CN103342471B - A kind of Photoelectric nanometer composite membrane material and its preparation method and application - Google Patents
A kind of Photoelectric nanometer composite membrane material and its preparation method and application Download PDFInfo
- Publication number
- CN103342471B CN103342471B CN201310282504.2A CN201310282504A CN103342471B CN 103342471 B CN103342471 B CN 103342471B CN 201310282504 A CN201310282504 A CN 201310282504A CN 103342471 B CN103342471 B CN 103342471B
- Authority
- CN
- China
- Prior art keywords
- conductive glass
- electrode
- composite membrane
- carbon nanotube
- membrane material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of Photoelectric nanometer composite membrane material.This material is compounded with the tetrahydroxy phenyl porphyrin gold nano grain with nucleocapsid structure by the carbon nano tube surface in acidifying formed.This material can be used for the platform building photoelectron transfer in simulation biosystem.This material has excellent light acquisition performance, visible ray can be caught, and be converted to stable electric energy, and its electron transfer rate will far above only having carbon nanotube or porphyrin gold nano grain, at 546nm wave band, there is best reactive behavior, can be used for the structure of dye sensitization solar battery and some photoelectric devices.
Description
Technical field
The invention belongs to field of compound material, be specifically related to a kind of Photoelectric nanometer composite membrane material preparation method and application.
Background technology
Charge movement is process basic in biological phenomena, and itself and electron transmission are closely relevant, and the redox processes of biomacromolecule has decisive role for the energy transformation of life entity and substance metabolism.Therefore, the research of the electron transmission mechanism of concerns about bio system, significant for announcement vital process essence.Porphyrin and its derivative represents the molecular biology content with general life-type enterprise on a molecular scale, and where where is it life just has Porphyrin Molecule.It is not only the chlorophyllous functional component of biomolecules, and is the behavior point of oxygen carrying protein (oxyphorase).In enzyme system, around protein surround by derivatives of porphyrin, the packaging assembly of this uniqueness is extremely important for the expression of its catalytic performance; In photosynthetical system, Porphyrin Molecule is arranged in ring texture, and the porphyrin aggregate of this structure shows perfect light energy use efficiency.Because porphyrins has unique electronic structure and photoelectric properties, and there is good light and thermally stable and be easy to the features such as cutting modification, so there is very large application potential in hitech materials field.
In recent years, core-shell nanoparticles becomes the study hotspot of analysis science, materialogy, biology and medical field because of peculiar property that it is different from single component colloidal particle.Single dispersing core/shell nano composite material is extensively used as the aspects such as catalytic material, photonic crystal, medicine control conveying, when the strong Porphyrin Molecule absorbed is coated on around golden nanometer particle, due to intercoupling of precious metal surface plasma primitive and Porphyrin Molecule, effectively can realize collecting and handling of light, increase the absorption of sun power in photovoltaic cell, and to improve Charge transfer on interface speed further for the efficiency of conversion effectively improving solar cell be very favorable.
Summary of the invention
The object of this invention is to provide a kind of Photoelectric nanometer composite membrane material that can significantly improve Charge transfer on interface speed.
Another object of the present invention is to provide the preparation method and application of above-mentioned materials.
It is as follows that the present invention realizes technical scheme that above-mentioned purpose adopts:
A kind of Photoelectric nanometer composite membrane material, this material is compounded with the tetrahydroxy phenyl porphyrin gold nano grain with nucleocapsid structure by the carbon nano tube surface in acidifying formed.
The preparation method of above-mentioned Photoelectric nanometer composite membrane material, comprises the steps:
(1) process of carbon nanotube: carbon nanotube is joined in the mix acid liquor of sulfuric acid and nitric acid, supersound process 8 ~ 13h, then thin up leaves standstill 20 ~ 30h, filter, drying obtains the carbon nanotube of acidifying;
(2) preparation of tetrahydroxy phenyl porphyrin gold nano grain: by the tetrahydroxy phenyl porphyrin ethanolic soln of 0.2mmol/L and the HAuCl of 0.2mmol/L
4solution 2:1 mixing by volume, stirs, after reacting by heating 20 ~ 40min, with 0.2 μm of membrane filtration, filtrate centrifugation, namely obtains the tetrahydroxy phenyl porphyrin gold nano grain with nucleocapsid structure;
(3) process of carrier: mixing solutions conductive glass being placed in Ursol D, Sodium Nitrite and hydrochloric acid, take saturated calomel electrode as reference electrode, platinum electrode is to electrode, conductive glass is working electrode, interval at 0.4 ~-0.6V, cyclic voltammetry scan, obtains the surperficial keyed jointing conductive glass of aryl diazonium salts;
(4) carbon nanotube of the acidifying of step (1) gained and dicyclohexylcarbodiimide are joined in dimethyl sulfoxide (DMSO), put into by the conductive glass processed through step (3), heating 20 ~ 30h, takes out conductive glass again, respectively after water and ethanol purge, nitrogen dries up;
(5) the tetrahydroxy phenyl porphyrin gold nano grain of step (2) gained is scattered in ethanol, then by dispersant liquid drop on the conductive glass processed through step (4), lucifuge is placed drying and is obtained the Photoelectric nanometer composite membrane material of load on conductive glass.
Above-mentioned Photoelectric nanometer composite membrane material is used for the method studying Photo-induced electron transfer, and step is as follows:
(1) in potassium ferricyanide aqueous solution, using the probe of the scan-type electrochemical microscope as working electrode and reference electrode with build three-electrode system to electrode, using load, the conductive glass of described Photoelectric nanometer composite membrane material is as basal electrode;
(2) in scan-type electrochemical microscope, between working electrode and basal electrode, apply to be enough to make the Tripotassium iron hexacyanide to be reduced to the electrode potential of yellow prussiate of potash poor, under basal electrode is in illumination and non-illuminated conditions respectively, regulate working electrode to the distance of basal electrode, detect the change of electric current, obtain the feedback profile of electric current with distance change;
(3) in scan-type electrochemical microscope, take basal electrode as zero-potential point, apply negative potential to working electrode, under detection basal electrode is in illumination and non-illuminated conditions respectively, the time dependent response curve of electric current.
Above-mentioned Photoelectric nanometer composite membrane material can be used for the platform making dye sensitization solar battery or be used as to build photoelectron transfer in simulation biosystem.
Experimental result shows in photoinduction situation, the ITO conductive glass being modified with Photoelectric nanometer composite membrane material can with the probe molecule Tripotassium iron hexacyanide generation electrotransfer reaction in aqueous phase, and under the feedback model of distance with electric current, obtain typical positive regeeration curve, the Photoinduced electron transfer reaction that there occurs out-phase under light conditions is described.Under light On/Off pattern, photoelectric current is the state of more stable change, illustrate that this Photoelectric nanometer composite membrane material with guidance quality has excellent light acquisition performance, visible ray can be caught, and be converted to stable electric energy, and its electron transfer rate far above only having carbon nanotube or porphyrin gold nano grain, will have best reactive behavior at 546nm wave band, therefore this composite film material with three-dimensional structure can be used for the structure of dye sensitization solar battery and some photoelectric devices.
Accompanying drawing explanation
Fig. 1 is Photo-induced electron transfer schematic diagram, and right figure is Photo-induced electron transfer process under SECM pattern of the present invention.
Fig. 2 is the electrode device schematic diagram under SECM pattern of the present invention.
The uv absorption spectra of Fig. 3 tetrahydroxy phenyl porphyrin and tetrahydroxy phenyl porphyrin gold nano nucleocapsid structure.
The infrared absorpting light spectra of the acidified carbon nanotube processed of Fig. 4.
The stable state cyclic voltammogram of Fig. 5 SECM probe of the present invention in 5mmol/L potassium ferricyanide aqueous solution.
The cyclic voltammetric that differing materials modified by Fig. 6 ITO conductive glass characterizes, and electrolytic solution is 0.2M PBS (pH=7.0) 0.25mmol/L potassium ferricyanide solution.
The cyclic voltammogram of the ITO conductive glass after Fig. 7 diazotization.
The feedback profile figure of light and unglazed photograph is had under Fig. 8 SECM of the present invention pattern.
Under Fig. 9 SECM pattern of the present invention, the feedback profile figure of the ITO conductive glass that several differing materials of photoinduction is modified.
Under Figure 10 SECM pattern of the present invention, the feedback profile figure of the ITO conductive glass composite membrane of the light photoinduction Photoelectric nanometer composite membrane material modification of different wave length.
Figure 11 is the scanning electron microscope (SEM) photograph of tetrahydroxy phenyl porphyrin gold nano grain.
Figure 12 is the transmission electron microscope picture of tetrahydroxy phenyl porphyrin gold nano grain.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details.
Test instrument used
Scan-type electrochemical microscope SECM(CHI 900, CH instrument company of the U.S.), the probe employing diameter of SECM is the Pt ultramicroelectrode of 25 μm;
UV-1100 ultraviolet spectrophotometer, RF-540 fluorescence spectrophotometer; Nicolet Impact-400FT-IR infrared spectrum analyser; HAYASHI instrument company of light source (400 ~ 700nm): LA-410UV-3(Japan);
Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.); Automatic heat collecting type constant-temperature heating magnetic stirring apparatus (DF-101S, Great Wall, Zhengzhou scientific & trading Co., Ltd.); Magnetic stirring apparatus (ML-902, Shanghai Pujiang analytical instrument company).
photoelectric nanometer composite membrane material preparation process:
1) preparation of tetrahydroxy phenyl porphyrin
，R
1=R
2=R
3=R
4=OH；
Synthetic route as above, 3.0g 4-hydroxy benzaldehyde and 6.5ml phenyl aldehyde are successively added in the micro-propionic acid solution boiled of 300mL, rapid stirring, then slowly dropwise add new steaming pyrroles 6mL, about 30min dropwises, after reaction solution continues reflux 1h, stir and be cooled to 75 DEG C, add 75mL dehydrated alcohol, stirring is cooled to room temperature, uncovered hold over night, suction filtration, colourless to filtrate with a small amount of absolute ethanol washing filter cake.80 DEG C of vacuum-drying 8h, obtain the thick product of mixing porphyrin and are about 1.0g.Mixture is dissolved in a small amount of chloroform and alcohol mixeding liquid, be added on silica gel (100 ~ 160 order) pillar, take volume ratio as the chloroform-ethanol mixed solution of 1:9 be eluent, then carry out secondary column chromatography, obtain pure tetrahydroxy phenyl porphyrin (THPP).
2) preparation of tetrahydroxy porphyrin gold nano nucleocapsid structure
By the tetrahydroxy phenyl porphyrin ethanolic soln of 0.2mmol/L and the HAuCl of 0.2mmol/L
4solution mixes according to volume ratio 2:1, stir, 30min is heated at 100 DEG C, the color of solution first becomes green by pink, become scarlet again, stop heating, stirring is cooled to room temperature, obtain lower floor with 0.2 μm of membrane filtration and be suspended filtrate, this is suspended filtrate centrifugal in 6000r/min, be re-dispersed into again in ethanol, repeat this process 3 times, namely obtain having the tetrahydroxy phenyl porphyrin gold nano grain of nucleocapsid structure (as shown in FIG. 11 and 12, gained nano particle size is even, one deck tetrahydroxy phenyl porphyrin in golden core external parcel), refrigeration, lucifuge is for subsequent use.
3) process of carbon nanotube
Take untreated carbon nanotube 25mg(to be bought by market), add in the mixing solutions of the 27mL vitriol oil and concentrated nitric acid (volume ratio is 3:1), ultrasonic 10h under the condition of 20 DEG C.After ultrasonic, mixed solution joined in 500mL redistilled water and leave standstill 24h; Then the millipore filtration of 0.22 μm is used to carry out suction filtration, with distilled water wash until pH is neutral (being about 7.0); Last vacuum-drying, obtains the carbon nanotube of acidifying, introduces carboxylic group at the two ends of carbon nanotube.
4) pre-treatment of carrier ITO conductive glass
ITO conductive glass is used successively acetone, ethanol, each 15min of redistilled water supersound process, then rinse with redistilled water, nitrogen dries up for subsequent use.
At room temperature, by the hydrochloric acid soln (C of the Ursol D of 2mL 10 mmol/L
hCl=0.5 mol/L) be added to fast in the sodium nitrite solution of 20 μ L 0.1mol/L, in the dark stir 5min; Then reaction solution is poured in electrolyzer, first be 0.4 ~-0.6V at potential region, starting voltage is 0.4V, adopts three-electrode system with (saturated calomel is reference electrode, platinum electrode is to electrode, and conductive glass is working electrode) cyclic voltammetric technology scans; Then 120s is deposited at current potential under-0.6V.Now aryl diazonium salts has been connected on ITO conductive glass.
5) grafting of carbon nanotube and ITO conductive glass
Take the carbon nanotube 0.8mg that step 3) is handled well, dicyclohexylcarbodiimide (DCC) 2mg, measure dimethyl sulfoxide (DMSO) (DMSO) 4mL, add in round-bottomed flask, then put into the ITO conductive glass through step 4) process.At 65 DEG C, heat 24h, take out ITO conductive glass, with distilled water flushing, then ultrasonic 2s in ethanol, then use distilled water flushing, N
2dry up, for subsequent use.Aryl diazonium salts bonding on the carboxyl of carbon nanotube end and ITO conductive glass, thus make carbon nano-tube oriented grafting on ITO conductive glass.
6) compound
Get 0.1 μ L step 2) in the tetrahydroxy phenyl porphyrin gold nano grain dispersion liquid that formed, drip on the ITO conductive glass of step 5) process, be placed on the local 1h of lucifuge drying, volatilize, ITO conductive glass obtains Photoelectric nanometer composite membrane material.
the research of Photo-induced electron transfer
1) process of working electrode
Working electrode used under this experiment SECM pattern is the probe of SECM, i.e. Pt ultramicroelectrode, aluminium sesquioxide polishing powder respectively with 0.30 μm and 0.05 μm before each experiment is polished electrode on cotton gauze, improve the susceptibility of probe, then with redistilled water, probe tip is rinsed well.
2) by working electrode, reference electrode (Ag/AgCl, CHI111, CH instrument company of the U.S.), to electrode (platinum is to electrode) and basal electrode (above-mentioned load the ITO conductive glass of Photoelectric nanometer composite membrane material) by assembling shown in Fig. 2 and being connected with computer, working electrode is connected with the negative pole of power supply, basal electrode is connected with the positive pole of power supply, and medium solution when three-electrode system and basal electrode work adopts concentration to be the potassium ferricyanide solution of 1mmol/L.
3) poor to the electrode potential applying-0.1V between the probe (i.e. working electrode) and ITO conductive glass (i.e. basal electrode) of SECM, regulate working electrode to the distance of basal electrode, detect the electric current that flows through working electrode to change with the distance of two electrodes, obtain the feedback profile of distance-electric current, respectively the feedback profile of test substrate electrode under illumination and unglazed photograph.
4) take basal electrode as zero-potential point, the voltage of-0.1V is applied to working electrode, the distance of adjustment SECM probe and ITO conductive glass is between 10 ~ 100 μm, and by source alignment ITO conductive glass, when light source is opened, visible luminous energy is radiated at ITO conductive glass surface.Then, detect the change of electric current under light source On/Off pattern, obtain the time dependent response curve of electric current.
Left figure in Fig. 1 indicates in simulating nature circle the structure being positioned at chlorophyll capsula interna body structure, right figure is at SECM(scan-type electrochemical microscope) simple optical photoinduced electron transfer process on we build under pattern modeling interface, because porphyrin is that some biomacromolecules are (as chlorophyll, protoheme, vitamin B12) core group, so the present invention adopts the ITO conductive glass modified by Photoelectric nanometer composite membrane material to do basal electrode, the probe molecule in solution then adopts the Tripotassium iron hexacyanide.In the present invention, under photoinduction, the detailed process of transfer transport is as follows:
In above-mentioned electronic transfer process,
refer to the porphyrin gold nano grain (nanometer gold is core, and porphyrin is shell) with nucleocapsid structure,
representative is in the tetrahydroxy phenyl porphyrin of excited state, and Etip is the voltage that the probe tip of SECM in experiment applies basal electrode, when it reaches-0.1V, and Fe (CN)
6 3-be reduced into Fe (CN)
6 4-.Under light conditions,
absorption luminous energy transits to more high level and becomes
,
instability lose electronics become oxidation state (
), the electron transmission lost to the golden core of nucleocapsid structure,
with the Fe (CN) being diffused into basal electrode surface
6 4-there is bimolecular redox reaction.On the other hand, along with Fe in solution (CN)
6 3-the increase of concentration, by a series of transfer transport
can by the electron transmission lost be formed to carbon nanotube CNTs
, the electronics of generation will be delivered in the substrate of ITO conductive glass along carbon nanotube tube wall always.
Fig. 3 is the uv absorption spectra of tetrahydroxy phenyl porphyrin and tetrahydroxy phenyl porphyrin gold nano nucleocapsid structure, and dotted line is the ultra-violet absorption spectrum of tetrahydroxy phenyl porphyrin gold nano nucleocapsid structure.From spectrogram, Soret absorption peak is there is again and closes in porphyrin at about 420nm, and there is Q (belonging to π-π * transition) after 500nm with four absorption peaks, the Soret absorption peak of Porphyrin Molecule is not only there is in porphyrin gold nano composite structure, and there is new absorption peak about 560nm greatly, this peak is because the surface plasma resonance of golden nanometer particle and porphyrin Q are with absorbing coupling to be formed; Porphyrin with four absorption peaks, after generating porphyrin gold nano composite structure, becomes an absorption peak at Q (belonging to π-π * transition), and Q is with the disappearance of absorption peak may be the cause that symmetry strengthens.
Fig. 4 is through the infrared absorption peak of the carbon nanotube that ultrasonic acidification is crossed, 1650cm
-1be this kind of method process carbon nanotube on the characteristic peak of carbonyl (C=O).
Fig. 5 is the stable state cyclic voltammogram of SECM probe in 5mmol/L potassium ferricyanide aqueous solution, illustrates that SECM probe (Pt ultramicroelectrode) has good electrochemical behavior.
Fig. 6 is that ITO conductive glass is modified through differing materials, cyclic voltammogram in 0.2M PBS (pH=7.0) 0.25mmol/L potassium ferricyanide solution, is respectively the ITO conductive glass (AP/ITO) after the ITO conductive glass (CNTs/AP/ITO) of carbon nanotube in naked ITO conductive glass, grafting, diazotization from top to bottom.Each step that can be illustrated as membrane process fully occurs completely.
Fig. 7 is diazotizing cyclic voltammogram on ITO conductive glass, and solid line is the curve of first lap scanning, occurs reduction peak, illustrate in solution to there is aryl diazonium salts at-0.1V place; Dotted line is through the image after 120s scanning, illustrates that diazonium salt grafting is on ITO conductive glass.
Fig. 8 is the feedback profile of the distance-electric current of gained under SECM pattern, and coordinate L is normalized cumulant, L=d/a, wherein, the radius (12.5 μm) that d is distance between two electrodes, a is Pt ultramicroelectrode, dotted line is theoretical value, solid line is experimental measurements, and experiment is compared with notional result and met.The feedback profile that curve a is the ITO conductive glass modified with Photoelectric nanometer composite membrane material is basal electrode gained under light illumination; Curve b is the ITO conductive glass that this material is modified is the feedback profile of basal electrode gained under unglazed photograph; Can find out from these two curves, curve a is typical positive regeeration curve, describes and between this porphyrin composite membrane and the Tripotassium iron hexacyanide, there occurs Photo-induced electron transfer under illumination condition.
Fig. 9 is the feedback profile of various different modified membrane distance-electric current of gained under illumination condition.Curve is respectively (a to e) from top to bottom: Photoelectric nanometer composite membrane material/ITO, porphyrin gold nano grain/ITO, carbon nanotube/ITO, naked ITO and aryl diazonium salts/ITO.Three curves are positive regeeration above, and below two is reverse feedback, describes Photoelectric nanometer composite membrane material, more easily occurs in photoinduced condition, and the electron transfer rate of reaction is also faster.Corresponding heterogeneous electron transfer rate constant is as follows:
。
Figure 10 is the light of different wave length carries out photoinduced distance-electric current feedback profile to Photoelectric nanometer composite membrane material/ITO.Curve from top to bottom induction light wavelength as: 546nm, 531nm, 515nm, 487nm, 469nm and 419nm, illustrate that wave band is best at the inducing effect of light to this nano composite material of 546nm, energy level also more mates.Corresponding heterogeneous electron transfer rate constant is as follows:
。
Claims (1)
1. a preparation method for Photoelectric nanometer composite membrane material, described Photoelectric nanometer composite membrane material is compounded with the tetrahydroxy phenyl porphyrin gold nano grain with nucleocapsid structure by the carbon nano tube surface in acidifying formed, and it is characterized in that, comprise the steps:
(1) process of carbon nanotube: carbon nanotube is joined in the mix acid liquor of sulfuric acid and nitric acid, supersound process 8 ~ 13h, then thin up leaves standstill 20 ~ 30h, filter, drying obtains the carbon nanotube of acidifying;
(2) preparation of tetrahydroxy phenyl porphyrin gold nano grain: by the 2:1 mixing by volume of the HAuCl4 solution of the tetrahydroxy phenyl porphyrin ethanolic soln of 0.2mmol/L and 0.2mmol/L, stir, after reacting by heating 20 ~ 40min, with 0.2 μm of membrane filtration, filtrate centrifugation, namely obtains the tetrahydroxy phenyl porphyrin gold nano grain with nucleocapsid structure;
(3) process of carrier: mixing solutions conductive glass being placed in Ursol D, Sodium Nitrite and hydrochloric acid, take saturated calomel electrode as reference electrode, platinum electrode is to electrode, conductive glass is working electrode, interval at 0.4 ~-0.6V, cyclic voltammetry scan, obtains the surperficial keyed jointing conductive glass of aryl diazonium salts;
(4) carbon nanotube of the acidifying of step (1) gained and dicyclohexylcarbodiimide are joined in dimethyl sulfoxide (DMSO), put into by the conductive glass processed through step (3), heating 20 ~ 30h, takes out conductive glass again, respectively after water and ethanol purge, nitrogen dries up;
(5) the tetrahydroxy phenyl porphyrin gold nano grain of step (2) gained is scattered in ethanol, then by dispersant liquid drop on the conductive glass processed through step (4), lucifuge is placed drying and is obtained the Photoelectric nanometer composite membrane material of load on conductive glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310282504.2A CN103342471B (en) | 2013-07-05 | 2013-07-05 | A kind of Photoelectric nanometer composite membrane material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310282504.2A CN103342471B (en) | 2013-07-05 | 2013-07-05 | A kind of Photoelectric nanometer composite membrane material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342471A CN103342471A (en) | 2013-10-09 |
| CN103342471B true CN103342471B (en) | 2015-10-21 |
Family
ID=49277313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310282504.2A Expired - Fee Related CN103342471B (en) | 2013-07-05 | 2013-07-05 | A kind of Photoelectric nanometer composite membrane material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342471B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635143A (en) * | 2020-06-02 | 2020-09-08 | 东华大学 | Method for preparing porphyrin-based polymer electrochromic film through electrodeposition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849376A (en) * | 2014-03-20 | 2014-06-11 | 陇南师范高等专科学校 | Method of preparing porphyrin nanogold composite material with core-shell structure |
| JP6652740B2 (en) * | 2015-10-28 | 2020-02-26 | 日本電気硝子株式会社 | Manufacturing method of glass sheet with film |
| CN109847797A (en) * | 2019-01-28 | 2019-06-07 | 三峡大学 | A kind of preparation method and applications for the gold nano catalyst that porphyrin is stable |
| CN109926089A (en) * | 2019-03-22 | 2019-06-25 | 三峡大学 | The preparation method and application of the stable copper nanocatalyst of porphyrin |
| CN109926088A (en) * | 2019-03-22 | 2019-06-25 | 三峡大学 | The preparation method and application of the stable palladium nanocatalyst of porphyrin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691280A (en) * | 2009-10-30 | 2010-04-07 | 上海交通大学 | Method for preparing carbon nano tube film |
| CN102507685A (en) * | 2011-10-31 | 2012-06-20 | 西北师范大学 | Funtionalized carbon nanotube modified electrode and its preparation method and uses |
| CN102600774A (en) * | 2012-03-09 | 2012-07-25 | 北京化工大学 | Preparation method for water-soluble fluorescent nuclear shell nanometer particles |
| CN102621353A (en) * | 2012-04-13 | 2012-08-01 | 西北师范大学 | Method for studying light induced electron transfer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5417630B2 (en) * | 2009-07-08 | 2014-02-19 | 綜研化学株式会社 | Composition for solid electrolyte and solar cell using the same |
-
2013
- 2013-07-05 CN CN201310282504.2A patent/CN103342471B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691280A (en) * | 2009-10-30 | 2010-04-07 | 上海交通大学 | Method for preparing carbon nano tube film |
| CN102507685A (en) * | 2011-10-31 | 2012-06-20 | 西北师范大学 | Funtionalized carbon nanotube modified electrode and its preparation method and uses |
| CN102600774A (en) * | 2012-03-09 | 2012-07-25 | 北京化工大学 | Preparation method for water-soluble fluorescent nuclear shell nanometer particles |
| CN102621353A (en) * | 2012-04-13 | 2012-08-01 | 西北师范大学 | Method for studying light induced electron transfer |
Non-Patent Citations (1)
| Title |
|---|
| 不同类型卟啉自组装膜的制备及表征;杨建东等;《应用化学》;20130331;第30卷(第3期);第343-348页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635143A (en) * | 2020-06-02 | 2020-09-08 | 东华大学 | Method for preparing porphyrin-based polymer electrochromic film through electrodeposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342471A (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342471B (en) | A kind of Photoelectric nanometer composite membrane material and its preparation method and application | |
| Jiang et al. | Facile preparation of boron and nitrogen codoped green emission carbon quantum dots for detection of permanganate and captopril | |
| Xu et al. | A sensitive photoelectrochemical biosensor for AFP detection based on ZnO inverse opal electrodes with signal amplification of CdS-QDs | |
| CN106501336B (en) | A kind of optical electro-chemistry sensor and its preparation and application | |
| CN102749317B (en) | Surface enhanced Raman scattering probe based on carbon nanotube and preparation method thereof | |
| CN106093148B (en) | It is a kind of to visualize H in photic electric biosensor detection cell2The construction method of S | |
| Zheng et al. | An enzyme-free fluorescent sensing platform for the detection of uric acid in human urine | |
| Wang et al. | Self-powered sensing platform equipped with Prussian blue electrochromic display driven by photoelectrochemical cell | |
| Peng et al. | Photoelectrochemical sensor based on zinc phthalocyanine semiconducting polymer dots for ultrasensitive detection of dopamine | |
| CN110358535B (en) | Fluorescence carbon dot nanoprobe for detecting hydrogen sulfide and imaging hydrogen sulfide in living cells based on internal filtering effect and using method thereof | |
| Xu et al. | Renewable photoelectrochemical cytosensing platform for rapid capture and detection of circulating tumor cells | |
| CN103926234A (en) | Single-layer nanogold surface-enhanced Raman activity substrate and preparation method thereof | |
| Cai et al. | Enhanced electrochemiluminescence of porphyrin-based metal–organic frameworks controlled via coordination modulation | |
| CN1858117A (en) | Tetrahydro quinoline functional dye containing thiophene bridge chain | |
| Zhuge et al. | Visible-light photoelectrochemical sensor for glutathione based on CoFe2O4-nanosphere-sensitized copper tetraaminophthalocyanine–graphene oxide | |
| CN104076072A (en) | High-sensitivity photoelectrochemical sensor made from iridium oxide-ferriporphyrin-titanium oxide and preparation method for sensor | |
| CN111965355A (en) | Cathode photoelectrochemistry immunosensor and preparation method and application thereof | |
| Wu et al. | ZIF-8 encapsulated upconversion nanoprobes to evaluate pH variations in food spoilage | |
| CN108896631B (en) | Method for constructing photoelectrochemical aptamer sensor with copper sulfide-titanium dioxide heterojunction structure as support | |
| Fang et al. | Electrocatalytic excitation and Co-reaction acceleration synergistic amplification signal of hydrazide-conjugated carbon dots for an electrochemiluminescence immunoassay | |
| Xiao et al. | Highly efficient sequential light-harvesting system constructed by macrocycle-based nanoparticles for tunable photoluminescence | |
| CN109142486A (en) | A kind of preparation method of the Photoelectrochemistrbiosensor biosensor for microRNA detection | |
| Wu et al. | Catalytic hairpin assembly coupled with Ir (III) complex sensitization strategy for split-type photoelectrochemical biosensing | |
| Dong et al. | Zirconium dioxide as electrochemiluminescence emitter for D-dimer determination based on dual-quenching sensing strategy | |
| CN111551596B (en) | Preparation method of photoelectric chemical sensor for efficiently and sensitively detecting kanamycin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151021 Termination date: 20160705 |