Electropolymerized Metalloporphyrin Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis

Pailleret, Alain; Bédioui, Féthi

doi:10.1007/978-0-387-28430-9_8

Cited by 7 publications

(4 citation statements)

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“…Many studies have shown that binuclear complexes and other multimetal-centered complexes catalyze the oxygen reduction reaction at higher onset potentials with a mostly four-electron mechanism and outperform the activity of their monomeric units. − This improvement was attributed to the vicinity of the metallic centers, which at the optimum distance can bind oxygen by two metal ions . Accordingly, we postulated that electropolymerization of the cobalt corroles will result in dense corrole layers which will bring the catalytic centers close together to enable concerted reactions and thus increase the activity and selectivity toward the four-electron process by virtue of cooperative effects similar to those described above.…”

Section: Introductionmentioning

confidence: 98%

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

et al. 2018

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Fuel cells are considered as the only viable solution for long-range electromobility, but very rare and expensive platinum is currently required for catalyzing the bottleneck reaction therein: oxygen reduction. Within the search for catalysts that are not based on precious metals, cobalt corroles were uncovered to fulfill the requirements of high selectivity and low overpotential. We now report on the electropolymerization of a specifically designed catalyst, a cobalt(III) complex of tris(4-aminophenyl)corrole, upon which 3D polymeric structures were obtained. Much better catalytic activity was obtained by this approach in comparison to monomeric catalyst, manifested by significantly lower overpotentials, as well as higher selectivity to the desired 4e–/4H+ pathway. The performance in an alkaline environment makes it the most active molecular catalyst for the oxygen reduction reaction reported to date.

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Section: Introductionmentioning

confidence: 98%

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

et al. 2018

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“…Электроосаждение порфиринов, как правило, приводит к образованию проводящих пленок с ковалентной связью порфириновых фрагментов. [12,30,[42][43][48][49][50][51] В последнее время нами разработан метод активированного супероксид анион-радикалом электрохимического осаждения пленок на основе тетра(аминофенил) порфиринов из растворов ДМСО. [52] В настоящей работе мы более подробно исследуем электрохимические свойства MnClT(3-NH 2 Ph)P и MnClT(4-NH 2 Ph)P в растворах ДМСО и особенности электрохимического осаждения пленок с использованием супероксида.…”

Section: Introductionunclassified

Electrodeposition and Characterization of Polyporphyrin Films Based on Mn Complexes of Amino-substituted Tetraphenylporphyrins

Parfenyuk¹,

Tesakova²,

Chulovskaya³

et al. 2019

MHC

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В работе представлены результаты исследования электрохимического осаждения и физико-химических свойств полипорфириновых пленок, осажденных на стеклоуглероде, платине, золоте и ITO-электродах из дихлорметана (ДХМ), этанола и диметилсульфоксида (ДМСО). В качестве прекурсоров использованы хлориды Mn(III) 5,10,15,20-тетракис(3-аминофенил)порфина и Mn(III) 5,10,15,20-тетракис(4-аминофенил)порфина. Показано, что из ДМСО полипорфириновая пленка формируется в области потенциалов электровосстановления кислорода. В ДХМ и этаноле образование пленок на рабочих электродах в процессе электроокисления порфирина-мономера наблюдается в области потенциалов от 0 до +2 В. Процесс электрополимеризации изучен с использованием метода кварцевого микробаланса. Прирост массы пленки MnClT(3-NH 2 Ph)P при осаждении из ДХМ в потенциостатическом режиме в 1,9 раза больше, чем в потенциодинамическом. Поверхность пленок изучена с использованием метода сканирующей электронной микроскопии. Определено количество электронов, участвующих в процессе электрополимеризации. В работе подробно исследованы электрохимические свойства MnClT(3-NH 2 Ph)P и MnClT(4-NH 2 Ph)P в растворах ДМСО и особенности электрохимического осаждения пленок с использованием супероксид анион-радикала. На Pt, ITO и Au электродах происходит формирование полипорфириновой пленки, ассоциированное с пиком электровосстановления кислорода. Наблюдаемые нами изменения на циклических вольтамперограммах растворов порфиринов в ДМСО, насыщенных кислородом, вероятно, указывают на формирование оксокомлексов, в которых металл приобретает устойчивую степень окисления. Материал электрода влияет на амплитуды токов RedОx процессов, величину прироста массы и процессы десорбции осажденного слоя. Скорость взаимодействия O 2 •с MnClT(4-NH 2 Ph)P более высокая, чем с MnClT(3-NH

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“…[24][25][26][27][28] Among the molecular systems utilized to form polymers films, redox-and photo-active metalloporphyrins and metallophthalocyanines are highly sought out due to their biological relevance, and materials and optoelectronic applications. 29 Different strategies have been developed to build metalloporphyrin-and metallophthalocyanines-based multilayered structures and architectures. In large majority of the cases, these tetrapyrrole metal complexes are functionalized to carry one or more entities of amine, pyrrole or thiophene electropolymerizable monomer groups.…”

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confidence: 99%

“…In large majority of the cases, these tetrapyrrole metal complexes are functionalized to carry one or more entities of amine, pyrrole or thiophene electropolymerizable monomer groups. 29 In the case of biomimetic catalytic and photoelectrochemical studies, the resulting electroactive metal tetrapyrrole carrying polymer films have shown to prevent the embedded complexes from degradation, allow controlled access of substrate molecules to the reactive centers, and improve the overall supported catalytic/photocatalytic activity. The electropolymerized metal tetrapyrrole films also offer robust materials for analytical tools, especially sensing of environmental and bioanalytes.…”

mentioning

confidence: 99%

Electropolymerizable meso-Tetrakis Biphenyl-Bis(bithiophene) Zinc Porphyrin: Ground and Excited State Properties in Solution and in Films with Axially Coordinated C₆₀

Ganesan

Shao

Seetharaman

et al. 2020

ECS J. Solid State Sci. Technol.

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An electropolymerizable zinc porphyrin carrying eight entities of peripheral bithiophene, 4 was newly designed and synthesized. In this design, the bithiophene entities were separated by a biphenyl spacer to minimize ground state interactions perturbing porphyrin π-electronic structure. By multi-cyclic voltammetry, thin-films of 4 were formed on transparent FTO electrode and were characterized by optical, electrochemical and STM measurements. Further, the ability of zinc porphyrin in 4 to axially coordinate phenyl imidazole functionalized fullerene, C60Im both in solution and on the film interface was performed and characterized. Fluorescence quenching of zinc porphyrin both in solution and in the film was observed upon binding of C60Im. Femtosecond transient absorption studies revealed excited state charge separation for the dyad in solution wherein the measured rate of charge separation, k CS and charge recombination, k CR were found to be 2 × 1010 s−1 and 1.2 × 109 s−1, respectively. In contrast, transient absorption studies performed on the dyad in the film were suggestive of energy transfer with minimal contributions from electron transfer. The present study brings out the importance of modulating photochemical reactivity of donor-acceptor dyad in film as compared to that in solution.

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Electropolymerized Metalloporphyrin Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis

Cited by 7 publications

References 229 publications

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

Electrodeposition and Characterization of Polyporphyrin Films Based on Mn Complexes of Amino-substituted Tetraphenylporphyrins

Electropolymerizable meso-Tetrakis Biphenyl-Bis(bithiophene) Zinc Porphyrin: Ground and Excited State Properties in Solution and in Films with Axially Coordinated C₆₀

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Electropolymerized Metalloporphyrin Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis

Cited by 7 publications

References 229 publications

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

Efficient Bio-Inspired Oxygen Reduction Electrocatalysis with Electropolymerized Cobalt Corroles

Electrodeposition and Characterization of Polyporphyrin Films Based on Mn Complexes of Amino-substituted Tetraphenylporphyrins

Electropolymerizable meso-Tetrakis Biphenyl-Bis(bithiophene) Zinc Porphyrin: Ground and Excited State Properties in Solution and in Films with Axially Coordinated C60

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Electropolymerizable meso-Tetrakis Biphenyl-Bis(bithiophene) Zinc Porphyrin: Ground and Excited State Properties in Solution and in Films with Axially Coordinated C₆₀