CN111073007A - Preparation of organic polymer and ruthenium coordination polymer hybrid film and photoelectric property thereof - Google Patents

Preparation of organic polymer and ruthenium coordination polymer hybrid film and photoelectric property thereof Download PDF

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CN111073007A
CN111073007A CN201811226913.XA CN201811226913A CN111073007A CN 111073007 A CN111073007 A CN 111073007A CN 201811226913 A CN201811226913 A CN 201811226913A CN 111073007 A CN111073007 A CN 111073007A
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organic polymer
film
ruthenium
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hybrid film
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高丽华
王红玲
李寒峰
任若琪
叶怀尧
王克志
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Beijing Technology and Business University
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Abstract

An organic polymer and ruthenium coordination polymer hybrid film with good stability and photoelectric conversion performance relates to a preparation method of an organic polymer/ruthenium coordination polymer hybrid film and photoelectrochemical activity evaluation. The film is prepared from poly (4-styrenesulfonic acid-copolymerization-maleic acid) anions and a triphenylamine-containing poly-pyridine mononuclear ruthenium complex through dual functions of static electricity and electropolymerization. The light intensity is 100mW/cm2Is irradiated with white light (730nm & gt, lambda & gt 325nm) to generate 14.4 mu A/cm when a bias voltage of-0.3V (vs SCE) is applied2The photocurrent (A) shows good photoelectric conversion performance, and is expected to be applied to the development of solar cells.

Description

Preparation of organic polymer and ruthenium coordination polymer hybrid film and photoelectric property thereof
Technical Field
The invention belongs to the field of electrochemistry, relates to a hybrid film formed by two components, and particularly relates to a preparation method and photoelectrochemical properties of the hybrid film of an organic polymer and a ruthenium coordination polymer.
Background
At present, with the increasing attention paid to energy and environmental protection problems, the development of the solar cell industry is accelerated. In the field of solar cells, single crystal silicon solar cells are generally used, however, silicon materials are high in price, energy consumption is high in the production and manufacturing process of silicon plates, environmental pollution is caused, and the wide application of the solar cells is seriously influenced. Therefore, the main direction of development of solar cells in the future is to find a novel solar cell material which is cheap, clean, environment-friendly, good in stability, easy to manufacture in a large area and has a good photovoltaic effect.
The organic polymer has the characteristics of various types, easy cutting of structures, light weight, low cost, low energy consumption in production, small environmental pollution and the like, and shows potential application prospects in the field of solar cells. However, the materials have the disadvantages of short service life and low photoelectric conversion efficiency, and the requirements of battery development cannot be met. Through hybridization of two or more materials, molecular-level compounding of materials with different properties and complementation and optimization of properties can be realized, so that the hybrid material has wide application prospect.
The nail complex has the characteristics of abundant photophysical and photochemical properties, high excited state reactivity, long service life, good stability and the like, and is often used as a photosensitizer in a dye-sensitized solar cell. We have reported the preparation of some nail (II) complex-based electrostatic self-assembled hybrid thin film modified electrodes and the photoelectric conversion properties of such films (Jianan Min Qi, Hui LiWang, Li Hua Gao, Hao Lin, Ke Zhi Wang.A. New organic-organic film based on purified ruthenium (II) complex and [ BW ]11Zn(H2O)O39]7-，Materials letters，2015，153，33-35.Honglei Zhang，Jianmin Qi，Lihua Gao，Kezhi Wang，A hybridelectrostatically self-assembled film based on dinuclear ruthenium(II)polypyridyl complex and europium-substituted tungstoborate，Colloids andSurfacesA：Physicochem.Eng.Aspects 2016，492，119-126.Huaiyao Ye，Jianmin Qi，RuiSun，Lihua Gao，Kezhi Wang.Photoelectric active hybrid film based onRuIIterpyridyl complex and EuIIIsubstituted Keggin polyoxometalate of[Eu(BW11O39)2]15-Electrochimica Acta, 2017, 256, 291-. Research results show that the film can generate stable cathode photocurrent under illumination, but the structure of the nail complex forming the hybrid film has great influence on the photoelectric conversion performance of the film. Therefore, the photoelectric conversion performance of the thin film material can be improved by optimizing the structure of the ruthenium complex. In addition, we have found that: although the method of assembling two film-forming components to an electrode by an electrostatic self-assembly method is simple, it takes a long time to prepare a multilayer thin film having a high photoelectric conversion efficiency.
The electrochemical polymerization method can utilize precursor molecules to directly generate coupling reaction on the surface of an electrode so as to prepare a film on the electrode. The method has the advantages of short time consumption and low cost, can directly generate a stable cross-linked polymer film without a catalyst, and can adjust the thickness and the shape of the film by adjusting electrochemical parameters. However, the bonding force between the polymer film directly obtained on the conductive glass by the electrochemical polymerization method and the conductive glass is poor. Through a large number of experimental explorations, firstly, an anionic polymer is combined on conductive glass through electrostatic interaction, then, an electrochemical polymerization method is applied to polymerize a mononuclear nail complex into a nail coordination polymer, and a hybrid film containing an organic polymer and the nail coordination polymer is prepared, and researches show that: the film material is an electrode material with good photoelectric conversion performance. At present, the hybrid film material is not reported.
Disclosure of Invention
The invention aims to prepare an organic polymer/ruthenium coordination polymer hybrid film with good photoelectric conversion performance.
The technical scheme of the invention is as follows:
firstly, cleaning a conductive glass substrate, then immersing the substrate into an ethanol solution of 3-aminopropyl-triethoxysilane for 8 hours, taking out the substrate, washing the substrate by absolute ethanol, immersing the substrate into 2mg/mL aqueous solution of sodium poly (4-styrenesulfonate-co-maleic acid) (molecular weight 20000g/mol, abbreviated as PSS-co-MA) for 1 hour, fully washing the substrate by distilled water, and drying the substrate by blowing. At this time, a layer of PSS-co-MA anion is electrostatically adsorbed on the conductive glass substrate. Then, dissolving the mononuclear nail complex into dichloromethane solution containing tetrabutylammonium hexafluorophosphate to enable the concentration of the mononuclear nail complex to be 1mmol/L, and carrying out electrochemical polymerization by controlling the scanning speed and the number of scanning cycles within a certain potential range, so that the mononuclear nail complex is polymerized on the surface of a conductive glass electrode deposited with a layer of PSS-co-MA to form nail coordination polymer films with different thicknesses.
The organic polymer adopted by the invention is sodium poly (4-styrenesulfonic acid-co-maleic acid) (molecular weight 20000g/mol, abbreviated as PSS-co-MA).
The molecular formula of the mononuclear nail complex adopted by the invention is [ RuL3](ClO4)2The structural formula is as follows:
Figure BSA0000172347020000021
the organic polymer/nail coordination polymer hybrid film prepared by the invention is prepared for the first time, and the organic polymer anions and the nail coordination polymer cations are combined together through the dual functions of static electricity and polymerization. Compared with the prior art, the film has better stability than a pure electropolymerization film and better photoelectric conversion performance than a hybrid film formed by self-assembling an organic polymer and a mononuclear nail complex through pure static electricity. Therefore, the organic polymer/nail coordination polymer hybrid film has potential application prospect in the field of photoelectric conversion.
Drawings
FIG. 1 polymerization of 1-turn PSS-co-MA/{ RuL3}nUv-vis absorption spectrum of the hybrid film.
FIG. 2 polymerization of 1-turn PSS-co-MA/{ RuL3}nThe hybrid film produces a photocurrent-time curve under illumination. Light source: 100mW/cm2White light, bias voltage: -0.3V to +0.5V, electrode area: 0.28cm2Supporting electrolyte solution: 0.1mol/L of Na2SO4Solution (pH 2).
FIG. 3 polymerization of 1-turn PSS-co-MA/{ RuL3}nThe relationship between the photocurrent generated by the hybrid film and the bias potential applied to the electrode is-0.3V- + 0.5V. Light source: 100mW/cm2White light, electrode area: 0.28cm2Supporting electrolyte solution: 0.1mol/L of Na2SO4Solution (pH 2).
Detailed Description
Example 1: PSS-co-MA/{ RuL3}nPreparation of hybrid films
Pretreatment of the substrate:
(1) selecting conductive glass with the size of 1cm multiplied by 3cm, cleaning the conductive glass with distilled water after being cleaned by a detergent, and drying the conductive glass by blowing.
(2) Uniformly mixing concentrated ammonia water, 30% hydrogen peroxide and distilled water according to the volume ratio of 1: 5, heating to 70 ℃, immersing and heating the clean conductive glass substrate for 20 minutes, taking out, fully cleaning with distilled water, and drying with air.
(3) Preparing 5% ethanol solution of 3-aminopropyl-triethoxysilane, immersing the substrate treated in the step (2) in the ethanol solution for 8 hours for silanization, taking out the substrate, cleaning the substrate with absolute ethanol, and drying the substrate with air. The silanized substrate was immersed in a hydrochloric acid solution having a pH of 2 for 20 minutes to protonate, and after taking out, the substrate was washed with distilled water and air-dried.
PSS-co-MA/{RuL3}nPreparation of hybrid film:
and (4) immersing the substrate treated in the step (3) into a 2mg/mL PSS-co-MA aqueous solution for 1 hour, fully washing with distilled water, and drying. At this time, a layer of PSS-co-MA anion is electrostatically adsorbed on the conductive glass substrate. The method comprises the steps of taking conductive glass assembled with a layer of PSS-co-MA as a working electrode, a platinum electrode as a counter electrode, a silver wire as a reference electrode, and inserting 1mmol/L of mononuclear nail complex [ RuL ]3](ClO4)2Introducing nitrogen into the dichloromethane solution (containing 0.1mol/L tetrabutylammonium hexafluorophosphate) for 15 minutes, and scanning for one circle at the scanning speed of 0.025V/s within the range of the scanning potential of 0.0V to +2.2V to obtain the PSS-co-MA/{ RuL3}nHybrid films.
The UV-visible absorption spectrum of the film was measured by a CARY-50 type UV-visible spectrophotometer manufactured by Warran, USA. FIG. 1 shows PSS-co-MA/{ RuL, which are assembled in one turn3}nThe ultraviolet-visible absorption spectrum of the hybrid film shows that: the films showed characteristic absorption of the pinned coordination polymer at 380 and 474nm, indicating PSS-co-MA/{ RuL3}nHybrid films were successfully prepared.
Example 2: photocurrent testing of thin films
The measurement of photocurrent is carried out on CHI 660D electrochemical analyzer of Shanghai Chenghua apparatus, Inc., and the light source system is 500W ultrahigh pressure spherical xenon lamp high brightness light source system of Beijing Changtong Tech technology, Inc.; simulating sunlight in photocurrent test with light intensity of 100mW/cm2White light (730nm & gt lambda & gt 325nm), incident light intensity was measured using a calibrated radiometer from standard silicon cells of the university of Beijing teachers optical instruments factory.
The PSS-co-MA/{ RuL prepared in example 1 was reacted at room temperature3}nThe hybrid film is used as a working electrode, the platinum wire is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and the electrode is placed in 0.1mol/L Na2SO4In an aqueous solution (pH 2), the light intensity was 100mW/cm2(iii) white light (730nm > lambda > 325nm) illumination of PSS-co-MA/{ RuL3}nThe hybrid film is changed in the range of-0.3V- +0.5V to change the applied bias potential, and the photocurrent-induction time curve of the film is measured, the generated photocurrent-induction time curve is shown in figure 2, and the relationship curve of the photocurrent and the bias potential obtained from figure 2 is shown in figure 3. The results show that when the light intensity is 100mW/cm2(ii) white light illumination PSS-co-MA/{ RuL3}nWhen the film is used, the film can generate stable cathode photocurrent within the bias potential range of-0.3V- +0.5V, and the photocurrent response is rapid when the light source is switched on and off for many times. The density of photocurrent generated by the film can reach 10.3 muA/cm under the condition of no external potential2Applying a negative bias potential, PSS-co-MA/{ RuL3}nThe photocurrent generated by the film is enhanced, and the photocurrent density of the film is increased to 14.4 muA/cm when the external bias potential is-0.3V2. The electropolymerization is comparable to electrostatic self-assembled filmsThe film shows enhanced photoelectric conversion performance and is expected to be applied to the development of solar cells.

Claims (3)

1. An organic polymer and ruthenium coordination polymer hybrid film is prepared by depositing organic polymer anions on ITO conductive glass through electrostatic interaction, and polymerizing triphenylamine-containing polypyridine ruthenium mononuclear complex on organic polymer anion layer through double actions of electropolymerization and electrostatic interaction to obtain ruthenium coordination polymer, and is characterized in that: the film consists of poly (4-styrenesulfonic acid-co-maleic acid) anion (PSSMA) and ruthenium coordination polymer cation, wherein the molecular formula of the mononuclear ruthenium complex is [ RuL3](ClO4)2The structural formula is as follows:
Figure FSA0000172347010000011
2. the preparation method of the organic polymer and ruthenium coordination polymer hybrid film as claimed in claim 1 comprises the following steps: firstly, assembling a layer of organic polymer anions on conductive glass through silanization and electrostatic interaction, inserting the organic polymer anions serving as a working electrode, Ag/AgCl serving as a reference electrode and a platinum wire serving as a counter electrode into an electrochemical cell containing a mononuclear nail complex solution with a certain concentration, and performing cyclic voltammetry scanning by controlling the scanning rate and the number of scanning cycles within a certain scanning potential range to obtain organic polymer/ruthenium coordination polymer hybrid films with different thicknesses.
3. Use of a film according to claim 1, characterized in that: the hybrid film is used for a working electrode of a photoelectrochemical cell.
CN201811226913.XA 2018-10-22 2018-10-22 Preparation of organic polymer and ruthenium coordination polymer hybrid film and photoelectric property thereof Pending CN111073007A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115806677A (en) * 2022-11-15 2023-03-17 广东工业大学 Ruthenium polymer with photo-thermal conversion performance and preparation method thereof

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US20170044325A1 (en) * 2014-05-02 2017-02-16 National Institute For Materials Science Organic/Heterometallic Hybrid Polymer, Process for Producing Same, Film of Organic/Heterometallic Hybrid Polymer, Organic/Multimetallic Hybrid Polymer, Process for Producing Same, and Film of Organic/Multimetallic Hybrid Polymer
CN108676149A (en) * 2018-03-30 2018-10-19 北京师范大学 A kind of the high-efficiency electrochemical polymerization preparation and application of ruthenium complex film

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CN104465098A (en) * 2014-11-13 2015-03-25 昆明理工大学 ITO substrate modified by amphiphilic ruthenium complex monomolecular film and preparation method of ITO substrate
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115806677A (en) * 2022-11-15 2023-03-17 广东工业大学 Ruthenium polymer with photo-thermal conversion performance and preparation method thereof
CN115806677B (en) * 2022-11-15 2023-09-01 广东工业大学 Ruthenium polymer with photo-thermal conversion performance and preparation method thereof

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