Electrodeposition of ruthenium N-pyrrole bipyridine films on carbon felt electrodes and application as catalysts in alcohol electrooxidation

Claudemir Batalini; Wagner Ferraresi De Giovani

doi:10.22481/exon.v11i2.20579

Autores

Claudemir Batalini Universidade Federal de Mato Grosso
Wagner Ferraresi De Giovani Universidade de São Paulo

DOI:

https://doi.org/10.22481/exon.v11i2.20579

Palavras-chave:

Eletrodos modificados, Eletroxidação, Filmes polipirrólicos, Rutênio

Resumo

Pesquisas visando o emprego de tecnologias sustentáveis alinhadas com os princípios da Química Verde estão sendo cada vez mais conduzidas nos meios acadêmicos e industriais. As eletroxidações catalíticas de álcoois são processos importantes devido sua relação com pesquisas em geração de energia. Com o objetivo de explorar um sistema catalítico seletivo num processo químico menos agressivo ao meio ambiente, foram preparados filmes N-pirrolbipiridínicos de rutênio poli-cis-[Ru(L)2(OH2)2] 2+ (L=4- metil-4’-pirrol-1-il-butil-2,2’-bipiridina), em eletrodos de feltro de carbono, por eletropolimerização anódica do monômero cis-[Ru(L)2Cl2] e posterior indução eletroquímica ao aquacomplexo. Esses eletrodos de feltro de carbono modificados por deposição desses filmes foram utilizados como eletrocatalisadores em oxidações de álcoois, a potencial constante de +1,15 V (vs ECS), em meio aquoso nos pHs 6,8 e 8,1. Os álcoois utilizados e seus produtos de oxidação foram: álcool benzílico (benzaldeído), cicloexanol (cicloexanona), 1-feniletanol (acetofenona) e álcool p-metoxibenzílico (pmetoxibenzaldeído). As reações ocorreram com total seletividade na obtenção dos produtos, com rendimentos satisfatórios.

Downloads

Não há dados estatísticos.

Referências

S. J. Konopka; B. McDuffie, Diffusion coefficients of ferri- and ferrocyanide ions in aqueous media, using twin-electrode thin-layer electrochemistry, Anal. Chem., 42 (14), (1970), 1741-1746.

P. R. Moses; L. Wier; R. W. Murray, Chemically modified tin oxide electrode, Anal. Chem., 47 (12), (1975), 1882-1886.

G. A. Edwards; A. J. Bergren; M. D. Porter, Chemically modified electrodes, in: Handbook of electrochemistry, cap. 8, pp. 295-327, Elsevier, 2007.

H. D. Abruña, Coordination chemistry in two dimensions: chemically modified electrodes, Coord. Chem. Rev., 86, (1988), 135-189.

C.-C. Ti; A. K. Sundramoorthy; S.-M. Chen, Electrochemical preparation, characterization, and electrocatalytic studies of Nafion–ruthenium oxide modified glassy carbon electrode, Journal of Solid State Electrochemistry, 13 (3), (2009), 397-406.

R. Bernasconi; L. Magagnin, Review - Ruthenium as diffusion barrier layer in electronic interconnects: current literature with a focus on electrochemical deposition methods, Journal of Electrochemical Society, 166 (1), (2019), D3219-D3225.

W. X. Qian; E. L. Jin; W. L. Bao; Y. M. Zhang, Clean and highly selective oxidation of alcohols in an ionic liquid by using an ion-supported hypervalent iodine (III) reagent, Angew. Chem. Int. Ed., 44, (2005), 952-955.

A. Heidarnezhad; F. Zamani, Chromium containing Fe3O4/polyacrylonitrile–ethylenediamine as a magnetically recoverable catalyst for alcohol oxidation, Cat. Commun., 60, (2015), 105-109.

K. L. Brown, Electrochemical preparation and characterization of chemically modified electrodes, in: Voltammetry, edited by Nobanathi Wendy Maxakato, Sandile Surprise Gwebu and Gugu Hlengiwe Mhlongo, Intechopen, 2018.

B. Karimi; M. Rafiee; S. Alizadeh; H. Vali, Eco-friendly electrocatalytic oxidation of alcohols on a novel electro generated TEMPO-functionalized MCM-41 modified electrode, Green Chemistry, 17 (2), (2015), 991-1000.

K. Ganesh; K. B. Akshaya; A. Varghese; A. T. Mathew, An aqueous phase TEMPO-mediated electrooxidation of benzyl alcohol at β-CD-PPy-modified carbon fibre paper electrode, Electrocatalysis, 11 (1), (2020), 1-13.

R. -A. Fallahpour, The higher oligopyridines and their metal complexes, Curr. Org. Synth., 3 (1), (2006), 19-39.

E. C. Constable, Higher oligopyridines as a structural motif in metallosupramolecular chemistry, Prog. Inorg. Chem., 42, (1994), 67-138.

C. Kaes; A. Katz; M. W. Hosseini, Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2,2´-bipyridine units, Chem. Rev., 100 (10), (2000), 3553-3590.

E. C. Constable; C. E. Housecroft, The early years of 2,2’-bipyridine - a ligand in its own lifetime, Molecules, 24, (2019), 3951-3990.

E. C. Constable; C. E. Housecroft, More hydra than Janus - non-classical coordination modes in complexes of oligopyridine ligands, Coord. Chem. Rev., 350, (2017), 84–104.

T. Yang; H. Yin; L.-H. Gao; K.-Z. Wang; D. Yan, Chapter Seven - Recent advances in electrodes modified with ruthenium complexes for electrochemical and photoelectrochemical water oxidation, Advances in Inorganic Chemistry, 74, (2019), 305-341.

V. G. Gude, Microbial Fuel Cells as a Platform Technology for Sustainable Wastewater Treatment, in: Progress and recent trends in microbial fuel cells, cap. 18, pp. 375-398, 2018.

M. Dakkach; X. Fontrodona; T. Parella; A. Atlamsani; I. Romero; M. Rodríguez, Polypyrrolefunctionalized ruthenium carbene catalysts as efficient heterogeneous systems for olefin epoxidation, Dalton Trans., 43 (26), (2014), 9916-9923.

D. Curran; J. Grimshaw; S. D. Perera, Poly(pyrrole) as a support for electrocatalytic materials, Chem. Soc. Rev., 20 (3), (1991), 391-404.

T. Morita; R. M. V. Assumpção, Manual de soluções, reagentes e solventes, 2 ed., São Paulo (SP): Ed. Blucher, 2007.

D. T. Sawyer; J. L. Roberts, Experimental Electrochemistry for Chemists, pp. 212, New York: John Wiley & Sons, 1974.

W. F. De Giovani; A. Deronzier, Films of poly{pyrrole-[RuII(bpy)2Cl2]}; their transformations into films containing cis- or trans-[RuII(bpy)2(H2O)2] 2+, [RuII(bpy)2(MeCN)2] 2+ and [{RuIII(bpy)2(H2O)}2O]4+ complexes, application to electrocatalysis (bpy = 2,2’-bipyridine), J. Chem. Soc., Chem. Commun., 19, (1992), 1461-1463.

J. C. Dobson; T. J. Meyer, Redox properties and ligand loss chemistry in aqua/hydroxo/oxo complexes derived from cis- and trans-[(bpy)2RuII(OH2)2] 2+, Inorg. Chem., 27 (19), (1988), 3283-3291.

K. J. Takeuchi; G. J. Samuels; S. W. Gersten; J. A. Gilbert; T. J. Meyer, Multiple oxidation states of ruthenium and osmium based on dioxo/diaqua couples, Inorg. Chem., 22 (9), (1983), 1407-1409.

M. N. C. Dunand-Sauthier; A. Deronzier; H. Le Bozec; M. Navarro, Electrochemistry of cis-diaquo ruthenium (II) complexes with substituted 2,2’-bipyridine ligands in a non-coordinating solvent. Application to the elaboration of corresponding functionalized polypyrrole films, J. Electroanal. Chem., 410 (1), (1996), 21-29.

D. Erdman; Y. Pineda-Galvan; Y. Pushkar, Mechanistic analysis of water oxidation catalyst cis- [Ru(bpy)2(H2O)2] 2+:effect of dimerization, Catalysts, 7 (2), (2017), 39-48.

M. Navarro; W. F. De Giovani; J. R. Romero, Synthesis of aldehydes, ketones and carboxylic acids by selective oxidations of alcohols using a polypyridyl complex of ruthenium (IV), Synth. Commun., 20, (1990), 399-406.

K.-C. Cheung; W.-L. Wong; D.-L. Ma; T. -S. Lai; K. -Y. Wong, Transition metal complexes as electrocatalysts - Development and applications in electro-oxidation reactions, Coord. Chem. Rev., 251 (17-20), (2007), 2367-2385.

Z. Ma; F. Zaera, Heterogeneous Catalysis by Metals. Encyclopedia of Inorganic and Bioinorganic Chemistry, John Wiley & Sons, 2011.

J. R. Steter; A. J. Motheo; J. R. Romero, Electrocatalytic oxidation of organic substrates at carbon electrodes modified with a ruthenium-containing azo phenol polymer, J. Electrochem. Soc., 161 (10), (2014), E142-E150, 2014.

A. R. Guadalupe; X. Chen; B. P. Sullivan; T. J. Meyer, Oxo complexes, pH effects, and catalysis in films formed by electropolymerization, Inorg. Chem., 32 (24), (1993), 5502-5512.

J. A. Moss; R. M. Leasure; T. J. Meyer, Electrocatalysis in photochemically activated electropolymerized thin films, Inorg. Chem., 39 (6), (2000), 1052-1058.