CN102231449B - Photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and preparation method thereof - Google Patents

Photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and preparation method thereof Download PDF

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CN102231449B
CN102231449B CN2011101006618A CN201110100661A CN102231449B CN 102231449 B CN102231449 B CN 102231449B CN 2011101006618 A CN2011101006618 A CN 2011101006618A CN 201110100661 A CN201110100661 A CN 201110100661A CN 102231449 B CN102231449 B CN 102231449B
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quantum dot
dendrimer
titanium dioxide
pamam
preparation
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CN102231449A (en
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朱以华
张建梅
杨晓玲
陆金丹
沈建华
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East China University of Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention provides a photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and a preparation method thereof. The photoelectrochemical biofuel cell comprises the following parts: an anode chamber containing an anode, a cathode chamber containing a cathode, a membrane material to separate the anode chamber and the cathode chamber, and an outer circuit. The anode and the cathode are formed by loading modifiers on basic materials; and the enzyme is immobilized on a quantum dot / titanium dioxide composite layer, and the quantum dot and titanium dioxide are connected through a coupling agent. The invention has following characteristics of high output performance, high utilization efficiency of incident light, cheap and easily available raw materials. In addition, nano platinum is employed as a catalyst to realize a maximum surface area and a maximum catalysis efficiency.

Description

A kind of preparation method of the photoelectrochemicalbiofuel biofuel cell based on quantum dot, titanium dioxide and enzyme
Technical field
The present invention relates to a kind of enzyme base biological fuel cell, relate in particular to the photoelectrochemicalbiofuel biofuel cell of a kind of quantum dot, titanium dioxide and enzyme, and its preparation method.
Background technology
Along with the worsening shortages of the energy, development of new clean energy resource and readjust the energy structure and become global common recognition.Enzyme base biological fuel cell is by using enzyme as catalyst, the reproducible energy source such as combined sugar and organic acid, be oxidation and the Reduction of oxygen of fuel, in the lower generating of stable condition (normal temperature, pH neutrality), be considered to the cleaning of 21 century first-selection, efficient generation mode.But enzyme base biological fuel cell is also remoter from practical application at present, mainly is because its output power density far can not meet the demands.
Chinese patent CN101494296A(2009) a kind of biological fuel cell and method for making thereof, electronic equipment, enzyme-immobilized electrode and method for making thereof are disclosed.It is that electron mediator is fixed on the male or female of biological fuel cell with enzyme, and the concentration of finding to be fixed on the electron mediator in the Catalytic Layer on the electrode is set as the Michaelis constant of the enzyme reaction of Michaelis constant Km(take electron mediator as substrate of the relative enzyme of electron mediator) more than 10 times, can obtain maximum current value.Electron mediator preferably has the compound of quinone skeleton.
Because electron mediator is in its life-span, stability and the problem that the active aspect of enzyme is existed, Chinese patent CN101351913A discloses a kind of Direct electron transfer that uses enzyme in biological anode, biological-cathode and biological fuel cell.Utilization be fixed on the electrode can metastatic electron electronic conductor, such as material with carbon element, metallic conductor, semiconductor, mesoporous material etc., realized directly transmitting fast of electronics, thereby improved the performance of biological fuel cell.
In order further to improve the output power density of enzyme base biological fuel cell, US Patent No. 2007/0184309A1 discloses a kind of photoelectricity biological fuel cell that is mainly used in photolysis water hydrogen, improvements have been to use for reference the principle of solar cell, have adopted the TiO of dye sensitization 2As the light anode, consisted of a kind of photoelectrochemicalbiofuel biofuel cell of mixing, not only utilize biological respinse that the chemical energy in the fuel is converted into electric energy, utilize simultaneously illumination that light energy conversion is electric energy, its performance is better than with the solar cell of same electrode and fuel and biological fuel cell.
But, there is the researcher to find, quantum dot such as CdS, CdSe, PbS etc. can replace dyestuff as sensitising agent, absorb visible light, make electronics to wider semiconductor such as TiO 2Or SnO 2Upper transfer, the solar cell properties that they make is more excellent.Simultaneously, there is research to find TiO 2Pattern also to the utilance that strengthens incident light and promote the charge carrier conversion to play an important role.The TiO of one dimension 2The TiO that nanotube is piled up more at random 2Nano particle has better electronics transmission path, and its electricity conversion is higher.
In addition, it is stock that the negative electrode of biological fuel cell adopts graphite, carbon cloth or carbon paper usually, but direct result of use not good (particularly take oxygen as electron acceptor) can improve by adhering to high activated catalyst the present platinum that mostly uses.Contain that platinum electrode is easier is combined with oxygen, catalytic oxygen participates in electrode reaction, can reduce the diffusion of oxygen anode simultaneously.Adopt the nanometer platinum powder can make its surface area maximization as catalyst, and surface area is larger, its efficient is just larger.But platinum t nano powder Main Problems is: owing to contact with each other between particle and the particle, so that total surface area reduces.
Summary of the invention
In order to solve problems of the prior art, the present invention proposes a kind of photoelectrochemicalbiofuel biofuel cell based on quantum dot, titanium dioxide and enzyme, and open its preparation method.
Technical scheme of the present invention is:
A kind of photoelectrochemicalbiofuel biofuel cell based on quantum dot, titanium dioxide and enzyme comprises following part: the membrane material and the external circuit that include the anode chamber of anode, the cathode chamber that includes negative electrode, the described anode chamber of separation and described cathode chamber;
Described anode and described negative electrode are that the load trim consists of on stock; Described stock is selected from one or more in carbon felt, carbon fiber, carbon paper, the carbon cloth; Preferred carbon paper wherein;
The trim of described anode includes the composite structure of quantum dot/titanium dioxide/enzyme, and wherein, enzyme immobilization is connected by coupling agent between quantum dot and titanium dioxide on quantum dot/titanium dioxide composite bed;
The trim of described negative electrode is that metal platinum is encapsulated in the PAMAM/Pt composite catalyst that forms in the Polyamidoamine Dendrimers in 3～7 generations.
Described membrane material is amberplex, and described enzyme is selected from one or more in glucose oxidase, LO, horseradish peroxidase, cholesterol oxidase, the xanthine oxidase.
Described amberplex is cation-exchange membrane, such as Nafion film (perfluorinate high molecular polymer sulfonate cation-exchanger, E.I.Du Pont Company's product).
Described titanium dioxide is titania nanoparticles or titanium dioxide nanofiber.
Described quantum dot is selected CdS, the CdSe in the Polyamidoamine Dendrimers that is encapsulated in described 3～7 generations, one or more among the CdTe.
It is coupling agent TG-2(phosphatic type monoalkoxy class titanate esters that described coupling agent is selected titanate esters) the improved phosphatic type monoalkoxy of TG-3(class titanate esters), TG-38S(pyrophosphoric acid type monoalkoxy class titanate esters), TG-27(compound phosphoric acid type monoalkoxy class titanate esters) in a kind of.
Described chemical-biological fuel refers to contain for the enzyme of selecting the solution of the substrate of the described enzyme of selecting.As select glucose oxidase, then chemical-biological fuel refers to glucose.
The preparation method of above-mentioned photoelectrochemicalbiofuel biofuel cell based on quantum dot, titanium dioxide and enzyme comprises the steps:
1) preparation of the Polyamidoamine Dendrimers in 3～7 generations
The large molecule of method synthesizing tree-like is dispersed in employing, is hocketed by Michael addition reaction and amidation process by ethylenediamine and methyl acrylate, whenever finishes once complete Michael addition reaction and amidation process, and then dendrimer increases a generation;
The polyamide-amide that is initially ethylenediamine is dissolved with absolute methanol, and after the logical nitrogen deoxygenation, under-40～0 ℃, preferably-30 ℃, drip methyl acrylate, react after 12～96 hours decompression distillation, obtain colourless or faint yellow pulpous state viscous fluid, namely obtain the dendrimer polyamide-amide in half generation;
Ethylenediamine is dissolved with absolute methanol, and logical nitrogen deoxygenation drips half for PAMAM solution down-40～0 ℃ (preferably-30 ℃); Behind the low-temp reaction 12～96 hours, system is risen to room temperature, continue reaction after 12～96 hours, to its decompression distillation, obtain colourless or faint yellow pulpous state viscous fluid, namely obtain the dendrimer polyamide-amide in whole generation;
Above-mentioned steps repeats, until obtain the Polyamidoamine Dendrimers in 3～7 generations, i.e. and dendrimer PAMAM;
2) preparation of dendrimer/platinum composite catalyst
The concentration that step 1) is obtained is that the aqueous solution and the concentration of the dendrimer PAMAM of 0.5～50 μ M is 1 * 10 -6～5 * 10 -1M(is 0.1M preferably) the platinum ion aqueous solution, be that evenly mix 1:12～64 in molar ratio, with the pH value of weak acid (such as citric acid) regulator solution between 3～5, so that the amido complexing of metal ion and described dendrimer PAMAM inside; Adding concentration is preferably 0.3M of 0.1～0.5M(again) reducing agent (such as hydrazine hydrate, sodium borohydride etc.), reduce ionizable metal salt among the described dendrimer PAMAM, can make the dendrimer compound that is packaged with the nano zero-valence platinum; The particle diameter of described dendrimer PAMAM is generally several nanometers, be encapsulated in the particle diameter of the zero-valent metal in the dendrimer less than the particle diameter of dendrimer, therefore also be several nanometers, the particle diameter of the Pt nanoparticle of the PAMAM encapsulation in general 4 generations is at 0.5～4nm;
3) preparation of the quantum dot of dendrimer encapsulation
The concentration that step 1) is obtained is that the aqueous solution and the concentration of the dendrimer PAMAM of 0.5～50 μ M is 1 * 10 -6～5 * 10 -1M(is 0.1M preferably) Cd 2+The aqueous solution, stoichiometric proportion n in molar ratio Cd 2+/ n PAMAMThe preferred 2.5:1 of=2～7:1() evenly mix, (preferred 35 ℃) stir the preferred 12h of 6～24h(under 20～60 ℃), make Cd 2+With the abundant coordination of PAMAM, then be down to room temperature, add and Cd 2+The Na of Isoequivalent weight 2S or Se powder or Te powder, the preferred 1h of rapid stirring reaction 0.5～3h(), then can obtain respectively the quantum dot of transparent CdS or CdSe or CdTe;
4) preparation of titanium dioxide
Titania nanoparticles is selected commercially available P25, the Degussa product.
Tetrabutyl titanate is mixed with the ethanolic solution that concentration is 0.01～0.5M, get this solution 10mL, add gluey template P123, excipient polyvinylpyrrolidone (PVP, MW～1,300,000), wherein, the mol ratio of tetrabutyl titanate, gluey template P123 and polyvinylpyrrolidone is that 2～7:2～4:1(is preferably 3:2.5:1), vigorous stirring under the room temperature obtains the bright colloidal sol of homogeneous; This colloidal sol is used for electrostatic spinning, fiber preferred 4h of (preferred 550 ℃) calcining 2～8h(under 400～800 ℃ that electrospinning is obtained), optional 3 ℃ of heating rate/min), can obtain the one-dimentional structure nanometer titanium dioxide fiber;
5) coupling between quantum dot and titanium dioxide
Nanometer titanium dioxide fiber in the step 4) is mixed with 1 * 10 -6～5 * 10 -1The TiO of M 2The aqueous solution is got the described TiO of 100mL 2The aqueous solution and 0.05mL coupling agent stirring reaction 15min; Then, the quantum dot solution 5mL that adds the dendrimer encapsulation that obtains in the step 3) continues to stir 15min, can realize the coupling between quantum dot and titanium dioxide, obtains quantum dot/titanium dioxide coupled complex; Described coupling agent is that titanate esters is a kind of among coupling agent TG-2, TG-3, TG-38S, the TG-27;
6) preparation of anode
According to the size of anode chamber, the stock of a suitable size of cutting, the quantum dot that obtains in this stock dropping step 5)/titanium dioxide coupled complex is so that the load capacity of quantum dot reaches 0.01～5mg/cm 2, optimum 0.8mg/cm 2After it parches, immobilised enzymes again; Enzyme is mixed with the phosphate buffer (PBS solution) of 1mg/mL, and dripping has on the stock of quantum dot/titanium dioxide coupled complex in above-mentioned load, and the load capacity by the amount regulation and control enzyme that drips is 10～90U/cm 2(preferred 30U/cm 2);
7) preparation of negative electrode
According to the size of cathode chamber, the stock of a suitable size of cutting again drips step 2 at this stock) in dendrimer/platinum composite catalyst of obtaining so that the load capacity of platinum reaches 0.001～0.5mg/cm 2(preferred 0.2mg/cm 2).
The spinning parameter of described electrostatic spinning is as follows: spinning voltage 10kV, and spinning is apart from 20cm, and the colloidal sol flow is 3mL/h; Step 1) adds several n-butanols as the entrainer of excessive ethylenediamine in vacuum distillation process.
The present invention is applicable to the enzyme base biological fuel cell of two chambers configuration, and its anode chamber, cathode chamber and external circuits etc. carry out with reference to conventional method.
Below be the structural formula of 4.0 generation dendrimers (G4.0), in generation, begin to count take ethylenediamine as nuclear (core), take the initial reaction product of ethylenediamine and methyl acrylate as G0.0 for it.From the structural formula of this dendrimer, also can find out the structural formula of G0.0, G1.0, G2.0, G3.0 in 4.0 generation.
Advantage of the present invention and effect:
The above-mentioned photoelectrochemicalbiofuel biofuel cell based on quantum dot, titanium dioxide and enzyme that makes has following features: (1) combines the solar cell of dye sensitization with the concept of enzyme biological fuel cell, not only the chemical energy with organic-fuel is converted into electric energy, and luminous energy also is converted into electric energy, be conducive to improve the output performance of biological fuel cell; (2) select semiconductor-quantum-point to come sensitization titanium dioxide as sensitising agent, little quantum dot can be converted to electronics with photon at faster speed, and large quantum dot can absorb more incident photon, has improved the utilization ratio of incident light; (3) select commercially available Degussa P25 titania nanoparticles, raw material is cheap and easy to get; The titania fiber of electrostatic spinning technique preparation has the structure of one dimension, more is conducive to the transmission of electronics; (4) adopt dendrimer PAMAM to encapsulate quantum dot as template, realized the confinement reaction in the dendrimer inner chamber, effectively controlled the particle diameter of quantum dot; Simultaneously, by choosing the PAMAM of different algebraically, can regulate and control the particle diameter of quantum dot: algebraically is lower, and particle diameter is less, and algebraically is higher, and particle diameter is larger; (5) similar, adopt dendrimer PAMAM encapsulation Pt nano particle to modify fuel battery negative pole as catalyst, the Pt of dendrimer encapsulation not only particle diameter is little by (2～4nm) but also good dispersion.Adopt this nanometer Pt can make its surface area maximization, maximizing efficiency as catalyst.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
Step (1): the 20g ethylenediamine is dissolved in the 100mL methyl alcohol, stirs, logical nitrogen 15min drips the methyl acrylate of 1.36mol with constant flow pump under-30 ℃, under the low temperature behind the reaction 48h, temperature is raised to room temperature (20 ° of C) allows its slaking 48h.After reacting completely, being lower than decompression distillation desolventizing methyl alcohol and excessive methyl acrylate under 45 ° of C, 0.1MPa, obtain 0.5G PAMAM.
The 0.5G PAMAM of above-mentioned 25mmol is dissolved in the 100mL methyl alcohol, contains in the ethylenediamine methanol solution of 200mmol with the constant flow pump dropping, behind the 48h low-temp reaction, add again the 48h room temperature reaction.After same question response is complete, be lower than 45 ° of C, decompression distillation under the 0.1MPa adds simultaneously and removes after n-butanol and ethylenediamine form azeotropic mixture, obtains 1G PAMAM.
Repeat above-mentioned building-up process, can obtain half generation or whole generation PAMAM dendrimer of the different algebraically from 0.5G to 7G.
5 generation dendrimer PAMAM of step (1) preparation are mixed with the aqueous solution of 50 μ M, use weak acid, such as citric acid, the pH value of regulator solution is 5.Measuring 20mL5 pours in the small beaker of 50mL for the PAMAM dendrimer aqueous solution.
Step (2): continuing to add concentration in small beaker is the K of 0.1M 2PtCl 4The aqueous solution, dendrimer PAMAM and K 2PtCl 4Mol ratio be 1:30.Stir, reaction is 72 hours under the room temperature.
Step (3): add again the K that compares 2PtCl 420 times of amounts excessive, concentration is the reducing agent NaBH of 0.3M 4The aqueous solution, the pH value to 8 of the hydrochloric acid conditioning solution of usefulness 0.1M is reduced into the zeroth order nano particle with complexing metal ion in dendrimer.Reduction reaction occurs rapidly, then solution is poured in the bag filter, and dialysis is 24 hours in a large amount of water environments, therebetween through repeatedly changing water.Obtain the compound that inside has encapsulated the dendrimer PAMAM of nano-metal particle.This compound is mixed with the aqueous solution of 2mg/mL, is placed in the small beaker of 50mL.
Step (4): getting 10mL concentration is the G4.0PAMAM methanol solution of 0.1mol/L, regulates its pH about 7.0, adds an amount of chromic nitrate methanol solution, makes n Cd 2+/ n PAMAMBe 2.5,35 ℃ and stir 12h, make Cd 2+With the abundant coordination of pamam dendrimer molecule, then be down to room temperature, add and Cd 2+Na etc. amount 2S(V CH3OH: V H2OThe solution of=9:1), rapid stirring reaction 1h guarantees to obtain transparent CdS quantum dot, and product is deposited in 4 ℃ of environment.
Step (5): prepare the tetrabutyl titanate ethanolic solution 50mL of 0.05M, add successively the P123 of 0.6g, the PVP of 0.3g, vigorous stirring under the room temperature obtains the bright colloidal sol of homogeneous.Get this colloidal sol 10mL, be used for electrostatic spinning, spinning voltage 10kV, spinning is apart from 20cm, and the colloidal sol flow is 3mL/h.The fiber that electrospinning is obtained 550 ℃ of lower calcining 4h (3 ℃ of heating rates/min), obtain titania fiber, diameter is about 200nm, is distributed with the duct on the fiber, specific area is large.
Step (6): get the TiO in the step (5) 2Fiber 40mg is mixed with the aqueous solution of 100mL0.05mmol/L; Get 5mL TiO 2The aqueous solution and 0.05mL coupling agent TG-2, stirring reaction 15min; Add PAMAM-CdS solution 5mL and continue to stir 15min.After reacting completely, obtain Quantum dots CdS/titanium dioxide compound solution.
Step (7): according to the size of anode chamber, the carbon paper of a suitable size of cutting drips the Quantum dots CdS that obtains in the step (6)/titanium dioxide compound solution on the carbon paper, so that the load capacity of quantum dot reaches 0.8mg/cm 2Glucose oxidase is mixed with the PBS(phosphate buffer of 1mg/mL) solution, dripping has on the carbon paper of Quantum dots CdS/titanium dioxide compound in above-mentioned load, and the load capacity of enzyme is 30U/cm 2Obtain the anode modification thing, i.e. the carbon paper of Quantum dots CdS/titania fiber/multienzyme complex in load.
Step (8): according to the size of cathode chamber, the carbon paper of a suitable size of cutting drips the dendrimer/platinum composite catalyst that obtains in the step (3), so that the load capacity of platinum reaches 0.2mg/cm on this carbon paper again 2Obtain the cathodic modification thing, i.e. the carbon paper of dendrimer/platinum composite catalyst in load.
Step (9): separate anode chamber and cathode chamber with the Nafion film as proton exchange membrane (PEM), the photoelectrochemicalbiofuel biofuel cell of structure quantum dot/titanium dioxide/enzyme.Adopting the xenon lamp of 150W is light source, Keithley2400 multifunctional digital source table test battery performance.Take glucose as fuel, the short circuit current that records battery reaches 480 μ A/cm 2, open circuit voltage is 0.6V.
Embodiment 2
With " adding and Cd 2+Se powder etc. amount " " adding and Cd in the step of replacing (4) 2+Na etc. amount 2S "; And omit step (5); With " the TiO in the step (5) in " P25 titania nanoparticles " step of replacing (6) 2Fiber " repeat each step among the embodiment 1, obtaining at last the anode modification thing is the carbon paper that Quantum dots CdS e/P25 titanium dioxide/multienzyme complex in load, take glucose as fuel, the short circuit current that records battery reaches 450 μ A/cm 2, open circuit voltage is 0.5V.
Comparative Examples
With the enzyme of load same amount on the carbon paper of blank as the anode modification thing, with platinum (particle diameter is about the 200nm) particle of the electro-deposition of bare carbon paper load same amount preparation as the cathodic modification thing, repeat each step among the embodiment 1, take glucose as fuel, the short circuit current that records battery only is 6 μ A/cm 2, open circuit voltage only is 0.2V.

Claims (2)

1. the preparation method based on the photoelectrochemicalbiofuel biofuel cell of quantum dot, titanium dioxide and enzyme is characterized in that, comprises the steps:
1) preparation of the Polyamidoamine Dendrimers in 3～7 generations
The large molecule of method synthesizing tree-like is dispersed in employing, is hocketed by Michael addition reaction and amidation process by ethylenediamine and methyl acrylate, whenever finishes once complete Michael addition reaction and amidation process, and then dendrimer increases a generation;
The polyamide-amide that is initially ethylenediamine is dissolved with absolute methanol, and after the logical nitrogen deoxygenation, under-40～0 ℃, drip methyl acrylate, react after 12～96 hours decompression distillation, obtain colourless or faint yellow pulpous state viscous fluid, namely obtain the dendrimer polyamide-amide in half generation;
Ethylenediamine is dissolved with absolute methanol, and logical nitrogen deoxygenation is-40～0 ℃ of lower dropping partly for PAMAM solution; Behind the low-temp reaction 12～96 hours, system is risen to room temperature, continue reaction after 12～96 hours, to its decompression distillation, obtain colourless or faint yellow pulpous state viscous fluid, namely obtain the dendrimer polyamide-amide in whole generation;
Above-mentioned steps repeats, until obtain the Polyamidoamine Dendrimers in 3～7 generations, i.e. and dendrimer PAMAM;
2) preparation of dendrimer/platinum composite catalyst
The concentration that step 1) is obtained is that the aqueous solution and the concentration of the dendrimer PAMAM of 0.5～50 μ M is 1 * 10 -6～5 * 10 -1The platinum ion aqueous solution of M is that evenly mix 1:12～64 in molar ratio, uses the pH value of weak acid regulator solution between 3～5, so that the amido complexing of metal ion and described dendrimer PAMAM inside; Add again the reducing agent that concentration is 0.1～0.5M, reduce ionizable metal salt among the described dendrimer PAMAM, can make the dendrimer compound that is packaged with the nano zero-valence platinum; The particle diameter of described dendrimer PAMAM is generally several nanometers, and the particle diameter of the Pt nanoparticle of the PAMAM encapsulation in 4 generations is at 0.5～4nm;
3) preparation of the quantum dot of dendrimer encapsulation
The concentration that step 1) is obtained is that the aqueous solution and the concentration of the dendrimer PAMAM of 0.5～50 μ M is 1 * 10 -6～5 * 10 -1The Cd of M 2+The aqueous solution, stoichiometric proportion n in molar ratio Cd 2+/ n PAMAM=2～7:1 evenly mixes, and under 20～60 ℃, stirs 6～24h, makes Cd 2+With the abundant coordination of PAMAM, then be down to room temperature, add and Cd 2+The Na of Isoequivalent weight 2S or Se powder or Te powder, rapid stirring reacts 0.5～3h, then can obtain respectively the quantum dot of transparent CdS or CdSe or CdTe;
4) preparation of titanium dioxide
Titania nanoparticles is selected commercially available P25, the Degussa product;
Tetrabutyl titanate is mixed with the ethanolic solution that concentration is 0.01～0.5M, get this solution 10mL, add gluey template P123, MW～1,300,000 excipient polyvinylpyrrolidone, wherein, the mol ratio of tetrabutyl titanate, gluey template P123 and polyvinylpyrrolidone is 2～7:2～4:1, vigorous stirring under the room temperature obtains the bright colloidal sol of homogeneous; This colloidal sol is used for electrostatic spinning, and the fiber calcining 2～8h under 400～800 ℃ with electrospinning obtains can obtain the one-dimentional structure nanometer titanium dioxide fiber;
5) coupling between quantum dot and titanium dioxide
Nanometer titanium dioxide fiber in the step 4) is mixed with 1 * 10 -6～5 * 10 -1The TiO of M 2The aqueous solution is got the described TiO of 100mL 2The aqueous solution and 0.05mL coupling agent stirring reaction 15min; Then, the quantum dot solution 5mL that adds the dendrimer encapsulation that obtains in the step 3) continues to stir 15min, can realize the coupling between quantum dot and titanium dioxide, obtains quantum dot/titanium dioxide coupled complex; Described coupling agent is that titanate esters is a kind of among coupling agent TG-2, TG-3, TG-38S, the TG-27;
6) preparation of anode
According to the size of anode chamber, the stock of a suitable size of cutting, the quantum dot that obtains in this stock dropping step 5)/titanium dioxide coupled complex is so that the load capacity of quantum dot reaches 0.01～5mg/cm 2After it parches, immobilised enzymes again; Enzyme is mixed with the phosphate buffer of 1mg/mL, and dripping has on the stock of quantum dot/titanium dioxide coupled complex in load, and the load capacity by the amount regulation and control enzyme that drips is 10～90U/cm 2
7) preparation of negative electrode
According to the size of cathode chamber, the stock of a suitable size of cutting again drips step 2 at this stock) in dendrimer/platinum composite catalyst of obtaining so that the load capacity of platinum reaches 0.001～0.5mg/cm 2
2. preparation method according to claim 1 is characterized in that, the spinning parameter of described electrostatic spinning is as follows: spinning voltage 10kV, and spinning is apart from 20cm, and the colloidal sol flow is 3mL/h; Step 1) adds several n-butanols as the entrainer of excessive ethylenediamine in vacuum distillation process.
CN2011101006618A 2011-04-21 2011-04-21 Photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and preparation method thereof Expired - Fee Related CN102231449B (en)

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