摘要
The photo-electro-chemical （PEC） splitting of water requires semiconductor materials with a minimum energy gap of 1.23 eV along with conduction and valence bands overlapping the oxidation of H20 and reduction of H＋ respectively. This work overcomes the limitations of stoichiometric titania by manufacturing fine scale fibres that exhibit a compositional gradient of oxygen vacancies across the fibre length. In such a fibre configuration the fibre end that is chemically reduced to a relatively small extent performs as the photoanode and the oxygen vacan- cies enhance the absorption of light. The fibre end that is reduced the most consists of Magn61i phases and exhibits metallic electrical conductivity that enhances the electron-hole separation. The structure and composition of the functionally graded fibres, which were manufactured through extrusion, pressureless sintering and carbo-thermal reduction, are studied using XRD and electron microscopy. Electrochemical impedance spectroscopy measure- ments were performed in a three-electrode electrochemical system and showed that the oxygen vacancies in the functionally graded fibres affect the fiat band potential and have increased carrier density. The efficiency of the system was evaluated with PEC measurements that shows higher efficiency for the functionally graded fibres com- pared to homogeneous TiO2 or Magn61i phase fibres. The functionally graded and fine scale fibres have the potential to be used as an array of active fibres for water splitting applications.
The photo-electro-chemical （PEC） splitting of water requires semiconductor materials with a minimum energy gap of 1.23 eV along with conduction and valence bands overlapping the oxidation of H20 and reduction of H＋ respectively. This work overcomes the limitations of stoichiometric titania by manufacturing fine scale fibres that exhibit a compositional gradient of oxygen vacancies across the fibre length. In such a fibre configuration the fibre end that is chemically reduced to a relatively small extent performs as the photoanode and the oxygen vacan- cies enhance the absorption of light. The fibre end that is reduced the most consists of Magn61i phases and exhibits metallic electrical conductivity that enhances the electron-hole separation. The structure and composition of the functionally graded fibres, which were manufactured through extrusion, pressureless sintering and carbo-thermal reduction, are studied using XRD and electron microscopy. Electrochemical impedance spectroscopy measure- ments were performed in a three-electrode electrochemical system and showed that the oxygen vacancies in the functionally graded fibres affect the fiat band potential and have increased carrier density. The efficiency of the system was evaluated with PEC measurements that shows higher efficiency for the functionally graded fibres com- pared to homogeneous TiO2 or Magn61i phase fibres. The functionally graded and fine scale fibres have the potential to be used as an array of active fibres for water splitting applications.
基金
the European Union’s Seventh Framework Programme(FP7/2007-2013)/ERC Grant Agreement no.320963 on Novel Energy Materials,Engineering,Science and Integrated Systems(NEMESIS)
supported by The European Union under FP7 Project309846,"Photocatalytic Materials for the Destruction of Recalcitrant Organic Industrial Waste–PCATDES"
