Abstract
Carbon dioxide was photocatalytically reduced to produce methanol in an aqueous solution using 254 nm UV irradiation.
Titania and Cu-loaded titania were synthesized by an improved sol–gel method using a homogeneous hydrolysis technique.
The grain size of TiO2 and Cu/TiO2 were uniform and average diameters were approximately 20 nm. Photocatalytic reduction
was conducted in a quartz reactor with a UV lamp irradiating at the center. XPS analysis reveals that Cu 2p3/2 is 933.4 eV
indicating primary Cu2O species on the TiO2 supports. EDX and XPS revealed that most copper clusters were on the TiO2
surface. The optimum amount of copper loading was 2.0 wt.% for the highest dispersion among catalysts. The methanol yield
of 2.0 wt.% Cu/TiO2 was 118mol/g following 6 h of UV illumination. The yield was much higher than those of sol–gel
TiO2 and Degussa P25, whose yields were 4.7 and 38.2mol/g, respectively. The methanol yield reached a steady-state
250mol/g after 20 h of irradiation. Experimental results indicated that the methanol yield was significantly increased by
adding NaOH. The caustic solution dissolved more CO2 than did pure water. In addition, the OH− in aqueous solution also
served as a strong hole scavenger. The redistribution of the electric charge and the Schottky barrier of Cu and TiO2 facilitates
electron trapping via supported Cu. The photocatalytic efficiency of Cu/TiO2 was markedly increased because of the lowering
the re-combination probability for hole–electron pairs. The highest quantum and energy efficiencies achieved were 10 and
2.5%, respectively. © 2002 Elsevier Science B.V. All rights reserved.