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Master's Dissertation
DOI
https://doi.org/10.11606/D.85.2020.tde-27122019-133317
Document
Author
Full name
Victor Farneze de Camargo
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2019
Supervisor
Committee
Oliveira Neto, Almir (President)
Oliveira, Hueder Paulo Moisés de
Ottoni, Cristiane Angelica
Title in Portuguese
Síntese de eletrocatalisadores de PtRh/C-ITO pelo método de borohidreto de sódio para eletrooxidação do etanol em meio alcalino
Keywords in Portuguese
eletrocatalisadores de PtRh/C-ITO
eletrooxidação do etanol
ITO
meio alcalino
Abstract in Portuguese
Eletrocatalisadores de PtRh/C-ITO foram preparados em uma única etapa, usando H2PtCl6.6H2O e RhCl3.xH2O como fonte dos metais, borohidreto de sódio como agente redutor e uma mistura física de 85% de carbono Vulcan XC-72 e 15% In2O3.SnO2 (indium tin oxide - ITO) como suporte. PtRh/C-ITO preparados neste trabalho foram caracterizados por difração de raios X (DRX), microscopia eletrônica de transmissão (MET), espectroscopia de fotoelétrons excitados por raios X (XPS), espectroscopia in situ de infravermelho com transformada de Fourier (ATR-FTIR), voltametria cíclica, cronoamperometria e testes de performance em uma célula a combustível de etanol direto (DEFC). Espectros de difração de raios X para todos eletrocatalisadores de PtRh/C-ITO indicaram um deslocamento nos picos da Pt(fcc), mostrando que o Rh foi incorporado na matriz da Pt. Histogramas obtidos pelas imagens do MET para PtRh/C-ITO mostraram nanopartículas, com tamanho entre 3,0 e 4,0 nm, homogeneamente distribuídas sobre o suporte. Resultados do XPS da PtRh(70:30)/C-ITO mostraram a presença de uma mistura de espécies de diferentes estados de oxidação (Sn0 e SnO2), o que pode favorecer a oxidação de espécies intermediarias adsorvidas, através do mecanismo bifuncional. PtRh(90:10)/C-ITO foi a mais ativa nos estudos eletroquímicos devido a maior produção de CO2, indicando possuir maior seletividade na quebra da ligação C-C. Experimentos em DEFC mostraram que os valores de densidades de potência obtidas com PtRh(70:30)/C-ITO e PtRh(90:10)/C-ITO foram maiores do que com o Pt/C, indicando um efeito benéfico na adição de Rh a Pt, além do ITO no suporte de carbono.
Title in English
Synthesis of PtRh/C-ITO electrocatalysts prepared with sodium borohidride method for ethanol electrooxidation in alkaline media
Keywords in English
alkaline media
ethanol electrooxidation
ITO
PtRh/C-ITO electrocatalysts
Abstract in English
PtRh/C-ITO electrocatalysts were prepared in a single step process, using H2PtCl6.6H2O and RhCl3.xH2O as metal sources, sodium borohydride as a reducing agent, and a solid mixture of 85% Vulcan XC-72 and In2O3.SnO2 (indium tin oxide - ITO) as support. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR), cyclic voltammetry, chronoamperometry, and performance test on direct ethanol fuel cell (DEFC). X-ray diffraction patterns for all PtRh/C-ITO indicated a shift in Pt(fcc) peaks, showing that Rh was incorporated into Pt lattice. Transmission electron microscopy for PtRh/C-ITO showed nanoparticles homogeneously distributed over the support with particles size between 3.0 nm and 4.0 nm. The XPS results for PtRh(70:30)/C-ITO showed the presence of mixed oxidation states of Sn0 and SnO2, which could favor the oxidation of intermediates adsorbed by bifunctional mechanism. PtRh/C-ITO (90:10) was more active in electrochemical studies considering the higher quantities of CO2 produced, which indicates a greater selectivity of this electrocatalyst to break C-C bonds. Experiments in direct alkaline ethanol fuel cells showed that power density values obtained for PtRh/C-ITO (70:30) and PtRh/C-ITO (90:10) were higher than obtained for Pt/C, indicating a beneficial effect of Rh addition to Pt and the C-ITO support.
 
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Publishing Date
2020-01-21
 
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