CN104821405A - Titanium dioxide nanotube modified electrode with PSII assembled surface, preparation method and application thereof - Google Patents

Titanium dioxide nanotube modified electrode with PSII assembled surface, preparation method and application thereof Download PDF

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CN104821405A
CN104821405A CN201510107503.3A CN201510107503A CN104821405A CN 104821405 A CN104821405 A CN 104821405A CN 201510107503 A CN201510107503 A CN 201510107503A CN 104821405 A CN104821405 A CN 104821405A
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psii
electrode
titanium dioxide
preparation
modified electrode
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CN104821405B (en
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李峻柏
李姣
冯熙云
蔡鹏�
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Institute of Chemistry CAS
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Abstract

The invention discloses a titanium dioxide nanotube modified electrode with a PSII (photosystem II) assembled surface, a preparation method and application thereof. The preparation method comprises the steps of: 1) transferring a suspension liquid of titanium dioxide nanotubes dispersed in an organic solvent to the surface of a bare electrode, and conducting drying and film forming so as to obtain a titanium dioxide nanotube modified electrode; 2) transferring a PSII solution dissolved in a buffer solution to the film surface, and performing drying to obtain the titanium dioxide nanotube modified electrode with a PSII assembled surface. In the invention, natural cellulose is selected as the template, and the synthesized material has a large specific surface area and a multistage network structure, thus being beneficial to adsorption of PSII on the electrode surface modified by the material. The PSII is directly assembled on the nano-tubular titanium dioxide modified electrode surface, thus being more beneficial to the direct action of PSII and titanium dioxide. Dye sensitization of titanium dioxide is unnecessary, and the dye pollution to the environment is reduced. With very superior photocurrent response under the excitation of red light and white light, the electrode is stable.

Description

A kind of surface-assembled titanic oxide nanometer tube modified electrode having PSII and preparation method thereof and application
Technical field
The present invention relates to a kind of PSII modified electrode and preparation method thereof and application, particularly relate to a kind of surface-assembled titanic oxide nanometer tube modified electrode having PSII and preparation method thereof and application.
Background technology
At occurring in nature, photosynthesis is the basis that living nature is depended on for existence, is also the important bridge of earth carbon oxygen cycle.Photosynthesis in the middle of plant, mainly under the irradiation of visible ray, through light reaction and dark reaction, utilizes photosynthetic pigments, and carbon dioxide and water are converted into organic substance, and discharges the biochemical process of oxygen.Wherein, Photosystem I I (PSII) is the many subunits photosynthetic pigments albumen composition be present in thylakoid membrane, as a kind of important memebrane protein in photosynthesis chain, have and efficiently draw and transmit electronics in water, produce oxygen, and produce the effect that proton gradient drives ATP synthesis.The efficiency that PSII produces electron-hole is under light illumination very high, is the efficient enzyme of solar energy water oxidation.Therefore, PSII can be used for Prof. Du Yucang solar energy clean energy resource system as natural catalyst.At present, protein film Optical Electro-Chemistry (PF-PEC) is widely used in manually preparing based in the electrode system of PSII as a kind of simple and convenient technology, and it is adsorbed on having photoactive PSII on electrode surface for studying and obtaining photoelectric current.At present, on electrode, the approach of effectively fixing PSII has following several: the first approach assembles PSII on nano structure electrode.The electrode of nanostructure can increase the effective surface area of electrode to the full extent, PSII is embedded in the material of nanostructure, thus increases the assembling amount of PSII.The second approach is the electrode surface assembling PSII modifying self assembled monolayer.This mode can make PSII NW-TFT at the electrode surface of functionalization, thus is conducive to the orientation transmission of electronics.The third approach modifies redox polymers on electrode, by PSII embedded polymer thing.This system can make electronics effectively transmit between the PSII embedded and electrode by the kind changing polymer.4th kind of approach is the poly-isoelectric substance replacing sedimentary facies counter charges by the method for layer assembly on electrode, PSII is embedded in different layers, thus effectively drives electronics to transmit between the layers.But, the existing Technical comparing complexity that electrode surface is modified, or in electrode production process, certain harm is produced to environment.At present, for the electrode of PSII protein film PhotoelectrochemicalTechnique Technique mainly through ITO electrode, the gold electrode and platinum electrode etc. of finishing or process.
Titanium dioxide has the performance of photocatalytic water under ultraviolet excitation, and dye-sensitized titania can carry out photocatalytic water under the irradiation of visible ray.But, at present PSII and titanium dioxide are carried out compound and be used for photocatalytic water and produce the research of photoelectric current but very limited.
Summary of the invention
An object of the present invention is to provide a kind of surface-assembled and have titanic oxide nanometer tube modified electrode of PSII (photosystem II, Photosystem I I) and preparation method thereof and application.PSII is the many subunits photosynthetic pigments albumen composition be present in thylakoid membrane, as a kind of important memebrane protein in photosynthesis chain, has and efficiently draws and transmit electronics in water, produce oxygen, and produce the effect that proton gradient drives ATP synthesis.The present invention utilizes native cellulose as the template of surface sol-gel legal system for nanotube-shaped titanium dioxide, the nanotube-shaped titanium dioxide prepared has larger specific area and multistage network structure, to PSII, there is good suction-operated, be conducive to PSII and titanium dioxide direct effect, the composite modified electrode prepared all has very superior photocurrent response under the exciting of ruddiness or white light simultaneously.
A kind of surface-assembled provided by the invention has the preparation method of the titanic oxide nanometer tube modified electrode of PSII, comprises the steps:
(1) suspension of dispersion titania nanotube is in a solvent transferred to the surface of bare electrode, film forming after dry, obtains titanic oxide nanometer tube modified electrode;
(2) the PSII solution be dissolved in cushioning liquid is transferred to the surface of described film, after drying, namely obtains the titanic oxide nanometer tube modified electrode that described surface-assembled has PSII.
Above-mentioned preparation method, in step (1), the transfer amount of described suspension can be 10 ~ 30 μ L, specifically can be 20 μ L;
Described titania nanotube is added ultrasonic disperse 5 ~ 20min in solvent, specifically can be 10min, described suspension can be obtained;
Described solvent is any one in ethanol, acetone, methyl alcohol, toluene and water;
In described suspension, the concentration of described titania nanotube is 5 ~ 20mg/mL, specifically can be 10mg/mL.
Above-mentioned preparation method, in step (1), described titania nanotube prepares by following method: take cellulose as template, by surface sol-gel method at described fiber surface parcel titanium dioxide nano-film, described template is removed in calcining in atmosphere again, specifically can adopt the quantitative filter paper interweaved by micron order fleece;
The temperature of described calcining can be 450 ~ 550 DEG C, specifically can be 500 DEG C; Programming rate can be 1 ~ 3 DEG C/min, specifically can be 1 DEG C/min; Calcination time can be 4 ~ 8h, specifically can be 6h;
Controlled the thickness of described titanium dioxide nano-film by the cycle-index controlling described surface sol-gel method, the number of plies obtaining described titania nanotube can be 5 ~ 20 layers, specifically can be 5 ~ 10 layers, 10 ~ 20 layers, 5 layers, 10 layers or 20 layers; The diameter of described titania nanotube can be 50 ~ 200nm; The diameter forming the titanium dioxide granule of its tube wall can be 5 ~ 20nm, specifically can be 10 ~ 14nm, 10nm, 11nm or 14nm.
The titania nanotube that above-mentioned preparation method prepares replicates the multistage network structure of described fiber, has larger specific area, and the adsorbance of PSII can increase greatly.
Above-mentioned preparation method, in step (1), described bare electrode is any one in ITO electrode, gold electrode and platinum electrode;
Described drying is that high pure nitrogen dries up or air dries.
Above-mentioned preparation method, in step (2), the transfer amount of described PSII solution can be 10 ~ 30 μ L, specifically can be 10 ~ 20 μ L, 20 ~ 30 μ L, 10 μ L, 20 μ L or 30 μ L;
In described PSII solution, chlorophyllous concentration can be 0.5 ~ 2mg/mL, specifically can be 1mg/mL, described PSII obtains by extracting in spinach or blue-green algae, described cushioning liquid is MES cushioning liquid or PBS, and its pH value can be 6.0 ~ 7.5, specifically can be 6.5;
Described drying is that high pure nitrogen dries up or air dries, and preserves 1h before described drying in 4 DEG C, to reach the abundant absorption of PSII albumen in modified electrode nanostructure hole and to keep PSII protein active.
Invention further provides the titanic oxide nanometer tube modified electrode that a kind of surface-assembled utilizing above-mentioned preparation method to prepare has PSII, contrasted by the electrode system of assembling PSII with not modified electrode surface and the modified electrode that is only modified with titania nanotube, modified electrode of the present invention obviously can produce stronger density of photocurrent.
Above-mentioned surface-assembled has the titanic oxide nanometer tube modified electrode of PSII preparing the application in photoelectrochemical cell or solar energy photocatalytic water.
In above-mentioned application, adopt ruddiness or white light as exciting light, the intensity of described exciting light can be 5 ~ 100mW/cm 2, specifically can be 10 ~ 20mW/cm 2, 10mW/cm 2or 20mW/cm 2, by adding 800nm and/or 550nm filter to obtain the exciting light that wave-length coverage is ruddiness or white light between xenon source and electrochemical cell.
Tool of the present invention has the following advantages:
(1) select native cellulose as the template of surface sol-gel legal system for nanotube-shaped titanium dioxide in the present invention, its wide material sources, cheap, the quantitative filter paper selected is interwoven by many micron order fleeces, and these micron order fibers are interwoven by many nano-scale fiber bindings, there is multi-layer fibrous reticular structure, there is using it as the material synthesized by template larger specific area and multistage network structure, be conducive to the electrode surface absorption PSII modified with it.
(2) in the present invention by the electrode surface that PSII direct-assembling is modified at nanotube-shaped titanium dioxide, be more conducive to PSII and titanium dioxide direct effect, simultaneously without the need to dye-sensitized titania, decrease the pollution of Dyes on Environment.
(3) the titanic oxide nanometer tube modified electrode of the PSII/ prepared in the present invention all has very superior photocurrent response under the exciting of ruddiness and white light, and electrode is more stable.
Accompanying drawing explanation
Fig. 1 is electron scanning micrograph and the transmission electron microscope photo of five layers, ten layers, 20 layers titania nanotube of preparation in embodiment 1, wherein Fig. 1 (a), (c) and (e) are respectively the electron scanning micrograph of five layers, ten layers and 20 layers titania nanotube, and Fig. 1 (b), (d) and (f) are respectively the transmission electron microscope photo of five layers, ten layers and 20 layers titania nanotube.
Fig. 2 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified five layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent that produces at the Direct electron transfer (DET) having modified five layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 1.
Fig. 3 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified five layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent produced at indirect electron transfer (MET) having modified five layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 1.
Fig. 4 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified ten layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent that produces at the Direct electron transfer (DET) having modified ten layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 2.
Fig. 5 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified ten layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent produced at indirect electron transfer (MET) having modified ten layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 2.
Fig. 6 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified 20 layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent that produces at the Direct electron transfer (DET) having modified 20 layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 3.
Fig. 7 is at the electrode of not modified electrode surface assembling PSII, the electrode having modified 20 layers of nanotube-shaped titanium dioxide and the block diagram of density of photocurrent produced at indirect electron transfer (MET) having modified 20 layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode in embodiment 3.
Fig. 8 is at the electrode of not modified electrode surface assembling PSII with modifying five layers of nanotube-shaped titanium dioxide electrodes surface-assembled PSII electrode and to excite at continuous red light the photoelectric current attenuation curve in time of lower generation in embodiment 4.Illustration is the photoelectric current attenuation curve of the simple PSII modified electrode amplified.
Embodiment
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In following embodiment, bare electrode used is ITO electrode, specifically can adopt ITO electro-conductive glass, and ITO electro-conductive glass used is all pretreated as follows: commercial ITO electro-conductive glass glass cutter is cut into 0.6 × 1.2cm 2size, first ultrasonic 20min in ultra-pure water, then uses EtOH Sonicate 20min, then dries up with high pure nitrogen.
In following embodiment, use three-electrode system electrochemical workstation to carry out electrochemical analysis test to the electrode prepared: work electrode be respectively the preparation-obtained electrode at not modified electrode surface assembling PSII, the nanotube-shaped titanium dioxide of finishing electrode and modifying the nanotube-shaped titanium dioxide electrodes surface-assembled electrode of PSII, be platinum electrode to electrode, reference electrode is saturated calomel electrode (SCE);
Electrolyte used is for containing 50mM KCl, 10mM MgCl 2, 3mM CaCl 2with the aqueous solution of 20mM MES, pH is 6.5.The bias-voltage adding 0.25V between work electrode and reference electrode is stood in by electrochemical operation.
In following embodiment, light source used is xenon lamp, obtains by the filter adding 800nm and/or 550nm between electrochemical cell and xenon lamp lamp source the exciting light that wave-length coverage is ruddiness or white light.
In following embodiment, electro-chemical test all at room temperature carries out.
The preparation of embodiment 1, PSII/ five layers of titanic oxide nanometer tube modified electrode and electro-chemical test thereof
(1) from spinach, PSII is extracted according to following step:
Prepare following solution respectively: BBY-1: containing 40mM NaCl, 0.2wt%BSA, 2mM MgCl 2, the 20mM Tricine-NaOH solution (pH=7.8) of 2mM vitamin C and 400mM sucrose; BBY-2: containing 10mMNaCl, 0.2%BSA and 5mM MgCl 220mM Tricine-NaOH solution (pH=7.8); BBY-3: containing 15mM NaCl, 5mM MgCl 2with the 20mM MES-NaOH solution (pH=6.5) of 400mM sucrose; BBY-3T: prepare 20% (w/v) Tritox-100 with BBY-3; BBY-4: containing 15mM NaCl, 5mM MgCl 2, the 20mM MES solution (pH=6.5) of 400mM sucrose and 500mM betaine.
Following steps are all carried out under 4 DEG C and greenism light.All appts, glassware and centrifuge tube etc. all need precooling, and leaching process completes in 5h.
After spinach is clean, in refrigerator, 4 DEG C of lucifuges place more than 5h.
The leaf of spinach cleaned is removed arteries and veins in leaf, is torn into fritter, granular to millet with BBY-1 homogenate according to the ratio (100g the leaf of spinach: 300mLBBY-1) of 1:3, by 8 layers of filtered through gauze; Filtrate centrifugal 1min under 400g rotating speed, to remove mesophyll cell, gets supernatant; Centrifugal 15min under 6000rpm rotating speed, gets precipitation and is chloroplaset; By the resuspended precipitation of 100mL BBY-2, stir 15min to make chloroplaset broken; By this suspension-turbid liquid centrifugal 2min under 250g rotating speed, get supernatant; Centrifugal 15min under 7000g rotating speed, gets and is precipitated as thylakoid membrane again; Precipitation will be changed resuspended with 15mL BBY-3; Amount volume, surveys chlorophyllous content with ultraviolet-visible spectrophotometer, adds BBY-3 and regulates chlorophyll concentration to be 2mg/mL; Slow dropping BBY-3T, is 25:1 to Tritox-100/ chlorophyll (w/w), slowly stirs 10min; Under 10000g rotating speed, centrifugal 1min, gets supernatant liquor; Under 35000g rotating speed, centrifugal 30min, precipitation 40mL BBY-3 is resuspended, then under 35000g rotating speed centrifugal 20min, to supernatant redgreen; Resuspended with being less than 5mL BBY-4 again, obtain PSII and store liquid.
It is 3.2mg/mL that the PSII obtained stores liquid through the known wherein chlorophyll content of ultraviolet-visible spectrophotometer test.With pH for obtained PSII diluting stock solutions to chlorophyll content is 1mg/mL by the 6.5 concentration MES cushioning liquid that is 20mM, for subsequent use.
(2) preparation of titania nanotube
1) take volume ratio as the toluene of 1:1 and ethanol be solvent, configuration concentration is the butyl titanate solution of 100mM, and at room temperature stirs 1h.
2) middling speed quantitative filter paper conventional for laboratory is placed in Suction filtration device, with ethanol purge filter paper 3 times, vacuum is drained.
3) to step 2) Suction filtration device in add 20mL step 1) the butyl titanate solution prepared, suction filtration half solution, makes solution impregnation native cellulose, and remains the surface of liquid level higher than native cellulose, leave standstill 3min, this is deposition process.
4) low vacuum suction filtration butyl titanate solution is to liquid level a little more than its surface, adds alcohol solvent rapidly, rinse 6 times, and adds this solvent of 20mL, leave standstill 3min, low vacuum suction filtration, then add ultra-pure water rinse 4 times, and add the ultra-pure water of 20mL, leave standstill 3min, this is hydrolytic process.Vacuum filtration 15min in atmosphere after hydrolysis is dry to filter paper.
5) step 3) and 4) middle liquid level should all the time higher than its surface.This deposits, is hydrolyzed to cyclic process, circulates 5 times, obtains the filter paper fibre of titanium dioxide nano-film parcel.
6) by step 5) in deposited titanium deoxid film filter paper be placed in vacuum drying chamber dried overnight at 60 DEG C; Calcine 6h at 500 DEG C in atmosphere, heating rate is 1 DEG C/min, obtains nanotube-shaped titanic oxide material.
The electron scanning micrograph of five layers of nanotube-shaped titanic oxide material of above-mentioned preparation is as shown in Fig. 1 (a), transmission electron microscope photo is as shown in Fig. 1 (b), as known in the figure, five layers of nanotube-shaped titanic oxide material prepared by the present embodiment replicate the multistage network structure of filter paper fibre, titania nanotube diameter is 50-200nm, and the titanium dioxide granule size of composition nanotube walls is about 11nm.
By the nanotube-shaped titanic oxide material ultrasonic disperse of above-mentioned preparation in ethanol, ultrasonic time is 10min (power is 100W), and the suspension concentration obtained is 10mg/mL, for subsequent use.
(3) preparation of PSII/ five layers of titanic oxide nanometer tube modified electrode:
A, comparison electrode: the electrode of not modified electrode surface assembling PSII
Be that the PSII solution liquid-transfering gun transferase 12 0 μ L of 1mg/mL is extremely through pretreated ITO conductive glass surface by the chlorophyll content after dilution, take out place 1h in 4 DEG C of refrigerators after, dry up with high pure nitrogen, obtain the electrode at not modified electrode surface assembling PSII.
B, comparison electrode: nanotube-shaped titanium dioxide modified electrode
By the titania nanotube suspension liquid-transfering gun transferase 12 0 μ L of 10mg/mL to through pretreated ITO conductive glass surface, dry in atmosphere, obtain the electrode having modified nanotube-shaped titanium dioxide.
C, modified electrode of the present invention:
By 10mg/mL titania nanotube suspension liquid-transfering gun transferase 12 0 μ L to through pretreated ITO conductive glass surface, dry in atmosphere, obtain the electrode having modified titania nanotube;
Be that the PSII solution liquid-transfering gun transferase 12 0 μ L of 1mg/mL is to the ITO electrode surface modifying nanotube-shaped titanium dioxide by the chlorophyll content after dilution, take out place 1h in 4 DEG C of refrigerators after, and dry up with high pure nitrogen, obtain at the electrode modifying nanotube-shaped titanium dioxide electrodes surface-assembled PSII.
(4) electro-chemical test of PSII/ five layers of titanic oxide nanometer tube modified electrode
Respectively with the above-mentioned three kinds of electrodes prepared for work electrode, three-electrode system is formed with saturated calomel electrode (SCE) and platinum electrode, with electrochemical workstation measuring current-time service curve, applying voltage is 0.25V, and the time interval is 20-100s.
Electrolyte used is for containing 50mM KCl, 10mM MgCl 2, 3mM CaCl 2with the aqueous solution of 20mM MES, pH is 6.5.The bias-voltage adding 0.25V between work electrode and reference electrode is stood in by electrochemical operation.
Between electrochemical cell and xenon lamp lamp source, add the filter of 550nm and 800nm to obtain wave-length coverage for ruddiness, intensity is 10mW/cm 2exciting light; The filter only placing 800nm obtains the exciting light that wave-length coverage is white light, and intensity is 20mW/cm 2.
A, Direct electron transfer
Using above-mentioned three kinds of electrodes as work electrode, respectively with ruddiness and white light for exciting light measurement obtains the block diagram of Direct electron transfer (DET) photocurrent response value as shown in Figure 2.As shown in Figure 2, the electrode that nanotube-shaped titanium dioxide is modified produces photocurrent response hardly under the exciting of ruddiness, can produce and be about 500nA/cm under the exciting of white light 2photocurrent response value; And under ruddiness and white light excite, all only can produce small photocurrent response at the electrode system of not modified electrode surface assembling PSII; The density of photocurrent of the titanic oxide nanometer tube modified electrode of PSII/ generation under the exciting of ruddiness is 6 times of the electrode system that simple PSII modifies; The density of photocurrent of the titanic oxide nanometer tube modified electrode of PSII/ generation under the exciting of white light is the electrode of simple PSII modification and 2.5 times of titanic oxide nanometer tube modified electrode photoelectric current density sum, proves that the titanic oxide nanometer tube modified electrode of PSII/ can be used for photolysis water hydrogen.
B, indirect electron shift
Add the chloro-Isosorbide-5-Nitrae-benzoquinones (DCBQ) of 1mM 2,5-bis-in the electrolytic solution as redox mediator, measurement obtains the block diagram of indirect electron transfer (MET) photocurrent response value as shown in Figure 3.As shown in Figure 3, the density of photocurrent that the density of photocurrent shifting the generation of (MET) approach by indirect electron produces than Direct electron transfer (DET) obviously increases; The titanic oxide nanometer tube modified electrode of PSII/ all has more superior indirect electron transfer (MET) photocurrent response under the exciting of ruddiness and white light, proves that the titanic oxide nanometer tube modified electrode of PSII/ can be used for photolysis water hydrogen.
Embodiment 2, the titania nanotube number of plies are on the impact of photocurrent response value
In order to contrast the carbon dioxide nanotube number of plies to the impact of photocurrent response, preparing PSII/ five layers of titanic oxide nanometer tube modified electrode, PSII/ ten layers of titanic oxide nanometer tube modified electrode and PSII/ 20 layers of titanic oxide nanometer tube modified electrode respectively and testing the response of its photoelectric current.
(1) preparation of PSII/ ten layers of titanic oxide nanometer tube modified electrode and electro-chemical test thereof
Prepare ten layers of titania nanotube substantially identical with parameter with the step of five layers of titania nanotube in embodiment 1, difference is: during nanotube-shaped titanic oxide material for the preparation of electrode face finish, increase to 10 times in the cycle-index of filter paper fibre surface deposition, hydrolyzed titanium dioxide nano thin-film, obtain the filter paper fibre of ten layers of titanium dioxide nano-film parcel.
The electron scanning micrograph of ten layers of nanotube-shaped titanic oxide material is as shown in Fig. 1 (c), transmission electron microscope photo is as shown in Fig. 1 (d), as known in the figure, ten layers of nanotube-shaped titanic oxide material prepared by the present embodiment replicate the multistage network structure of filter paper fibre, titania nanotube diameter is 50-200nm, and the titanium dioxide granule size of composition nanotube walls is about 10nm.
Each modified electrode is prepared according to the step in embodiment 1, at ten layers of titanic oxide nanometer tube modified electrode surface assembling PSII, Direct electron transfer (DET) and the indirect electron of measuring this electrode system respectively using ruddiness and white light as exciting light shift (MET) photocurrent response value.Direct electron transfer (DET) and indirect electron transfer (MET) test result are respectively as shown in Figure 4 and Figure 5.Basically identical in test result and embodiment 1.Under the exciting of ruddiness and white light, all there is more superior Direct electron transfer (DET) from the titanic oxide nanometer tube modified electrode of Fig. 4 and Fig. 5, PSII/ and indirect electron shifts (MET) photocurrent response.
(2) preparation of PSII/ 20 layers of titanic oxide nanometer tube modified electrode and electro-chemical test thereof
Prepare 20 layers of titania nanotube substantially identical with step with the parameter of five layers of titania nanotube in embodiment 1, difference is: during nanotube-shaped titanic oxide material for the preparation of electrode face finish, increase to 20 times in the cycle-index of filter paper fibre surface deposition, hydrolyzed titanium dioxide nano thin-film, obtain the filter paper fibre of titanium dioxide nano-film parcel.
The electron scanning micrograph of 20 layers of nanotube-shaped titanic oxide material of above-mentioned preparation is as shown in Fig. 1 (e), transmission electron microscope photo is as shown in Fig. 1 (f), as known in the figure, the 20 layers of titania nanotube diameter prepared are 50-200nm, and the titanium dioxide granule size of composition nanotube walls is about 14nm.
At 20 layers of titanic oxide nanometer tube modified electrode surface assembling PSII, Direct electron transfer (DET) and the indirect electron of measuring this electrode system respectively using ruddiness and white light as exciting light shift (MET) photocurrent response value.Direct electron transfer (DET) and indirect electron transfer (MET) test result are respectively as shown in Figure 6 and Figure 7.Basically identical in test result and embodiment 1,2.Under the exciting of ruddiness and white light, all there is more superior Direct electron transfer (DET) from the titanic oxide nanometer tube modified electrode of Fig. 6 and Fig. 7, PSII/ and indirect electron shifts (MET) photocurrent response.
Embodiment 3, PSII modification amount are on the impact of photocurrent response value
The step of the present embodiment is substantially identical with embodiment 1 with parameter, difference is: when the electrode surface assembling PSII modifying nanotube-shaped titanium dioxide, the PSII solution liquid-transfering gun being 1mg/mL by the chlorophyll content after dilution shifts 10 μ L, 20 μ L and 30 μ L respectively to the ITO electrode surface having modified five layers of nanotube-shaped titanium dioxide, obtains the modified electrode with different PSII modification amount.Electrochemical results shows, when modification amount is 10 μ L, 20 μ L and 30 μ L, the photocurrent response difference produced is little, and this mainly to occur in and between the PSII of modified electrode surface contact and electrode due to effective transmission of electronics.
Embodiment 4, electrode stability
The step of the present embodiment is substantially identical with embodiment 1 with parameter, and difference is: during electro-chemical test, the electrode modified as the exciting light difference titanic oxide nanometer tube modified electrode of Continuous irradiation PSII/ and simple PSII with ruddiness.Measurement obtains Direct electron transfer (DET) photocurrent response value, and curve is as shown in Figure 8 over time.As shown in Figure 8, the titanic oxide nanometer tube modified electrode of PSII/ is obviously longer than in the half-life that continuous red light excites lower photoelectric current to decay in time the half-life that simple PSII modified electrode excites lower photoelectric current to decay in time at continuous red light.Therefore, the stability of the titanic oxide nanometer tube modified electrode of PSII/ that prepared by the present invention is significantly improved.

Claims (8)

1. surface-assembled has a preparation method for the titanic oxide nanometer tube modified electrode of PSII, comprises the steps:
(1) suspension of dispersion titania nanotube is in organic solvent transferred to the surface of bare electrode, film forming after dry, obtains titanic oxide nanometer tube modified electrode;
(2) the PSII solution be dissolved in cushioning liquid is transferred to the surface of described film, after drying, namely obtains the titanic oxide nanometer tube modified electrode that described surface-assembled has PSII.
2. preparation method according to claim 1, is characterized in that: in step (1), and the transfer amount of described suspension is 10 ~ 30 μ L;
Described titania nanotube is added ultrasonic disperse 5 ~ 20min in solvent, described suspension can be obtained;
Described solvent is any one in ethanol, acetone, methyl alcohol, toluene and water;
In described suspension, the concentration of described titania nanotube is 5 ~ 20mg/mL.
3. preparation method according to claim 1 and 2, it is characterized in that: in step (1), described titania nanotube prepares by the following method: take cellulose as template, by surface sol-gel method at described fiber surface parcel titanium dioxide nano-film, more described template is removed in calcining in atmosphere;
The temperature of described calcining is 450 ~ 550 DEG C, and programming rate is 1 ~ 3 DEG C/min, and calcination time is 4 ~ 8h;
The thickness of described titanium dioxide nano-film is controlled by the cycle-index controlling described surface sol-gel method, the number of plies obtaining described titania nanotube is 5 ~ 20 layers, the diameter of described titania nanotube is 50 ~ 200nm, and the diameter forming the titanium dioxide granule of its tube wall is 5 ~ 20nm.
4. the preparation method according to any one of claim 1-3, is characterized in that: in step (1), and described bare electrode is any one in ITO electrode, gold electrode and platinum electrode;
Described drying is that high pure nitrogen dries up or air dries.
5. the preparation method according to any one of claim 1-4, is characterized in that: in step (2), and the transfer amount of described PSII solution is 10 ~ 30 μ L;
In described PSII solution, chlorophyllous concentration is 0.5 ~ 2mg/mL, and described PSII obtains by extracting in spinach or blue-green algae, and described cushioning liquid is MES cushioning liquid or PBS, and its pH value is 6.0 ~ 7.5;
Described drying is that high pure nitrogen dries up or air dries, and preserves 1h before described drying in 4 DEG C.
6. the surface-assembled that the preparation method according to any one of claim 1-5 prepares has the titanic oxide nanometer tube modified electrode of PSII.
7. surface-assembled according to claim 6 has the titanic oxide nanometer tube modified electrode of PSII preparing the application in photoelectrochemical cell or solar energy photocatalytic water.
8. application according to claim 7, is characterized in that: adopt ruddiness or white light as exciting light, the intensity of described exciting light is 5 ~ 100mW/cm 2.
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