Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer
The metallo-supramolecular polymer (MSP) is considered one of the most promising electrodes for electrochromic devices due to its intrinsically stable redox properties. Nevertheless, despite extensive work focusing on improving the electrochromic and electrochemical properties of MSPs, little experi...
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-12-01
|
| Series: | Polymers |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4360/15/24/4735 |
| _version_ | 1797379601224171520 |
|---|---|
| author | Xiaofang Fu Zhuohui Zhang Zhenhu Cao Alexandr Alexandrovich Rogachev Maxim Anatolievich Yarmolenko Tao Chen Hongtao Cao Hongliang Zhang |
| author_facet | Xiaofang Fu Zhuohui Zhang Zhenhu Cao Alexandr Alexandrovich Rogachev Maxim Anatolievich Yarmolenko Tao Chen Hongtao Cao Hongliang Zhang |
| author_sort | Xiaofang Fu |
| collection | DOAJ |
| description | The metallo-supramolecular polymer (MSP) is considered one of the most promising electrodes for electrochromic devices due to its intrinsically stable redox properties. Nevertheless, despite extensive work focusing on improving the electrochromic and electrochemical properties of MSPs, little experimental evidence exists from in-depth investigations on the anion-induced electrochromism of MSPs. Herein, Ru-based metallo-supramolecular polymer (polyRu) films with excellent electrochromic performance were fabricated through a novel electrochemical deposition method, and the electrochromic mechanism was further understood. The polyRu films possess fast reaction kinetics with a short switching time of 4.0 s (colored) and 2.8 s (bleached) and highly reversible redox properties due to the resulting impacts on the capacitive behaviors (containing surface, near-surface and intercalation pseudo-capacitance) of the perchlorate ions in the electrochromic process. Moreover, the electrochromic degradation of the polyRu films is considered to stem from the numerous nanopores in the film induced by ClO<sub>4</sub><sup>−</sup> transport and the exchange of counter anions from Cl<sup>−</sup> to ClO<sub>4</sub><sup>−</sup>. In addition, a physical model, revealing the transport of conduction ions and the evolution of the structure and properties of the polyRu film during the electrochromic process, is presented. It is observed that the charge balance of Ru<sup>3+</sup> and Ru<sup>2+</sup>, achieved through the adsorption/desorption of ClO<sub>4</sub><sup>−</sup> on the film, provides electrochromic and electrochemical reversibility to the polyRu film under positive/negative bias. Correspondingly, a transformation from polyRu·(Cl<sup>−</sup>)<sub>2n</sub> to polyRu·(ClO<sub>4</sub><sup>−</sup>)<sub>x</sub>(Cl<sup>−</sup>)<sub>2n−x</sub> in the polyRu film is induced by a counter anion exchange from Cl<sup>−</sup> to ClO<sub>4</sub><sup>−</sup>. Revealing the detailed perchlorate ion transfer kinetics and electrochromic mechanism in this film can offer new insights into the application of metallo-supramolecular polymers in electrochromic devices. |
| first_indexed | 2024-03-08T20:25:29Z |
| format | Article |
| id | doaj.art-e29e5cbb04ba4465b9ef81ba6d8a1985 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-08T20:25:29Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-e29e5cbb04ba4465b9ef81ba6d8a19852023-12-22T14:36:54ZengMDPI AGPolymers2073-43602023-12-011524473510.3390/polym15244735Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular PolymerXiaofang Fu0Zhuohui Zhang1Zhenhu Cao2Alexandr Alexandrovich Rogachev3Maxim Anatolievich Yarmolenko4Tao Chen5Hongtao Cao6Hongliang Zhang7Laboratory of Advanced Nano Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, ChinaLaboratory of Advanced Nano Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, ChinaNingbo Mi Ruo Electronic Technology Co., Ltd., Ningbo 315203, ChinaOptical Anisotropic Films Laboratory, Institute of Chemistry of New Materials of the National Academy of Sciences of Belarus, 220141 Minsk, BelarusDepartment of Radiophysics and Electronics, Francisk Skorina Gomel State University, 104, Sovetskaya Street, 246019 Gomel, BelarusLaboratory of Advanced Nano Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, ChinaLaboratory of Advanced Nano Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, ChinaLaboratory of Advanced Nano Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, ChinaThe metallo-supramolecular polymer (MSP) is considered one of the most promising electrodes for electrochromic devices due to its intrinsically stable redox properties. Nevertheless, despite extensive work focusing on improving the electrochromic and electrochemical properties of MSPs, little experimental evidence exists from in-depth investigations on the anion-induced electrochromism of MSPs. Herein, Ru-based metallo-supramolecular polymer (polyRu) films with excellent electrochromic performance were fabricated through a novel electrochemical deposition method, and the electrochromic mechanism was further understood. The polyRu films possess fast reaction kinetics with a short switching time of 4.0 s (colored) and 2.8 s (bleached) and highly reversible redox properties due to the resulting impacts on the capacitive behaviors (containing surface, near-surface and intercalation pseudo-capacitance) of the perchlorate ions in the electrochromic process. Moreover, the electrochromic degradation of the polyRu films is considered to stem from the numerous nanopores in the film induced by ClO<sub>4</sub><sup>−</sup> transport and the exchange of counter anions from Cl<sup>−</sup> to ClO<sub>4</sub><sup>−</sup>. In addition, a physical model, revealing the transport of conduction ions and the evolution of the structure and properties of the polyRu film during the electrochromic process, is presented. It is observed that the charge balance of Ru<sup>3+</sup> and Ru<sup>2+</sup>, achieved through the adsorption/desorption of ClO<sub>4</sub><sup>−</sup> on the film, provides electrochromic and electrochemical reversibility to the polyRu film under positive/negative bias. Correspondingly, a transformation from polyRu·(Cl<sup>−</sup>)<sub>2n</sub> to polyRu·(ClO<sub>4</sub><sup>−</sup>)<sub>x</sub>(Cl<sup>−</sup>)<sub>2n−x</sub> in the polyRu film is induced by a counter anion exchange from Cl<sup>−</sup> to ClO<sub>4</sub><sup>−</sup>. Revealing the detailed perchlorate ion transfer kinetics and electrochromic mechanism in this film can offer new insights into the application of metallo-supramolecular polymers in electrochromic devices.https://www.mdpi.com/2073-4360/15/24/4735electrochromic filmRu(II)-based metallo-supramolecular polymerkinetics of ion transportdegradation mechanismanion-induced electrochromism |
| spellingShingle | Xiaofang Fu Zhuohui Zhang Zhenhu Cao Alexandr Alexandrovich Rogachev Maxim Anatolievich Yarmolenko Tao Chen Hongtao Cao Hongliang Zhang Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer Polymers electrochromic film Ru(II)-based metallo-supramolecular polymer kinetics of ion transport degradation mechanism anion-induced electrochromism |
| title | Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer |
| title_full | Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer |
| title_fullStr | Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer |
| title_full_unstemmed | Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer |
| title_short | Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer |
| title_sort | mechanistic insights into anion induced electrochromism of ru ii based metallo supramolecular polymer |
| topic | electrochromic film Ru(II)-based metallo-supramolecular polymer kinetics of ion transport degradation mechanism anion-induced electrochromism |
| url | https://www.mdpi.com/2073-4360/15/24/4735 |
| work_keys_str_mv | AT xiaofangfu mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT zhuohuizhang mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT zhenhucao mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT alexandralexandrovichrogachev mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT maximanatolievichyarmolenko mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT taochen mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT hongtaocao mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer AT hongliangzhang mechanisticinsightsintoanioninducedelectrochromismofruiibasedmetallosupramolecularpolymer |