CN106025299B - A kind of electrochemical in-situ preparation method of porphyrin nano array - Google Patents
A kind of electrochemical in-situ preparation method of porphyrin nano array Download PDFInfo
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- CN106025299B CN106025299B CN201610387037.3A CN201610387037A CN106025299B CN 106025299 B CN106025299 B CN 106025299B CN 201610387037 A CN201610387037 A CN 201610387037A CN 106025299 B CN106025299 B CN 106025299B
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Abstract
The invention discloses a kind of electrochemical in-situ preparation methods of porphyrin nano array, belong to field of nano material preparation.The method that the present invention uses electrochemical deposition, it is acted on using the electropolymerization between porphyrin, by Porphyrin Molecule oriented growth in conductive substrates, it is formed in situ porphyrin nano array polymeric material, strong adhesive force between porphyrin nano array and conductive substrates prepared by this method, it is not easily to fall off, it can be directly used for photoelectrocatalysis, energy storage device, electronic component, chemical catalyst etc..The present invention has the advantages that preparation process is simple, and controllability is strong, porphyrin array electrode material stable structure, superior performance, easy to spread.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly to a kind of electrochemical in-situ preparation method of porphyrin nano array.
Background technology
In recent years, petroleum resources are more and more deficienter, and motor vehicle exhaust emission is growing day by day, and living environment go fromes bad to worse, and can hold
The exploitation of continuous property green energy resource and the high usage energy is extremely urgent.Fuel cell (Fuel Cell) is a kind of to send out fuel
Chemical energy caused by raw electrochemical reaction is directly translated into the converting system of electric energy, and there is green high-efficient, fuel to be easy to get, easily store up
The advantages of depositing and carrying and get more and more people's extensive concerning.Oxygen reduction electrode decides battery performance as the cathode of fuel cell
Quality, and the performance of catalyst directly influences the performance of oxygen reduction electrode.The common cathodic oxygen reduction of fuel cell is urged
Agent is mainly platinum, because its is of high cost, reserves are rare, and is easily poisoned by CO and limit its application.
Therefore, developing oxygen reduction catalyst that is efficient, economic and stablizing becomes the target of numerous researchers pursuit.Largely grind
It is considered as most potential fuel battery negative pole hydrogen reduction to study carefully some transition metal macrocyclic complexs such as discovery, porphyrin, phthalocyanine
One of catalyst material.Especially porphyrin has the conjugate planes structure of high degree of symmetry and excellent chemical stability, and it is tied
Structure is similar to enzyme, can be effectively promoted H2O2Decomposition, so as to improve the working efficiency of battery, it is often more important that it is in acidity
With show good catalytic reduction activity in alkaline medium to oxygen molecule, and it is at direct methanol fuel cell (DMFC)
In can occur to avoid reaction after because methanol from cathode to the anodic potentials that anode brings are diffused into bears shifting, this, which becomes, most has
Wish the oxygen reduction catalyst for replacing precious metal as fuel cell.
Redox reactions are also widely present in nature, and cytochromes and ferroheme are that catalytic oxygen restores in organism
The functional component of reaction, they are all the porphyrin aggregations being made of porphyrin, show good catalytic performance.At present for porphin
On the basis of the research of quinoline catalyst is largely focused on Porphyrin Molecule monomer directly as catalyst, and for porphyrin aggregation
Research report as oxygen reduction catalyst agent is less.
Invention content
The purpose of the present invention is to provide a kind of electrochemical in-situ preparation methods of porphyrin nano array.
Based on above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of electrochemical in-situ preparation method of porphyrin nano array, includes the following steps：
（1）The preparation of electrolyte solution
Tetrabutylammonium perchlorate is added in the mixed solvent of dichloromethane and pyridine composition, after being completely dissolved, adds four
Aminobenzene porphyrin [purity ＞ 95%, English name：Meso-Tetra (4-aminophenyl) Porphine, No. CAS：
22112-84-1 buys producer：Frontier Scientific, Inc., similarly hereinafter], stirring makes tetramino benzene porphyrin completely molten
Solution obtains electrolyte solution；
（2）The preparation of porphyrin nano array
Clean indium tin oxide-coated glass is immersed into step（1）Electrolyte solution in, using Ag/AgCl electrodes as reference
Electrode, Pt electrodes are received to carry out at least 5 times complete cyclic voltammetric polarization process in threeway electrolytic cell to electrode up to porphyrin
Rice array.
Step（1）The volume ratio of middle dichloromethane and pyridine is（90~95）︰（10~5）, and tetrabutylammonium perchlorate is in electricity
A concentration of 0.05-0.15mol/L in electrolyte solution, a concentration of 0.001- of the tetramino benzene porphyrin in electrolyte solution
0.002mol/L。
Step（2）Sweep speed is 0.02V/s ~ 0.05V/s in middle cyclic voltammetric polarization process.
The present invention provides a kind of electrochemical in-situ preparation methods of porphyrin nano array, are directly grown in conductive substrates
Porphyrin nano array can be used directly as electrode for optical electro-chemistry catalysis, biosensor and energy storage material.The present invention
Preparation process is simple, and porphyrin array and conductive substrates binding ability are strong, not easily to fall off.
Description of the drawings
Fig. 1 is the SEM figures for the porphyrin nano array being prepared in embodiment 1；
Fig. 2 is the redox reactions catalytic performance result figure of 1 mesoporphyrin nano-array of embodiment；
Fig. 3 is the SEM figures for the porphyrin nano array being prepared in embodiment 2；
Fig. 4 is the SEM figures for the porphyrin nano array being prepared in embodiment 3.
Specific embodiment
The advantages of in order to make the purpose of the present invention, technical process and have more clearly, by the following examples to this
Invention is described in detail, but the present invention is not limited only to the embodiment.
Embodiment 1
A kind of electrochemical in-situ preparation method of porphyrin nano array, includes the following steps：
（1）Conductive substrates pre-process
By tin indium oxide（ITO）Electro-conductive glass is cut into 1 × 2 square centimeter of size, successively with detergent, acetone, anhydrous second
Alcohol, deionized water are cleaned by ultrasonic, and remove surface impurity dirt, and spare with nitrogen drying.
（2）The preparation of electrolyte solution
10mmol tetrabutylammonium perchlorates are dissolved in 95mL dichloromethane, add 5mL pyridines, ultrasonic disperse 5min is stirred
10min is mixed, adds in 0.1mmol tetramino benzene porphyrin [purity ＞ 95%, English name later：meso-Tetra (4-
Aminophenyl) Porphine, No. CAS：22112-84-1 buys producer：Frontier Scientific, Inc., under
Together], ultrasonic disperse 10min, stir 30min, obtain claret clear solution, be protected from light be sealed it is spare.
（3）The preparation of porphyrin nano array
At 25 DEG C of room temperature, by processed clean tin indium oxide（ITO）Electro-conductive glass is immersed in above-mentioned electrolyte solution,
It is reference electrode that Ag/AgCl electrodes are inserted into threeway electrolytic cell, and Pt electrodes are to build three electrode work systems, so to electrode
Argon gas 30min is passed through in backward electrolyte solution, complete cyclic voltammetric polarization process, current potential model are carried out with electrochemical workstation
Enclose selection needs 10 complete cyclic voltammetric polarization process, prepares system in total in 0V ~ 1.6V, sweep speed selection 0.05V/s
It after obtaining porphyrin nano array, is rinsed well successively with dichloromethane, absolute ethyl alcohol, deionization, and guarantor is protected from light with nitrogen drying
It deposits.As shown in Figure 1 it can be seen that conductive glass surface has fibrous porphyrin nano line vertical-growth, and the composition array junctions that are evenly distributed
Structure, several, top, porphyrin line forms a node.Information in Fig. 1 demonstrates the feasibility of the method for the invention.
（4）The hydrogen reduction catalytic performance characterization of porphyrin nano array electrode material
Using platinum electrode be to electrode, Ag/AgCl electrodes as reference electrode, will be covered with the indium oxide of porphyrin nano array
Tin electro-conductive glass for working electrode form ORR performance tests used in three-electrode system, 0.1M NaOH solutions be electrolyte, first to
Nitrogen or oxygen 30min are passed through in electrolyte, ensures that test environment is respectively at the saturation state of nitrogen or oxygen, then using electricity
Gesture scanning range -1.2V ~ 0.8V, the cyclic voltammetry that sweep speed is 0.02V/s are tested.Experimental result is as shown in Figure 2（Fig. 2,
Abscissa represents ORR test scanning potential ranges, and ordinate represents current strength）, porphyrin nano array during oxygen saturation state
Electrode material current strength significantly becomes larger, and redox reactions have occurred, and illustrates that the porphyrin nano array material has oxygen also
The catalytic performance of original reaction makes it can be applied to fuel cell, ORR catalyst is used as in metal-air battery.
Embodiment 2
A kind of electrochemical in-situ preparation method of porphyrin nano array, includes the following steps：
（1）Conductive substrates pre-process
By tin indium oxide（ITO）Electro-conductive glass is cut into 1 × 2 square centimeter of size, successively with detergent, acetone, anhydrous second
Alcohol, deionized water are cleaned by ultrasonic, and remove surface impurity dirt, and spare with nitrogen drying.
（2）The preparation of electrolyte solution
15mmol tetrabutylammonium perchlorates are dissolved in 90mL dichloromethane, add 10mL pyridines, ultrasonic disperse 5min is stirred
10min is mixed, adds in 0.2mmol tetramino benzene porphyrins later, ultrasonic disperse 10min stirs 30min, it is transparent molten to obtain claret
Liquid, be protected from light be sealed it is spare.
（3）The preparation of porphyrin nano array
At 25 DEG C of room temperature, by processed clean tin indium oxide（ITO）Electro-conductive glass is immersed in above-mentioned electrolyte solution,
It is reference electrode that Ag/AgCl electrodes are inserted into threeway electrolytic cell, and Pt electrodes are to build three electrode work systems, so to electrode
Argon gas 30min is passed through in backward electrolyte solution.Complete cyclic voltammetric polarization process, current potential model are carried out with electrochemical workstation
Enclose selection needs 15 complete cyclic voltammetric polarization process, is prepared into total in 0V ~ 1.6V, sweep speed selection 0.04V/s
It to after porphyrin nano array, is rinsed well successively with dichloromethane, absolute ethyl alcohol, deionization, and guarantor is protected from light with nitrogen drying
It deposits.As shown in Figure 2 it can be seen that generating thicker fibrous porphyrin nano line and forming array in conductive glass surface vertical direction
Structure, and every porphyrin nano line top is thicker.Information in Fig. 3 demonstrates the feasibility of the method for the invention.
Embodiment 3
A kind of electrochemical in-situ preparation method of porphyrin nano array, includes the following steps：
（1）Conductive substrates pre-process
By tin indium oxide（ITO）Electro-conductive glass is cut into 1 × 2 square centimeter of size, successively with detergent, acetone, anhydrous second
Alcohol, deionized water are cleaned by ultrasonic, and remove surface impurity dirt, and spare with nitrogen drying.
（2）The preparation of electrolyte solution
5mmol tetrabutylammonium perchlorates are dissolved in 95mL dichloromethane, add 5mL pyridines, ultrasonic disperse 5min, stirring
10min adds in 0.2mmol tetramino benzene porphyrins later, and ultrasonic disperse 10min stirs 30min, obtains claret clear solution,
Be protected from light be sealed it is spare.
（3）The preparation of porphyrin nano array
At 25 DEG C of room temperature, by processed clean tin indium oxide（ITO）Electro-conductive glass is immersed in above-mentioned electrolyte solution,
It is reference electrode that Ag/AgCl electrodes are inserted into threeway electrolytic cell, and Pt electrodes are to build three electrode work systems, so to electrode
Argon gas 30min is passed through in backward electrolyte solution.Complete cyclic voltammetric polarization process, current potential model are carried out with electrochemical workstation
Enclose selection needs 5 complete cyclic voltammetric polarization process, is prepared into total in 0V ~ 1.6V, sweep speed selection 0.02V/s
It to after porphyrin nano array, is rinsed well successively with dichloromethane, absolute ethyl alcohol, deionization, and guarantor is protected from light with nitrogen drying
It deposits.As shown in Figure 3 it can be seen that conductive substrates surface vertical direction have finer fiber shape porphyrin nano line generation, be evenly distributed and
Forming array structure, while similar several porphyrin nanos line top flocks together to form node.Information in Fig. 4 demonstrates
The feasibility of the method for the invention.
Claims (1)
1. a kind of electrochemical in-situ preparation method of porphyrin nano array, which is characterized in that include the following steps：
（1）The preparation of electrolyte solution
By tetrabutylammonium perchlorate's addition dichloromethane and the mixed solvent of pyridine composition, the volume ratio of dichloromethane and pyridine is
（90~95）︰（10~5）, after being completely dissolved, tetramino benzene porphyrin is added, stirs, is completely dissolved tetramino benzene porphyrin, is obtained
Electrolyte solution, a concentration of 0.05-0.15mol/L of the tetrabutylammonium perchlorate in electrolyte solution, tetramino benzene porphyrin exist
A concentration of 0.001-0.002mol/L in electrolyte solution；
（2）The preparation of porphyrin nano array
Clean indium tin oxide-coated glass is immersed into step（1）Electrolyte solution in, using Ag/AgCl electrodes as reference electricity
Pole, Pt electrodes is carry out at least 5 times complete cyclic voltammetric polarization process up to porphyrin nano to electrode in threeway electrolytic cell
Array, in cyclic voltammetric polarization process, potential range is 0 ~ 1.6v, and sweep speed is 0.02V/s ~ 0.05V/s.
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| CN115275230A (en) * | 2022-08-09 | 2022-11-01 | 湘潭大学 | Heteroatom-loaded polymetallic porphyrin material, synthesis method thereof and application thereof in zinc-air battery |
| CN116947328A (en) * | 2023-06-08 | 2023-10-27 | 华南理工大学 | Preparation method of cuprous iodide/porphyrin graphite alkyne p-n heterojunction material, product and application thereof |
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| CN103308580A (en) * | 2013-05-14 | 2013-09-18 | 西北师范大学 | Novel use of porphyrin modified electrode |
Non-Patent Citations (1)
| Title |
|---|
| Electrocatalytic reduction of carbon dioxide on a cobalt tetrakis(4-aminophenyl)porphyrin modified electrode in BMImBF4;Diego Quezada等;《Royal Society of Chemistry》;20140520;第38卷(第8期);第3606-3612页 * |
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