Electrochemical transformation of alkanes, carbon dioxide and protons at iron-porphyrins and iron-sulfur clusters

• Main Author: Alenezi, Khalaf
• Published: University of East Anglia 2013
• Subjects: 540
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.590777

The work contained in this thesis focuses on (i) chemical and electrochemical alkane oxidation using Fe-porphyrin complexes as catalysts (ii) electrochemical and photoelectrochemical CO2 reduction using Fe-porphyrin complexes (iii) electrochemical and photoelectrochemical generation of hydrogen using iron-sulfur cluster. Chapter 1 gives a general overview of the electrochemical techniques which underpin the work presenedt in this thesis. Chapter 2 reports the chemical and electrocatalytic oxidation of hydrocarbons to alcohols and epoxides by using iron (III) porphyrins as catalysts. A series of new basket-handle thiolate Fe (III) porphyrins have been used to mediate anodic oxidation of hydrocarbons, specifically adamantane hydroxylation and cyclooctene epoxidation. The electrocatalytic and chemical catalytic activity oxidation of the thiolate porphyrins are benchmarked against Fe (III) tetraphenyl porphyrin chloride and its tetrapentafluorophenyl analogue. Chapter 3 describes the electrochemical and photoelectrochemical reduction of carbon dioxide to carbon monoxide. This chapter shows that iron (III) porphyrin complexes are capable of carrying out electrocatalytic reduction of carbon dioxide at both vitreous carbon and illuminated p-type silicon surfaces, with reasonable current efficiencies. At illuminated p-type silicon photovoltages of ca 500mV are obtained. 7 Chapter 4 describes the electrochemical and photoelectrochemical reduction of proton to H2 using [Fe4S4 (SPh)4]2- as an electrocatalyst at both vitreous carbon and at illuminated p-type Si electrodes.