CN105845944B - A kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell - Google Patents
A kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell Download PDFInfo
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- CN105845944B CN105845944B CN201610210563.2A CN201610210563A CN105845944B CN 105845944 B CN105845944 B CN 105845944B CN 201610210563 A CN201610210563 A CN 201610210563A CN 105845944 B CN105845944 B CN 105845944B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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
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Abstract
The invention belongs to photocatalytic fuel cell fields, disclose a kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell.The present invention modifies TiO with nano-tube/CdS2Electrode makees light anode, utilizes CdS/TiO2Electrode enhances the photochemical catalytic oxidation that ascorbic acid promotes glucose under visible light, realize cheap non-enzymatic catalysis agent in neutral environment under visible optical radiation to the photochemical catalytic oxidation of glucose, and a kind of photocatalytic fuel cell is had developed based on it, the battery maximum power is up to 35.6 μ Wcm under excited by visible light‑2, short circuit current is 568.2 μ Acm‑2, electricity conversion 10.3%.This method have it is at low cost, make the advantages such as fuel, the power of battery be big using biological substance in vivo.
Description
Technical field
The invention belongs to photocatalytic fuel cell fields, and in particular to a kind of excited by visible light nano-tube/CdS/TiO2Enhancing is anti-
Bad hematic acid/glucose fuel cell.
Background technology
Glucose is carbohydrate important in animal and plant body, is living cells energy source and metabolism is intermediate produces
Object.However the oxidability of glucose is weaker, often needs to carry out catalysis oxidation to it using certain catalyst.Currently used for Portugal
The substance of grape sugar catalysis oxidation includes mainly enzyme and non-enzymatic catalysis agent.
Glucose oxidase catalytic oxidation has many advantages, such as that high selectivity, reaction condition are mild, but enzyme catalyst holds
Easy in inactivation, production cost are high, it is desirable to achieve catalysis oxidation of the non-enzymatic catalysis agent to glucose.Non-enzymatic catalysis agent includes mainly gold
Category, metal oxide and metal complex.Common noble metal catalyst is although the catalytic activity to glucose is high, price
Costliness is easily poisoned, and therefore, it is difficult to realize large-scale commercial application.Titanium dioxide (TiO2) under alkaline condition to glucose
With stronger catalytic activity, but it is difficult to realize the catalysis oxidation of glucose in neutral conditions, and due to nano-TiO2
Energy gap it is big, mainly absorb ultraviolet light, and ultraviolet light only accounts for 3% or so in sunlight, it is therefore desirable to widen the suction of its light
The range of wavelengths of receipts, and it is desirable that realize its in neutral environment under visible optical radiation to the catalysis oxidation of glucose.Nanometer vulcanization
The energy gap of cadmium (CdS) is 2.42eV, is semi-conducting material a kind of important and that band gap is moderate, has in visible light region
Good optical absorptive character, and its conduction level ratio TiO2Height, be conducive to generate photo-generate electron-hole pair separation, can
For improving TiO2Photosensitive property.In addition, ascorbic acid is vitamin necessary to organism, to maintaining organism normal physiological
Function plays a crucial role, it is possible to promote the catalysis oxidation of glucose as prooxidant, therefore the present invention is to receive
Rice CdS modifies TiO2Electrode makees light anode, utilizes CdS/TiO2Electrode enhances the light that ascorbic acid promotes glucose under visible light
Catalysis oxidation, realize cheap non-enzymatic catalysis agent in neutral environment under visible optical radiation to the photochemical catalytic oxidation of glucose, and
A kind of high performance photocatalytic fuel cell is had developed based on it.
Invention content
In order to overcome shortcoming and defect existing in the prior art, realize in neutral environment under visible optical radiation to glucose
Photochemical catalytic oxidation, the purpose of the present invention is to provide a kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/grape
Sugared fuel cell.The battery is with CdS/TiO2Electrode makees light anode, and carbon felt makees cathode, and glucose makees fuel, and ascorbic acid fires
Material and the glycoxidative mediation agent of grape, sodium sulfite and vulcanized sodium make sacrifice agent, and sodium chloride makees electrolyte, trishydroxymethylaminomethane
Make buffer, oxygen makees oxidant, and structure forms photocatalytic fuel cell under visible optical radiation.
The object of the invention is achieved through the following technical solutions:
A kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell, the fuel cell be with
Nano-tube/CdS/TiO2Electrode makees light anode, makees cathode with carbon felt；Persistently lead to oxygen to be maintained under saturation oxygen atmosphere, in anode pool
Middle addition sodium chloride solution makees electrolyte solution, addition glucose makees fuel, addition ascorbic acid makees fuel and grape is glycoxidative
Mediation agent, addition sodium sulfite and vulcanized sodium make sacrifice agent, addition trishydroxymethylaminomethane makees buffer, add in cathode pool
Enter sodium chloride solution and trishydroxymethylaminomethane, structure forms photocatalytic fuel cell under visible optical radiation.
The fuel cell under visible optical radiation maximum power up to 35.6 μ Wcm-2, short circuit current is 568.2 μ A
cm-2, electricity conversion 10.3%.
Make buffer using trishydroxymethylaminomethane in the anode pool and cathode pool, make pH value of solution maintain 5~
9。
A concentration of 0~0.2mol/L of the sodium sulfite in electrolyte solution；The vulcanized sodium is in electrolyte solution
In a concentration of 0~0.1mol/L；A concentration of 0.001~0.4 mol/L of the ascorbic acid in electrolyte solution；It is described
Glucose a concentration of 0.001~0.4mol/L in electrolyte solution.
The additive amount of electrolyte solution is 2~100mL in the anode pool.
The intensity of the visible optical radiation is 0.18mWcm-2。
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) light anode used in the present invention makes simple, has high photocatalytic activity；
(2) present invention makees fuel with biological substance in vivo, and oxygen makees oxidant；
(3) present invention realizes the photochemical catalytic oxidation of ascorbic acid/glucose under visible optical radiation in neutral environment；
(4) photocatalytic fuel cell that the present invention is developed works normally at normal temperatures and pressures；
(5) maximum power of the photocatalytic fuel cell that builds of the present invention under excited by visible light is up to 35.6 μ Wcm-2,
Short circuit current is 568.2 μ Acm-2, electricity conversion 10.3%.
Description of the drawings
The photoelectric current of photocatalytic fuel cells of the Fig. 1 to be built in the embodiment of the present invention 1 changes over time curve, wherein 1,
2,3,4 sodium sulfite/vulcanized sodium and the measurement song containing glucose, ascorbic acid and ascorbic acid/glucose are corresponded respectively to
Line, 5 correspond to TiO2Experiment curv of the electrode in ascorbic acid/glucose；
Fig. 2 is that the current density of the photocatalytic fuel cell built in the embodiment of the present invention 1 is bent with the variation of cell voltage
Line, wherein 1,2,3,4,5 correspond respectively to buffer solution, sodium sulfite/vulcanized sodium and contain glucose, ascorbic acid and Vitamin C
Experiment curv of the acid/glucose under illumination condition, 6 correspond to experiment curv of the ascorbic acid/glucose under dark condition；
Fig. 3 is that the power density of the photocatalytic fuel cell built in the embodiment of the present invention 1 is bent with the variation of cell voltage
Line, wherein 1,2,3,4,5 correspond respectively to buffer solution, sodium sulfite/vulcanized sodium and contain glucose, ascorbic acid and Vitamin C
Experiment curv of the acid/glucose under illumination condition, 6 correspond to experiment curv of the ascorbic acid/glucose under dark condition.
Specific implementation method
With reference to specific embodiment, present invention be described in more detail.According to purpose of design of the present invention, allied substances
The variation of simple replacement and size shape, such as change the size of photocatalytic fuel cell of the present invention (as changed work
Electrode or to electrode size), change electrode appearance (being such as changed to square or other shapes), simply change sodium sulfite, vulcanization
Sodium, ascorbic acid or glucose dosage etc. should all belong to the scope of the present invention；Test method used in following embodiments is such as
It is the existing conventional method of the art without specified otherwise；Used material, reagent etc. are unless otherwise specified
The reagent and material commercially obtained.
Embodiment 1 builds excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell
The CdS/TiO of the present embodiment2Electrode is prepared by the following method to obtain：
(1) indium tin oxide-coated glass (substrate) is immersed to prepared TiO2It is lifted with certain speed after colloidal sol,
So that colloidal sol is attached in substrate, then the electrode is put into baking oven after freeze-day with constant temperature 12h and obtains TiO2Electrode.
(2) cyclic voltammetry electro-deposition techniques, in three-electrode system, working electrode TiO are used2Electrode, to electrode
For Ti electrode, reference electrode is saturated calomel electrode, and electrolyte is 0.01mol/L caddies, the 0.01mol/L sulphur of pH=2.0
The potential range of sodium thiosulfate solution, deposition is -0.3V~-0.9V, and the scanning number of turns is 100 circles, and it is 0.05V s to sweep speed-1；
(3) electrode deposited is put into freeze-day with constant temperature 12h in baking oven and obtains CdS/TiO2Electrode.
The structure of the present embodiment photocatalytic fuel cell, concrete operation step are as follows：
With CdS/TiO obtained2Electrode makees light anode, and carbon felt makees cathode, and persistently leads to oxygen to be maintained at saturation oxygen atmosphere
Under enclosing (oxidant), 0.1mol/L sodium chloride (electrolyte solution), 0.02mol/L trihydroxy methyl amino first are added in anode pool
Alkane (pH=7.20；Buffer solution), 0.02mol/L sodium sulfites (sacrifice agent), 0.01mol/L vulcanized sodium (sacrifice agent),
0.1mol/L glucose (fuel) and 0.1mol/L ascorbic acid (fuel and the glycoxidative mediation agent of grape) are added in cathode pool
0.1mol/L sodium chloride and 0.02mol/L trishydroxymethylaminomethanes are connected with saturation potassium chloride salt bridge between two ponds；
0.18mW·cm-2Structure forms photocatalytic fuel cell under visible optical radiation, i.e., excited by visible light nano-tube/CdS/TiO of the present invention2
Enhance ascorbic acid/glucose fuel cell.
The photochemical catalytic oxidation of embodiment 2 glucose and ascorbic acid
CdS/TiO in the photocatalytic fuel cell built to embodiment 12Electrode Ascorbic Acid and ascorbic acid promote Portugal
The photocatalysis of grape sugar, concrete operation step are as follows：
The CdS/TiO made with embodiment 12Electrode makees light anode, and carbon felt makees cathode, in the anode of photocatalytic fuel cell
A resistance box and voltmeter are connected between cathode, in sodium sulfite/vulcanized sodium under illumination/dark condition in survey calculation 300s
(1) and containing the electric current versus time curve in glucose (2), ascorbic acid (3) and glucose/ascorbic acid (4), to
Illustrate CdS/TiO2Electrode Ascorbic Acid and ascorbic acid promote the photocatalysis of glucose, while light anode being become
TiO2Electrode, the electric current in its 300s of survey calculation under illumination/dark condition in glucose/ascorbic acid change with time
Curve (5), to illustrate TiO2The effect of modified electrode, the results are shown in Figure 1.
The photoelectric current that curve 1 is shown is 19.9 μ Acm-2；After glucose is added, the photoelectric current that curve 2 is shown is 20.2 μ
A·cm-2, photoelectric current is almost unchanged, illustrates that individually existing glucose is difficult in CdS/TiO2Photochemical catalytic oxidation occurs on electrode；
After ascorbic acid is added, the photoelectric current that curve 3 is shown is 24.1 μ Acm-2, compared to curve 1, photoelectric current improves 21.1%,
Illustrate that ascorbic acid can be in CdS/TiO2Photochemical catalytic oxidation occurs on electrode, can be used as fuel；When glucose and anti-bad
When hematic acid exists simultaneously, the photoelectric current that curve 4 is shown is 26.4 μ Acm-2, compared to curve 1, photoelectric current increases 6.5 μ A
cm-2, 32.5% is improved, illustrates that ascorbic acid not only serves as fuel, and glucose photochemical catalytic oxidation can be promoted, and is catalyzed
Significant effect；Change light anode into TiO2Electrode, the electric current that curve 5 is shown maintain 13.6 μ Acm-2, illumination and dark condition
Under electric current almost without changing, illustrate TiO2Electrode is hardly by excited by visible light, when use CdS is to TiO2It carries out quick
After changing modification, the CdS/TiO2Electrode can be by excited by visible light, and photovoltaic effect is stronger.
3 excited by visible light nano-tube/CdS of embodiment/TiO2Enhance ascorbic acid/glucose fuel cell performance
Test to the photocatalytic fuel cell performance that embodiment 1 is built, concrete operation step are as follows：
Adjust the resistance value of resistance box between being connected to photocatalytic fuel cell anode and cathode, survey calculation photocatalytic fuel
The current density (Fig. 2) and power density (Fig. 3) of battery with voltage change curve.
In 0.18mWcm-2Under visible optical radiation, the short circuit current that curve 1 is shown is 7.4 μ Acm-2, open circuit potential is
0.4V reaches 1.6 μ Wcm of maximum power at 0.3V-2；After sacrifice agent is added, the short circuit current that curve 2 is shown is 34.1 μ
A·cm-2, open circuit potential 0.5V reaches 4.0 μ Wcm of maximum power at 0.3V-2, the addition of sacrifice agent makes battery most
It is high-power to improve 1.5 times；After glucose is added, the short circuit current that curve 3 is shown is 51.1 μ Acm-2, open circuit potential is
0.6V reaches 4.5 μ Wcm of maximum power at 0.4V-2, the variation of short circuit current, open circuit potential, maximum power etc. is little,
Illustrate that individually existing glucose is difficult in CdS/TiO2Photochemical catalytic oxidation occurs on electrode；After ascorbic acid is added, curve 4 is aobvious
The short circuit current shown is 454.6 μ Acm-2, open circuit potential 0.6V reaches 24.2 μ Wcm of maximum power at 0.1V-2, phase
Than in curve 2, maximum power improves 5.1 times；When glucose and ascorbic acid exist simultaneously, the short circuit that curve 5 is shown is electric
Stream is 568.2 μ Acm-2, open circuit potential 0.8V reaches 35.6 μ Wcm of maximum power at 0.2V-2, compared to curve
2, maximum power improves 8.0 times, illustrates that the non-enzymatic catalysis agent that the present invention makes realizes in neutral environment under visible optical radiation
The photochemical catalytic oxidation of ascorbic acid/glucose.The photocatalytic fuel cell that testing example 1 is built under dark condition, curve 6
The short circuit current of display is 340.9 μ Acm-2, open circuit potential 0.5V reaches 17.0 μ Wcm of maximum power at 0.1V-2,
Compared to curve 5, it is seen that the power that light excitation generates is 18.6 μ Wcm-2, electricity conversion 10.3%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (6)
1. a kind of excited by visible light nano-tube/CdS/TiO2Enhance ascorbic acid/glucose fuel cell, it is characterised in that：The fuel
Battery is with nano-tube/CdS/TiO2Electrode makees light anode, makees cathode with carbon felt；Persistently lead to oxygen to be saturated under oxygen atmosphere to be maintained at,
Addition sodium chloride solution, which makees electrolyte solution, in anode pool, addition glucose makees fuel, ascorbic acid is added makees fuel and Portugal
The glycoxidative mediation agent of grape, addition sodium sulfite and vulcanized sodium make sacrifice agent, addition trishydroxymethylaminomethane makees buffer, in the moon
Sodium chloride solution and trishydroxymethylaminomethane are added in the pond of pole, is connected with saturation potassium chloride salt bridge between two ponds, visible
Structure forms photocatalytic fuel cell under light radiation；
Nano-tube/CdS/the TiO2Electrode is prepared by the following method to obtain：
(1) indium tin oxide-coated glass is immersed to prepared TiO2It is lifted after colloidal sol, colloidal sol is made to be attached in substrate, then
The electrode is put into baking oven after freeze-day with constant temperature 12h and obtains TiO2Electrode；
(2) cyclic voltammetry electro-deposition techniques, in three-electrode system, working electrode TiO are used2Electrode is titanium electricity to electrode
Pole, reference electrode are saturated calomel electrode, and electrolyte is 0.01mol/L caddies, the 0.01mol/L thiosulfuric acids of pH=2.0
The potential range of sodium solution, deposition is -0.3V~-0.9V, and the scanning number of turns is 100 circles, and it is 0.05V s to sweep speed-1；
(3) electrode deposited is put into freeze-day with constant temperature 12h in baking oven and obtains CdS/TiO2Electrode.
2. a kind of excited by visible light nano-tube/CdS/TiO according to claim 12Enhance ascorbic acid/glucose fuel electricity
Pond, it is characterised in that：The fuel cell under visible optical radiation maximum power up to 35.6 μ Wcm-2, short circuit current 568.2
μA·cm-2, electricity conversion 10.3%.
3. a kind of excited by visible light nano-tube/CdS/TiO according to claim 12Enhance ascorbic acid/glucose fuel electricity
Pond, it is characterised in that：PH value of solution maintains 5~9 in the anode pool and cathode pool.
4. a kind of excited by visible light nano-tube/CdS/TiO according to claim 12Enhance ascorbic acid/glucose fuel electricity
Pond, it is characterised in that：A concentration of 0~0.2mol/L of the sodium sulfite in electrolyte solution；The vulcanized sodium is being electrolysed
A concentration of 0~0.1mol/L in matter solution；A concentration of 0.001~0.4mol/ of the ascorbic acid in electrolyte solution
L；The glucose a concentration of 0.001~0.4mol/L in electrolyte solution.
5. a kind of excited by visible light nano-tube/CdS/TiO according to claim 12Enhance ascorbic acid/glucose fuel electricity
Pond, it is characterised in that：The additive amount of electrolyte solution is 2~100mL in the anode pool.
6. a kind of excited by visible light nano-tube/CdS/TiO according to claim 12Enhance ascorbic acid/glucose fuel electricity
Pond, it is characterised in that：The intensity of the visible optical radiation is 0.18mWcm-2。
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| CN108063274B (en) * | 2017-10-24 | 2020-02-14 | 华南师范大学 | Novel sacrificial fuel cell, preparation method thereof and application of paired synthesis method in carbon dioxide recycling |
| CN111118532B (en) * | 2019-11-21 | 2021-12-10 | 华南师范大学 | Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell |
| CN113846335B (en) * | 2021-08-31 | 2023-06-02 | 华南师范大学 | Method for enhancing synergistic oxidation of sodium sulfite and glucose by using platinum-modified titanium dioxide electrode or nickel oxide electrode |
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| CN101007650A (en) * | 2007-01-19 | 2007-08-01 | 北京工业大学 | Method for rendering cadmium sulfide film surface hydrophility using illumination |
| CN104789984A (en) * | 2015-03-18 | 2015-07-22 | 华南师范大学 | Method for producing hydrogen by utilizing ascorbic acid to promote glucose photoelectrocatalytic oxidation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007650A (en) * | 2007-01-19 | 2007-08-01 | 北京工业大学 | Method for rendering cadmium sulfide film surface hydrophility using illumination |
| CN104789984A (en) * | 2015-03-18 | 2015-07-22 | 华南师范大学 | Method for producing hydrogen by utilizing ascorbic acid to promote glucose photoelectrocatalytic oxidation |
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| Ni/CdS/TiO2 nanotube array heterostructures for high performance photoelectrochemical biosensing;Huanhuan Huo等;《J. Mater. Chem. A》;20150205;第3卷;第5882-5888页 * |
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