Electrocatalytic reduction of bisulfite to hydrogen sulfide based on a water-soluble iron porphyrin

Kline, Martha A.; Barley, Mark H.; Meyer, Thomas J.

doi:10.1021/ic00261a005

Cited by 24 publications

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“…8B, right scale). Consequently, the nitrite should be reduced to dinitrogen while sulfite is being reduced to sulfide [45,48] and not to thiosulfate [49] as shown in Eqs. (3) and (4).…”

Section: Sulfite Response At Ph 47mentioning

confidence: 99%

Electrocatalysis on tetraruthenated nickel and cobalt porphyrins electrostatic assembled films

Mayer

Toma

Araki

2006

Journal of Electroanalytical Chemistry

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“…8B, right scale). Consequently, the nitrite should be reduced to dinitrogen while sulfite is being reduced to sulfide [45,48] and not to thiosulfate [49] as shown in Eqs. (3) and (4).…”

Section: Sulfite Response At Ph 47mentioning

confidence: 99%

Electrocatalysis on tetraruthenated nickel and cobalt porphyrins electrostatic assembled films

Mayer

Toma

Araki

2006

Journal of Electroanalytical Chemistry

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“…24,25 Such investigations can be conveniently performed by immobilizing molecular materials on a solid electrode surface. 26 They should be deposited preferentially as thin adherent, stable and electrochemically active films generated by dip-coating, electrostatic assembly or electropolimerization methods.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular conformational effects in the electrocatalytic properties of electrostatic assembled films of meso(3- and 4-pyridyl) isomers of tetraruthenated porphyrins

Mayer¹,

Eberlin²,

Tomazela³

et al. 2005

J. Braz. Chem. Soc.

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Meso (3-e 4-piridil)porfirinas coordenadas a quatro complexos [Ru(bipy) 2 Cl] + , M(3-TRPyP) e M(4-TRPyP), onde M = 2H + e Zn 2+ , foram obtidas e caracterizadas por métodos eletroquímicos, espectroscopia e espectrometria de massas. Os filmes eletrostaticamente montados camada por camada com ftalocianina de cobre tetrassulfonada, CuTSPc, apresentaram atividade eletrocatalítica diferenciada para a oxidação de sulfito e nitrito. Em geral, os filmes derivados dos isômeros M(4-TRPyP) são mais ativos para a oxidação de nitrito, enquanto aqueles contendo os isômeros M(3-TRPyP) são mais eficientes para a oxidação de sulfito. Os resultados revelaram uma influência significativa da geometria molecular no sítio ativo dos nanomateriais porfirínicos, que favorece os processos de transferência eletrônica nos derivados de M(3-TRPyP), através de mudanças no empacotamento molecular com a CuTSPc.Meso (3-and 4-pyridyl)porphyrins coordinated to four [Ru(bipy) 2 Cl] + complexes, M(3-TRPyP) or M(4-TRPyP), where M=2H + and Zn 2+ , have been obtained and characterized by electrochemistry, spectroscopy and mass spectrometry. Layer-by-layer electrostatic assembled films with tetrasulfonated phthalocyaninatecuprate(II) anion, CuTSPc, displayed distinct electrocatalytic activity towards sulfite and nitrite oxidation. In general, the films derived from the M(4-TRPyP) isomers are more effective for the oxidation of nitrite, whereas those containing the M(3-TRPyP) isomers are more efficient for the oxidation of sulfite. The results demonstrated the influence of molecular geometry on the active sites of porphyrinic nanomaterials, enhancing the electron-transfer process in the M(3-TRPyP) derivative. This effect results from changes in the chemical environment around the active sites, induced by the contrasting molecular packing interactions with CuTSPc.Keywords: supramolecular chemistry, metalloporphyrins, electrostatic assembled films, electrocatalysis, electrochemistry, mass spectrometry IntroductionMetalloporphyrins have been of great interest in the design of supramolecular systems because their electrochemical, photochemical and catalytic properties can be modulated by employing suitable ancillary bridging transition-metal complexes. [1][2][3][4][5][6][7] In such systems, the ancillary complexes can either modify the local environment around the porphyrin ring, improving the solvation and solubility properties, or act as cofactors in redox processes providing electron acceptor-donor sites and relays. They can also modify the intrinsic activity of the metalloporphyrin center by means of electronic interactions, and contribute with additional sites for intraand intermolecular interactions, allowing the assembly of higher order supramolecular structures and materials.The electrocatalytic properties of porphyrins in homogeneous and heterogeneous systems 7-20 have attracted considerable attention, particularly for multielectronic processes such as the 4-electron reduction of dioxygen to water; 21,22 and the reduction of dinitrogen 11,16,23 and...

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“…These results were similar to the results obtained by Kline et al. for a water‐soluble iron porphyrin. They also observed less than stoichiometric amounts of HS − (52 %).…”

Section: Resultsmentioning

confidence: 99%

“…The catalytic reduction of bisulfite by a water‐soluble iron porphyrin was report by Kline et al. . Yields of H 2 S were reported to be 52 % at pH 3.5, but the yields of other products were not reported.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Reduction of Bisulfite by Myoglobin/Surfactant Films

Abdelatty

Rahman

2017

Electroanalysis

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The voltammetry of bisulfite at a film formed with myoglobin was studied in aqueous solutions. A broad wave was observed for the reduction of bisulfite. Using controlled potential electrolysis, the reduction at potentials positive of the FeII/FeI wave formed dithionite exclusively. As the potential approached the region for the FeII/FeI reduction, bisulfite was reduced primarily to HS−. Even at the negative potentials, some dithionite was still formed, which could then be electrochemically reduced to thiosulfate. Analysis of the formation of HS−, dithionite and thiosulfate during the electrolysis was consistent with the parallel formation of HS− and dithionite, the latter of which was reduced to thiosulfate. Thiosulfate was verified by chemical analysis of the products from controlled potential electrolysis of the solution, and dithionite was observed spectroscopically using spectroelectro−chemistry.

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Electrocatalytic reduction of bisulfite to hydrogen sulfide based on a water-soluble iron porphyrin

Abstract: and thermal parameters, bond distances, and bond angles for both the green and blue forms of [CuL3](BF4)2 (8 pages). Ordering information is given on any current masthead page.

Cited by 24 publications

References 0 publications

Electrocatalysis on tetraruthenated nickel and cobalt porphyrins electrostatic assembled films

Electrocatalysis on tetraruthenated nickel and cobalt porphyrins electrostatic assembled films

Supramolecular conformational effects in the electrocatalytic properties of electrostatic assembled films of meso(3- and 4-pyridyl) isomers of tetraruthenated porphyrins

Catalytic Reduction of Bisulfite by Myoglobin/Surfactant Films

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