催化化学-光电催化与光催化.pptxVIP

Photoelectrochemical/Photoca- talytic Water splitting;;;Nature, 1972, 238, 37; Chem. Rev., 1995, 95, 735.;Environmentally clean chemical fuel;;Hydrogen Energy;;;Steam Methane Reforming (SMR);2NaCl + 2H2O Cl2 + H2 + 2NaOH;;Solar Thermolysis of Water;;Thermodynamics;Photoelectrochemical Water Splitting;;(Over-)Simplified Picture;Review of Oxidation/Reduction;(Over-)Simplified Picture;;费米能级;Fermi Levels Describe Energy of Carriers;24;Equilibration with Solution Redox Couples;Dark Current-Voltage Behavior;;;;;Band-edges move via surface dipoles;Semiconductors: Light Absorption;;Solar Spectrum:;;;Semiconductors: Carrier Collection;;Evaluations;;;;Surface Electrocatalysis;Tafel Slope and Exchange Current;;;Hydrogen Evolution Reaction;HER Overpotentials;Large loss for driving water oxidation reaction kinetics;Theory: electrocatalysis requires the stabilization of intermediates;Optimization vs. Design;;Thin Film OER Quantitative Comparison;;Stability: Pourbaix Diagrams;Photoelectrodes;;;Strong (visible) light absorption High chemical stability in the dark and under illumination Suitable band edge positions to enable reduction/oxidation of water Efficient charge transport in the semiconductor Low overpotentials for the reduction/oxidation reactions Low cost;;;Wide Band Gap Photocatalysts;Powdered photocatalysts;Example: Visible light activity via tuning materials properties;Particle PEC and Sacrificial Reagents;;;;;;G. Wang, et al. Nano Lett. 2011, 11, 3026;;;;;How to produce renewable energy sources form human urine?;Solar driven hydrogen releasing from human urine;;;;Urine solution Wang, et al. Energy Environ. Sci., 2012, 5, 8215.;;Similar idea;;Limitations: Unstable in aqueous solution due to chemical dissolution and photocorrosion;G. Wang, et al. Energy Environ. Sci., 2012, 5, 6180;;Oxygen-deficient WO3-x shown enhanced photoactivity;First example where WO3 can be stabilized for water oxidation without the need of oxygen evolution catalysts. G. Wang, et al. Energ