CN106637289B - CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and preparation and application - Google Patents

CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and preparation and application Download PDF

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CN106637289B
CN106637289B CN201510727312.7A CN201510727312A CN106637289B CN 106637289 B CN106637289 B CN 106637289B CN 201510727312 A CN201510727312 A CN 201510727312A CN 106637289 B CN106637289 B CN 106637289B
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titanium dioxide
quantum dots
cdse quantum
optoelectronic pole
nanometer rods
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CN106637289A (en
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赵国华
张亚军
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Tongji University
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Abstract

The present invention relates to CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and preparation and application, belong to optoelectronic pole Material Field.CdSe quantum dots uniform deposition with visible light characteristic is coated on titanic oxide nanorod array basal electrode surface, CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure optoelectronic pole is prepared.And CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is used for the oxidation of photoelectrocatalysis biomass derivatives and promotes hydrogen manufacturing.Compared with prior art, the present invention constructs out the glycoxidative promotion hydrogen manufacturing of CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure optoelectronic pole photoelectrocatalysis biomass derivatives grape.CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure optoelectronic pole not only shows excellent photoelectrochemical behaviour and repeatability, but also the glycoxidative hydrogen production activity of photoelectrocatalysis grape with superelevation.

Description

CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and preparation and application
Technical field
The present invention relates to a kind of optoelectronic pole materials, more particularly, to a kind of CdSe quantum dots sensitized titanium dioxide nanometer rods Optoelectronic pole and preparation and application.
Background technique
Since 21 century, solar energy receives researchers energetically as the inexhaustible energy Development and application, are such as converted into electric energy or hydrogen energy source for solar energy.Currently, the new energy of exploitation high-efficiency environment friendly, control System pollution reduces energy consumption, realizes that sustainable development is the eager desire of the people of the world.Therefore Hydrogen Energy has been converted solar energy into One of research hotspot and emphasis through becoming the world today.Currently, mainly passing through following three using decomposing water with solar energy hydrogen manufacturing A approach is realized: (1) light helps complex catalysis method.It is by manual simulation's photosynthesis hydrogen production by water decomposition process;(2) photocatalysis Semiconductor light-catalyst particle is suspended in water and carries out photolysis water hydrogen by hydrogen production by water decomposition, due to returning for photocatalyst granular It is complicated to receive and reuse uneconomical and process, limits its reusable property;(3) direct photoelectrochemical method.Pass through light sun Pole absorbs solar energy and is translated into electric energy, that is, is exactly that the excitation of light anode light generates light induced electron and hole pair, then Under the action of applying bias, photoelectron is efficiently promoted to be transferred to generation photoelectrocatalysis hydrogen production by water decomposition at cathode.
Since water is stable compound, generally require to apply during electro-catalysis hydrogen manufacturing than thermodynamics electrode potential The higher overpotential of 1.23V come drive water decomposition hydrogen production reaction occur.According to thermodynamic principles it is found that biomass derivatives species by In with relatively low oxidizing electrode potential, using the oxidation of biomass derivatives as substitution water oxygen, promote photoelectrocatalysis The application prospect of hydrogen production by water decomposition reaction is very extensive.In numerous photoelectrics, semiconductor material titanium dioxide is due to tool There is cheap a, stable chemical performance, environment compatibility is good and the characteristics such as photocatalytic activity height, it is considered to be most with prospects Photoelectrocatalysis agent material, but due to its wide forbidden band (3.2eV) make its can only occupied solar spectrum 5% ultraviolet light Spectrum is excited, to limit its application in real life.By the narrow-band semiconductor photoelectricity with visible light absorption In titanium dioxide electrodes surface, the light absorption and optical electro-chemistry that can significantly increase sample electrode are rung for catalyst nanoparticles modification It answers.Wherein, cadmium selenide is as typical N-shaped narrow-band semiconductor photoelectrocatalysis agent material (Eg=1.7eV), can be into visible light Row is effective to be absorbed and converts, but since its photostability is poor, greatly limits its application.
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 tool There are CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and the preparation and application of excellent visible light PhotoelectrocatalytiPerformance Performance, and The oxidation of efficient photoelectricity treater catalysis biomass derivative can be carried out by CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole Hydrogen manufacturing.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, by the cadmium selenide quantum with visible light characteristic Point uniform deposition is coated on titanic oxide nanorod array basal electrode surface, and CdSe quantum dots sensitization titanium dioxide is prepared Titanium nanorod heterojunction structure optoelectronic pole.CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure photoelectricity of the invention simultaneously Extremely heterojunction structure optoelectronic pole.
The preparation method of the CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, comprising the following steps:
(1) titanium dioxide nano-rod basal electrode is prepared:
Titanium source is instilled in acid solution, after persistently stirring 10~60min, above-mentioned mixed solution is transferred to polytetrafluoroethylene (PTFE) In inner liner stainless steel autoclave, then the clean FTO electrode of surface clean is placed in mixed solution, and its conducting surface It places downwards;50~200 DEG C of 3~6h of sustained response;When being cooled to room temperature, with secondary distilled water cleaning electrode surface, preparation Obtain titanium dioxide nano-rod basal electrode;
In this step, the titanium source be 99% or more purity butyl titanate, the acid solution be concentration 3~ The volume ratio of the HCl solution of 12mol/L, the titanium source and acid solution is 1:5~5:1.
(2) CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared:
The titanium dioxide nano-rod basal electrode that step (1) obtains is placed in Na2SeSO3、Cd(NO3)2It is mixed with sodium citrate It closes in solution, after (preferably 60 DEG C) 5~20min of water-bath 40~80 DEG C subsequent, with secondary distilled water cleaning sample electricity CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared in pole surface.
In this step, Na2SeSO3Solution preparation process is that Se powder is placed in Na2SO3Solution, 50~100 DEG C are refluxed overnight. Na2SeSO3Solution and Cd (NO3)2It is mixed in equal volume with sodium citrate mixed solution, Na2SeSO3The concentration of solution be 0.05~ 0.3mol/L, preferably 0.1mol/L, Cd (NO3)2In sodium citrate mixed solution, Cd (NO3)2Concentration be 0.01~ 0.05mol/L, preferably 0.02mol/L, the concentration of sodium citrate are 0.1~1mol/L, preferably 0.5mol/L.
The present invention is by the CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole and photoelectrocatalysis hydrogen producing technology It combines, realizes the oxidation of efficient photoelectricity treater catalysis biomass derivative and promote photoelectron transfer hydrogen manufacturing research.
The CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is used for photoelectrocatalysis biomass derivatives oxygen Change and 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, is sensitized with CdSe quantum dots Titanium dioxide nano-rod optoelectronic pole is used as reference electrode as cathode, saturated calomel electrode (SCE) as light anode, platinized platinum;
(2) prepare the KOH electrolyte solution containing biomass derivatives, the KOH concentration of electrolyte solutions be 0.1~ 1mol/L, concentration of the biomass derivatives in KOH electrolyte solution are 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.
The biomass derivatives are glucose.
Titanium dioxide even stick is modified in FTO by a simple step modified solvent-thermal method first in the present invention Titanium dioxide nano-rod basal electrode is prepared in basal electrode surface.Since titanium dioxide nano-rod has excellent photoelectricity Chemical stability, the characteristics such as big specific surface area and good bio-compatibility become the most commonly used photoelectricity of research and urge Agent material.Narrow-band semiconductor is nano-particle modified in titanium dioxide basal electrode surface, it can significantly improve sample electrode Optical absorption characteristic and its optical electro-chemistry activity and stability.In the present invention, by chemical bath deposition method, by cadmium selenide quantum The selenium with excellent visible light photoelectrochemical behaviour is prepared in titanium dioxide nano-rod basal electrode surface in point uniform deposition The quantum dot sensitized titanium dioxide nano-rod optical anode material of cadmium can not only significantly increase heterojunction structure light anode photoelectricity and urge The glycoxidative hydrogen production activity of metaplasia material derivant grape, and the easy photoetch of cadmium selenide in sample electrode can be effectively improved (density of photocurrent value is from 7.21 initial μ A/cm2, 3.66 μ A/cm are reduced to after the visible light in 5 periods circulation2) ask Topic.
The present invention constructs out CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure optoelectronic pole photoelectrocatalysis biology The glycoxidative promotion hydrogen manufacturing of matter derivative grape.CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure optoelectronic pole is not only in Reveal excellent photoelectrochemical behaviour and repeatability, i.e., its density of photocurrent value after the visible light loop test in 5 periods Still maintain 10.28 μ A/cm2.As a result the CdSe quantum dots sensitized titanium dioxide that the present invention is prepared is further demonstrated that Nanorod heterojunction structure optoelectronic pole 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 photoelectron is promoted to be transferred to Pt yin Hydrogen production by water decomposition at pole.
(2) CdSe quantum dots are uniformly wrapped on titanium dioxide nano-rod basal electrode surface by the present invention.Due to selenizing Cadmium quantum dot has excellent visible absorption and conversion characteristic, can significantly increase CdSe quantum dots sensitized titanium dioxide and receive Absorption and conversion characteristic of the rice stick heterojunction structure optoelectronic pole to visible light, further increase the photoelectrocatalysis hydrogen manufacturing of sample electrode Energy.
(3) modification of quantum size cadmium selenide nano particles is coated on titanium dioxide nano-rod basal electrode table by the present invention Face forms heterojunction structure optoelectronic pole, and by fast transfer light induced electron and hole pair, it is rotten to efficiently solve cadmium selenide visible light light Erosion problem significantly increases sample electrode stability of material problem.
(4) present invention will be using CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure as light anode photoelectrocatalysis The glycoxidative hydrogen manufacturing of grape, hydrogen output are up to 142.72 μm of ol/cm2, hydrogen output is 9.82 times of pure photodegradation water hydrogen manufacturing amount.
Detailed description of the invention
Fig. 1 is the shape appearance figure for the CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole that the present invention is prepared.
Fig. 2 is the glycoxidative promotion hydrogen manufacturing color of CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole photoelectrocatalysis grape Spectrogram.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method of CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, comprising the following steps:
(1) at room temperature, 0.35mL butyl titanate (99%) is added dropwise to 15mL6mol/LHCl solution dropwise In, after acutely persistently stirring 30min, above-mentioned mixed solution is transferred in 25mL polytetrafluoro inner liner stainless steel autoclave, Then the clean FTO electrode of surface clean is placed in mixed solution, and its conduction is placed downwards;It is held at 150 DEG C of constant temperature Continuous reaction 4h;When being cooled to room temperature, with secondary distilled water cleaning sample electrode surface, titanium dioxide nano-rod base is prepared Hearth electrode.
(2) titanium dioxide nano-rod basal electrode in step (1) is placed in brand-new 8ml0.1mol/LNa2SeSO3With it is identical Volume 0.02mol/LCd (NO3)2In 0.5mol/L sodium citrate mixed solution.Wherein, Na2SeSO3The preparation of solution Journey is that Se powder is placed in Na2SO3Solution, 80 DEG C are refluxed overnight.Then in 60 DEG C of water-baths of constant temperature after thermal response 15min, use is secondary CdSe quantum dots sensitized titanium dioxide nanometer rods composite heterogenous junction structure photoelectricity is prepared in distilled water cleaning sample electrode surface Pole.As shown in Figure 1, a large amount of CdSe quantum dots are modified in titanium dioxide nano-rod surface, not to its surface texture and nanometer The gap formed between stick results in blockage.
Embodiment 2
At room temperature, optical electro-chemistry is carried out on CHI660c electrochemical workstation using traditional three-electrode system It can test, using CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole prepared by embodiment 1 as light anode, platinized platinum conduct Cathode, saturated calomel electrode (SCE) are used as reference electrode.It is molten in the 0.5mol/LKOH electrolyte containing 0.1mol/L glucose In liquid, ampere i-t curve test is carried out to CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole.It is aoxidized compared to pure water (0.01mA/cm2), biomass derivatives glucose is easier to that oxidation reaction occurs at photoelectricity pole surface, and then increases sample electricity Density of photocurrent value (the 0.07mA/cm of pole2)。
Embodiment 3
It is equipped in three electrode reactors of self-control and vacuum air-channel in sealing gas circulating system, is prepared into embodiment 1 The CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole arrived is as light anode, and platinized platinum is as cathode and saturated calomel electrode (SCE) reference electrode, electrolyte solution are as follows: the 0.5mol/LKOH electrolyte solution containing 0.1mol/L glucose are used as.300W Visible filter is as visible light source and application -0.3V (vs.SCE) is biased at Pt cathode for the outfit of short arc Xe lamp.Finally lead to It crosses online gas-chromatography (GC) outfit thermal conductivity sensor (TCD) and carries out qualitative and quantitative determination to gas is collected.As shown in Figure 2 (in Fig. 2, curve is respectively 1h, 1.5h, 2h, 2.5h, 3h, 4h, 5h, 6h from bottom to top), at Pt cathode the yield of hydrogen with The incremental of reaction time shows the trend being gradually increased.CdSe quantum dots sensitized titanium dioxide nanorod heterojunction structure photoelectricity The glycoxidative hydrogen manufacturing amount of aurora electro-catalysis grape is up to 142.72 μm of ol/cm2, it is 9.82 times of photolysis water hydrogen amount.
Embodiment 4
A kind of CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, by the cadmium selenide quantum with visible light characteristic Point uniform deposition is coated on titanic oxide nanorod array basal electrode surface, and CdSe quantum dots sensitization titanium dioxide is prepared Titanium nanorod heterojunction structure optoelectronic pole.Specific preparation method the following steps are included:
(1) titanium dioxide nano-rod basal electrode is prepared:
1:5 by volume instills the butyl titanate of 99% or more purity in the HCl solution of concentration 3mol/L, continues After stirring 10min, above-mentioned mixed solution is transferred in polytetrafluoroethyllining lining stainless steel autoclave, it is then that surface is clear The FTO electrode of wash clean is placed in mixed solution, and its conduction is placed downwards;50 DEG C of sustained response 6h;It is cooled to room Titanium dioxide nano-rod basal electrode is prepared with secondary distilled water cleaning electrode surface in Wen Shi;
(2) CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared:
The titanium dioxide nano-rod basal electrode that step (1) obtains is placed in Na2SeSO3、Cd(NO3)2It is mixed with sodium citrate It closes in solution, wherein Na2SeSO3Solution and Cd (NO3)2It is mixed in equal volume with sodium citrate mixed solution, Na2SeSO3Solution Concentration be 0.05mol/L, Cd (NO3)2In sodium citrate mixed solution, Cd (NO3)2Concentration be 0.01mol/L, lemon The concentration of sour sodium is 0.1mol/L.Na2SeSO3Solution preparation process is that Se powder is placed in Na2SO3Solution, 50 DEG C are refluxed overnight system ?.After subsequent 40 DEG C of water-bath 20min, with secondary distilled water cleaning sample electrode surface, CdSe quantum dots are prepared Sensitized titanium dioxide nanometer rods optoelectronic pole.
In the present embodiment, CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole obtained is used for photoelectrocatalysis Portugal 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, is sensitized with CdSe quantum dots Titanium dioxide nano-rod optoelectronic pole is used as reference electrode as cathode, saturated calomel electrode (SCE) as light anode, platinized platinum;
(2) the KOH electrolyte solution containing glucose is prepared, KOH concentration of electrolyte solutions is 0.1mol/L, and glucose exists Concentration 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 CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, by the cadmium selenide quantum with visible light characteristic Point uniform deposition is coated on titanic oxide nanorod array basal electrode surface, and CdSe quantum dots sensitization titanium dioxide is prepared Titanium nanorod heterojunction structure optoelectronic pole.Specific preparation method the following steps are included:
(1) titanium dioxide nano-rod basal electrode is prepared:
1:1 by volume instills the butyl titanate of 99% or more purity in the HCl solution of concentration 8mol/L, continues After stirring 40min, above-mentioned mixed solution is transferred in polytetrafluoroethyllining lining stainless steel autoclave, it is then that surface is clear The FTO electrode of wash clean is placed in mixed solution, and its conduction is placed downwards;100 DEG C of sustained response 4.5h;It is cooled to When room temperature, with secondary distilled water cleaning electrode surface, titanium dioxide nano-rod basal electrode is prepared;
(2) CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared:
The titanium dioxide nano-rod basal electrode that step (1) obtains is placed in Na2SeSO3、Cd(NO3)2It is mixed with sodium citrate It closes in solution, wherein Na2SeSO3Solution and Cd (NO3)2It is mixed in equal volume with sodium citrate mixed solution, Na2SeSO3Solution Concentration be 0.1mol/L, Cd (NO3)2In sodium citrate mixed solution, Cd (NO3)2Concentration be 0.02mol/L, citric acid The concentration of sodium is 0.5mol/L.Na2SeSO3Solution preparation process is that Se powder is placed in Na2SO3Solution, 80 DEG C are refluxed overnight system ?.After subsequent 60 DEG C of water-bath 10min, with secondary distilled water cleaning sample electrode surface, CdSe quantum dots are prepared Sensitized titanium dioxide nanometer rods optoelectronic pole.
In the present embodiment, CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole obtained is used for photoelectrocatalysis Portugal 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, is sensitized with CdSe quantum dots Titanium dioxide nano-rod optoelectronic pole is used as reference electrode as cathode, saturated calomel electrode (SCE) as light anode, platinized platinum;
(2) the KOH electrolyte solution containing glucose is prepared, KOH concentration of electrolyte solutions is 0.5mol/L, and glucose exists Concentration 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 CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, by the cadmium selenide quantum with visible light characteristic Point uniform deposition is coated on titanic oxide nanorod array basal electrode surface, and CdSe quantum dots sensitization titanium dioxide is prepared Titanium nanorod heterojunction structure optoelectronic pole.Specific preparation method the following steps are included:
(1) titanium dioxide nano-rod basal electrode is prepared:
5:1 by volume instills the butyl titanate of 99% or more purity in the HCl solution of concentration 12mol/L, continues After stirring 60min, above-mentioned mixed solution is transferred in polytetrafluoroethyllining lining stainless steel autoclave, it is then that surface is clear The FTO electrode of wash clean is placed in mixed solution, and its conduction is placed downwards;200 DEG C of sustained response 3h;It is cooled to room Titanium dioxide nano-rod basal electrode is prepared with secondary distilled water cleaning electrode surface in Wen Shi;
(2) CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared:
The titanium dioxide nano-rod basal electrode that step (1) obtains is placed in Na2SeSO3、Cd(NO3)2It is mixed with sodium citrate It closes in solution, wherein Na2SeSO3Solution and Cd (NO3)2It is mixed in equal volume with sodium citrate mixed solution, Na2SeSO3Solution Concentration be 0.3mol/L, Cd (NO3)2In sodium citrate mixed solution, Cd (NO3)2Concentration be 0.05mol/L, citric acid The concentration of sodium is 1mol/L.Na2SeSO3Solution preparation process is that Se powder is placed in Na2SO3Solution, 100 DEG C be refluxed overnight it is obtained. After subsequent 80 DEG C of water-bath 5min, with secondary distilled water cleaning sample electrode surface, CdSe quantum dots sensitization is prepared Titanium dioxide nano-rod optoelectronic pole.
In the present embodiment, CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole obtained is used for photoelectrocatalysis Portugal 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, is sensitized with CdSe quantum dots Titanium dioxide nano-rod optoelectronic pole is used as reference electrode as cathode, saturated calomel electrode (SCE) as light anode, platinized platinum;
(2) the KOH electrolyte solution containing glucose is prepared, KOH concentration of electrolyte solutions is 1mol/L, and glucose exists Concentration 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 (7)

1. a kind of preparation method of CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole, which is characterized in that will have can The CdSe quantum dots uniform deposition of light-exposed characteristic is coated on titanic oxide nanorod array basal electrode surface, and selenium is prepared The quantum dot sensitized titanium dioxide nano-rod heterojunction structure optoelectronic pole of cadmium, comprising the following steps:
(1) titanium dioxide nano-rod basal electrode is prepared:
Titanium source is instilled in acid solution, after lasting stirring, it is high that above-mentioned mixed solution is transferred to polytetrafluoroethyllining lining stainless steel It presses in reaction kettle, then the clean FTO electrode of surface clean is placed in mixed solution, and its conduction is placed downwards;50 ~200 DEG C of 3~6h of sustained response;When being cooled to room temperature, with secondary distilled water cleaning electrode surface, titanium dioxide is prepared Nanometer rods basal electrode;
(2) CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole is prepared:
The titanium dioxide nano-rod basal electrode that step (1) obtains is placed in Na2SeSO3、Cd(NO3)2It is mixed with sodium citrate molten In liquid, after subsequent water-bath, with secondary distilled water cleaning sample electrode surface, CdSe quantum dots sensitization two is prepared TiOx nano stick optoelectronic pole.
2. the preparation method of CdSe quantum dots sensitized titanium dioxide nanometer rods light anode according to claim 1, special Sign is, titanium source described in step (1) is the butyl titanate of 99% or more purity, the acid solution be concentration 3~ The volume ratio of the HCl solution of 12mol/L, the titanium source and acid solution is 1:5~5:1.
3. the preparation method of CdSe quantum dots sensitized titanium dioxide nanometer rods light anode according to claim 1, special Sign is, Na in step (2)2SeSO3Solution and Cd (NO3)2It is mixed in equal volume with sodium citrate mixed solution, Na2SeSO3Solution Concentration be 0.05~0.3mol/L, Cd (NO3)2In sodium citrate mixed solution, Cd (NO3)2Concentration be 0.01~ 0.05mol/L, the concentration of sodium citrate are 0.1~1mol/L.
4. the preparation method of CdSe quantum dots sensitized titanium dioxide nanometer rods light anode according to claim 1, special Sign is that the temperature of water-bath is 40~80 DEG C in step (2), and the time of water-bath is 5~20min.
5. CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole obtained by preparation method is answered according to claim 1 With, which is characterized in that the CdSe quantum dots sensitized titanium dioxide nanometer rods optoelectronic pole spreads out for photoelectrocatalysis biomass Biological oxidation promotes hydrogen manufacturing, and the biomass derivatives are glucose.
6. applying according to claim 5, which is characterized in that specifically includes the following steps:
(1) it is equipped with three electrode reactors and vacuum air-channel in sealing gas circulating system, is sensitized dioxy with CdSe quantum dots Change titanium nanometer rods optoelectronic pole as light anode, platinized platinum is as cathode, and saturated calomel electrode is as reference electrode;
(2) the KOH electrolyte solution containing biomass derivatives 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.
7. applying according to claim 6, which is characterized in that in step (2), the KOH concentration of electrolyte solutions is 0.1 ~1mol/L, concentration of the biomass derivatives in KOH electrolyte solution are 0.05~0.3mol/L.
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