SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)

Electrocatalytic methods have been developed to perform CO2 and NO2- reduction, either in a separate or simultaneous way. These methods are a novel alternative to deplete CO2 and NO2- concentration. On the other hand, electroanalytical techniques can develop methods able to determine sulfite in wine...

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Autor: Dreyse-Silva, Paulina Andrea
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2011
País:Chile
OAI Identifier:oai:repositorio.anid.cl:10533/220344
Acceso en línea:https://hdl.handle.net/10533/220344
Access Level:acceso abierto
Palabra clave:Ciencias Naturales
Ciencias Químicas
Electroquímica
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dc.title.es_CL.fl_str_mv SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
SÍNTESIS Y CARACTERIZACIÓN DE PORFIRINAS SUSTITUIDAS CON COMPLEJOS POLIPIRIDÍNICOS DE Ru (II). DISEÑO DE ELECTRODOS MODIFICADOS PARA LA ELECTROCATÁLISIS DE CO2 Y NO2-, Y PARA EL ELECTROANÁLISIS DE OXOANIONES DE AZUFRE (IV)
dc.title.none.fl_str_mv Synthesis and characterizatión of substituted porphyrines with polyphyridine compounds of ru (ii). Design of modified electrodes for the electrocatalysis of co2 and no2-, and for the electro analysis of sulfur oxoanións (iv)
síntesis y caracterización de porfirinas sustituidas con complejos polipiridínicos de ru (ii). Diseño de electrodos modificados para la electrocatálisis de co2 y no2-, y para el electroanálisis de oxoaniónes de azufre (iv)
title SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
spellingShingle SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
Dreyse-Silva, Paulina Andrea
Ciencias Naturales
Ciencias Químicas
Electroquímica
title_short SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
title_full SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
title_fullStr SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
title_full_unstemmed SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
title_sort SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)
dc.creator.none.fl_str_mv Dreyse-Silva, Paulina Andrea
author Dreyse-Silva, Paulina Andrea
author_facet Dreyse-Silva, Paulina Andrea
author_role author
dc.contributor.advisor.none.fl_str_mv Campos-Vallete, Marcelo
Isaacs-Casanova, Mauricio Alejandro
dc.contributor.institution.es_CL.fl_str_mv UNIVERSIDAD DE CHILE
dc.subject.oecd1n.es_CL.fl_str_mv Ciencias Naturales
topic Ciencias Naturales
Ciencias Químicas
Electroquímica
dc.subject.oecd2n.es_CL.fl_str_mv Ciencias Químicas
dc.subject.oecd3n.es_CL.fl_str_mv Electroquímica
description Electrocatalytic methods have been developed to perform CO2 and NO2- reduction, either in a separate or simultaneous way. These methods are a novel alternative to deplete CO2 and NO2- concentration. On the other hand, electroanalytical techniques can develop methods able to determine sulfite in wines, which is of vital importance in the production of this beverage. Electrocatalytic and electroanalytical processes can be preformed with different catalysts, being macrocycles containing transitional metal interesting models because they are able to promote multiple electronic transfers. Consequently, is possible to develop the electrochemical reduction of contaminating agents and also to determinate different compounds like sulfite, with the use of metallic catalysts. In this Doctoral Thesis, new macrocycles were synthesized. These compounds consist of a tetrapyridylporphyrin coordinated to four Ru (II) complexes. The ligands of the Ru (II) complexes are 5-NO2-phenanthroline and the metals coordinated in the central cavity of the porphyrins are Ni (II) and Zn (II). A protocol for the electrochemical preparation of a conducting polymer from this macrocycle was also developed. The polymeric growth was characterized by cyclic voltammetry, IR spectroelectrochemistry, atomic force microscopy and Raman spectroscopy. Experimental results showed that the electropolymerization process takes place when nitro substituents are reduced. These polymeric films were evaluated in aqueous solution, and were very stable; therefore, these modified electrodes were used in the study of CO2 and NO2- electroreduction, and also for sulfite determinations. The electrochemical reduction of CO2 was studied with the polymeric catalysts and it was observed that the three coatings present catalytic activity for CO2 reduction. Controlled potential electrolysis experiments verify the production of formic acid and formaldehyde when polymeric metal free tetraruthenated porphyrin was used, and only formaldehyde when Ni (II) and Zn (II) macrocycles were used. Also, the nitrite electroreduction was studied, the results also evidenced that the three conductive polymers are active for nitrite reduction. Controlled potential electrolysis experiments verified the production of hydrazine, hydroxylamine and ammonia. All modified electrodes were more selective toward hidroxylamine production. The study of the simultaneous electrocatalytic reduction of CO2 and nitrite, showed that these conductive polymers films promote the formation of urea at -1,0 V. Finally, the conductive polymers of tetraruthenated porphyrins were evaluated in the electroanalysis of S (IV) oxoanions. The Ni (II) film was the most effective coating for sulfite determination. Two potential analytical methods were proposed one at pH 1,0 for sulfite reduction and other at pH 3,5 for sulfite oxidation, both methodologies present limits of detection comparable with current analytical methods.
publishDate 2011
dc.date.issued.es_CL.fl_str_mv 2011
dc.date.accessioned.none.fl_str_mv 2018-09-12T20:12:11Z
2022-08-17T19:14:03Z
dc.date.available.none.fl_str_mv 2018-09-12T20:12:11Z
2022-08-17T19:14:03Z
dc.type.none.fl_str_mv Tesis Doctorado
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dc.type.openaire.none.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.tesis.none.fl_str_mv Tesis
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status_str publishedVersion
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dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/10533/220344
identifier_str_mv 21060919
url https://hdl.handle.net/10533/220344
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spelling UNIVERSIDAD DE CHILEDreyse-Silva, Paulina Andrea2011https://hdl.handle.net/10533/220344http://purl.org/coar/access_right/c_abf2ElectroquímicaCiencias QuímicasCiencias NaturalesSYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)Campos-Vallete, MarceloIsaacs-Casanova, Mauricio AlejandroUNIVERSIDAD DE CHILEChileDreyse-Silva, Paulina Andrea2018-09-12T20:12:11Z2022-08-17T19:14:03Z2018-09-12T20:12:11Z2022-08-17T19:14:03Z2011Electrocatalytic methods have been developed to perform CO2 and NO2- reduction, either in a separate or simultaneous way. These methods are a novel alternative to deplete CO2 and NO2- concentration. On the other hand, electroanalytical techniques can develop methods able to determine sulfite in wines, which is of vital importance in the production of this beverage. Electrocatalytic and electroanalytical processes can be preformed with different catalysts, being macrocycles containing transitional metal interesting models because they are able to promote multiple electronic transfers. Consequently, is possible to develop the electrochemical reduction of contaminating agents and also to determinate different compounds like sulfite, with the use of metallic catalysts. In this Doctoral Thesis, new macrocycles were synthesized. These compounds consist of a tetrapyridylporphyrin coordinated to four Ru (II) complexes. The ligands of the Ru (II) complexes are 5-NO2-phenanthroline and the metals coordinated in the central cavity of the porphyrins are Ni (II) and Zn (II). A protocol for the electrochemical preparation of a conducting polymer from this macrocycle was also developed. The polymeric growth was characterized by cyclic voltammetry, IR spectroelectrochemistry, atomic force microscopy and Raman spectroscopy. Experimental results showed that the electropolymerization process takes place when nitro substituents are reduced. These polymeric films were evaluated in aqueous solution, and were very stable; therefore, these modified electrodes were used in the study of CO2 and NO2- electroreduction, and also for sulfite determinations. The electrochemical reduction of CO2 was studied with the polymeric catalysts and it was observed that the three coatings present catalytic activity for CO2 reduction. Controlled potential electrolysis experiments verify the production of formic acid and formaldehyde when polymeric metal free tetraruthenated porphyrin was used, and only formaldehyde when Ni (II) and Zn (II) macrocycles were used. Also, the nitrite electroreduction was studied, the results also evidenced that the three conductive polymers are active for nitrite reduction. Controlled potential electrolysis experiments verified the production of hydrazine, hydroxylamine and ammonia. All modified electrodes were more selective toward hidroxylamine production. The study of the simultaneous electrocatalytic reduction of CO2 and nitrite, showed that these conductive polymers films promote the formation of urea at -1,0 V. Finally, the conductive polymers of tetraruthenated porphyrins were evaluated in the electroanalysis of S (IV) oxoanions. The Ni (II) film was the most effective coating for sulfite determination. Two potential analytical methods were proposed one at pH 1,0 for sulfite reduction and other at pH 3,5 for sulfite oxidation, both methodologies present limits of detection comparable with current analytical methods.Los métodos electrocatalíticos que permiten reducir al CO2 y al ión NO2-, y ambas especies de manera simultánea, son una alternativa para poder disminuir las concentraciones de estas especies potencialmente contaminantes. Por otra parte, mediante técnicas electroanalíticas se pueden desarrollar métodos que permitan la cuantificación de oxoaniones de S (IV) en vinos, de manera confiable y precisa. Tanto para los procesos electrocatalíticos, como electroanalíticos, el uso de catalizadores es de vital importancia, siendo los macrociclos constituidos por metales de transición, los que presentan interesantes características desde el punto de vista de promover transferencias electrónicas múltiples. Por consiguiente, con el uso de catalizadores metálicos, es posible llevar a cabo la reducción de especies contaminantes, y también, lograr el desarrollo de métodos de determinación de analitos, como por ejemplo, oxoaniones de S (IV). En esta Tesis Doctoral, se trabajó en la síntesis de un tipo particular de macrociclos, denominados porfirinas tetrarutenadas. Los compuestos que se sintetizaron, consisten en tetrapiridilporfirinas con Ni (II), Zn (II) y sin metal en la cavidad central, y en la periferia de estas porfirinas se coordinaron complejos de Ru (II) con ligandos 5-NO2-fenantrolina. Los compuestos sintetizados, se caracterizaron mediante técnicas espectroscópicas y por voltametría cíclica, donde se pudo corroborar la efectividad de los métodos sintéticos empleados para su obtención. Con estas nuevas porfirinas tetrarutenadas, se modificaron electrodos de carbón vítreo mediante un proceso de electropolimerización. Las caracterizaciones realizadas para estos electrodos modificados, mediante voltametría cíclica, espectroelectroquímica IR, microscopía de fuerza atómica y espectroscopía Raman, revelaron la formación de polímeros conductores sobre estas superficies, a través de los grupos nitros presentes en la estructura de los complejos de Ru (II). Los recubrimientos poliméricos obtenidos, no experimentaron procesos de desorción en solución acuosa, condición necesaria para ser utilizados como catalizadores en investigacionees concernientes con la electrorreducción de CO2 y nitrito, y para el electroanálisis de especies de S (IV), en el medio señalado. Con los catalizadores poliméricos obtenidos, se estudió la reducción de CO2, encontrándose que los tres recubrimientos presentan actividad catalítica. Mediante experimentos de electrólisis a potencial controlado, se recolectaron los productos de reducción, y se determinó ácido fórmico y formaldehído con el uso del catalizador polimérico de porfirina tetrarutenada sin metal central, y solo se detectó formaldehído en el caso de los catalizadores con Ni (II) y Zn (II). También se estudió la reducción electrocatalítica del ión nitrito, y los resultados también mostraron que las tres superficies poliméricas son activas frente a la reducción de la especie en estudio. De acuerdo a los experimentos realizados por electrólisis a potencial controlado, se determinaron como productos de reducción: hidroxilamina, hidracina y amoniaco. Con el uso de todos los catalizadores, siempre fue mayor la concentración de hidroxilamina. El estudio de la reducción electrocatalítica de CO2 y nitrito, de manera simultánea, mostró la efectividad que estos films poliméricos presentan para promover la formación de urea, en un potencial de -1,0 V v/s Ag/AgCl. Finalmente, se evaluó la capacidad que presentan los polímeros conductores derivados de estas nuevas porfirinas tetrarutenadas, para ser utilizados como sensores de oxoaniones de S (IV). Se encontró que el recubrimiento más efectivo para determinar a estas especies, corresponde al de Ni (II), con el cual se diseñaron dos posibles métodos de determinación: a pH 1,0 en el sentido de la reducción, y a pH 3,5 en el sentido de la oxidación. Los límites de detección obtenidos son comparables con los métodos que se encuentran descritos en literatura.21060919https://hdl.handle.net/10533/220344instname: Conicytreponame: Repositorio Digital RI2.0info:eu-repo/grantAgreement//21060919info:eu-repo/semantics/dataset/hdl.handle.net/10533/93488info:eu-repo/semantics/openAccessCiencias NaturalesCiencias QuímicasElectroquímicaSYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED PORPHYRINES WITH POLYPHYRIDINE COMPOUNDS OF Ru (II). DESIGN OF MODIFIED ELECTRODES FOR THE ELECTROCATALYSIS OF CO2 AND NO2-, AND FOR THE ELECTRO ANALYSIS OF SULFUR OXOANIONS (IV)SÍNTESIS Y CARACTERIZACIÓN DE PORFIRINAS SUSTITUIDAS CON COMPLEJOS POLIPIRIDÍNICOS DE Ru (II). DISEÑO DE ELECTRODOS MODIFICADOS PARA LA ELECTROCATÁLISIS DE CO2 Y NO2-, Y PARA EL ELECTROANÁLISIS DE OXOANIONES DE AZUFRE (IV)Synthesis and characterizatión of substituted porphyrines with polyphyridine compounds of ru (ii). Design of modified electrodes for the electrocatalysis of co2 and no2-, and for the electro analysis of sulfur oxoanións (iv)síntesis y caracterización de porfirinas sustituidas con complejos polipiridínicos de ru (ii). 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