries out qualitative and quantitative survey to gas is collected
It is fixed.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (8)
1. a kind of carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole, which is characterized in that will have visible light special
The chromium strontium titanate doping nano cubic block of property uniformly modifies periodically ordered Nano tube array of titanium dioxide basal electrode surface, obtains
To chromium strontium titanate doping/titanium dioxide nanotube composite electrode, then the method coated by carbon source, at inert gas calcining
Carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole is prepared in reason；
Carbon-coating coats chromium strontium titanate doping/titania nanotube optoelectronic pole preparation method, comprising the following steps:
(1) preparation of periodically ordered Nano tube array of titanium dioxide basal electrode:
Using platinized platinum and titanium plate as cathode and an anode, in electrolyte solution, additional tank voltage is 20~80V, is carried out more
One-step electrochemistry anodization after anodization, is ultrasonically treated anodization product with secondary distilled water, then calcined crystalline anodization produces
Periodically ordered Nano tube array of titanium dioxide basal electrode is prepared in object；
(2) chromium strontium titanate doping/titanium dioxide nanotube composite electrode preparation:
The periodically ordered Nano tube array of titanium dioxide basal electrode that step (1) is prepared is placed in containing barium source and chromium source
Mixed solution in, then mixed solution and basal electrode are transferred in polytetrafluoroethyllining lining reaction kettle, carry out solvent heat
Reaction, after cooling, with secondary distilled water cleaning sample electrode surface, chromium strontium titanate doping/dioxy is prepared in drying and processing
Change titanium nanometer tube combination electrode；
(3) carbon-coating coats the preparation of chromium strontium titanate doping/titania nanotube optoelectronic pole:
Chromium strontium titanate doping/titanium dioxide nanotube composite electrode that step (2) obtains is soaked in progress carbon source packet in carbon source
It covers, is cleaned after taking-up with secondary distilled water, drying and processing, then through calcination processing in inert atmosphere, carbon-coating cladding chromium is prepared
Strontium titanate doping/titania nanotube optoelectronic pole.
2. carbon-coating according to claim 1 coats chromium strontium titanate doping/titania nanotube optoelectronic pole, feature exists
In in step (1), the electrolyte solution is to contain 0.1~1.0wt%NH4F and 1.0~3.0vol%H2The ethylene glycol of O
Solution.
3. carbon-coating according to claim 1 coats chromium strontium titanate doping/titania nanotube optoelectronic pole, feature exists
In in step (1), the temperature of the calcining is 400~600 DEG C, and when calcining heats up or the rate of cooling is 1~5 DEG C/min.
4. carbon-coating according to claim 1 coats chromium strontium titanate doping/titania nanotube optoelectronic pole, feature exists
In in step (2), the barium source includes Sr (OH)2·8H2O or Sr (NO3)2, the chromium source includes Cr (NO3)2·9H2O
Or Cr (OH)2, in the mixed solution containing barium source and chromium source, the concentration of Sr is 0.0001~0.0005mol/L, and the concentration of Cr is
0.001~0.005mol/L further includes the NaOH that concentration is 1~5mol/L in the mixed solution containing barium source and chromium source.
5. carbon-coating according to claim 1 coats chromium strontium titanate doping/titania nanotube optoelectronic pole, feature exists
In in step (2), the temperature for carrying out solvent thermal reaction is 50~200 DEG C, and the time is 10~60min.
6. carbon-coating according to claim 1 coats chromium strontium titanate doping/titania nanotube optoelectronic pole, feature exists
In in step (3), the carbon source is glucose solution, and concentration is 0.5~10mg/mL；The temperature of the calcining is
It 400~600 DEG C, heats up when calcining or the rate of cooling is 1~5 DEG C/min；Inert atmosphere is nitrogen or argon gas.
7. a kind of carbon-coating as described in claim 1 coats the application of chromium strontium titanate doping/titania nanotube optoelectronic pole,
Be characterized in that, described carbon-coating cladding chromium strontium titanate doping/titania nanotube optoelectronic pole for photoelectrocatalysis biomass and
The oxidation of its derivative promotes hydrogen manufacturing, specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel, in sealing gas circulating system with the carbon-coating cladding chromium doping
Strontium titanates/titania nanotube optoelectronic pole is as light anode, and platinized platinum is as cathode, and saturated calomel electrode is as reference electrode；
(2) the KOH electrolyte solution containing biomass and its derivative is prepared；
(3) 300W short arc Xe lamp is equipped with visible filter as visible light source, and application -0.3V is biased at cathode, finally
Thermal conductivity sensor, which is equipped with, by online gas-chromatography carries out qualitative and quantitative determination to gas is collected.
8. carbon-coating according to claim 7 coats the application of chromium strontium titanate doping/titania nanotube optoelectronic pole, special
Sign is that the biomass and its derivative are glucose, and the KOH concentration of electrolyte solutions is 0.1~1mol/L, institute
Concentration of the biomass and its derivative stated in KOH electrolyte solution is 0.05~0.3mol/L.
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| CN110164712B (en) * | 2019-06-20 | 2021-06-01 | 上海大学(浙江·嘉兴)新兴产业研究院 | Lithium ion capacitor electrode material and preparation method thereof |
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