Hydrogen production by the photoreforming of methanol and the photocatalytic water–gas shift reaction

Abstract We have examined the reforming of methanol and CO on Pd/P25 TiO₂ catalysts for hydrogen production, and compared it with rates for similarly supported Au and Cu catalysts. Both reactions proceed, but the photocatalytic water–gas shift (WGS) reaction is much slower than for methanol reforming. CO₂ is evolved as expected, but the yields can be much lower than for the expected stoichiometry (CH₃OH + H₂O → CO₂ + 3H₂). We show that this is due to dissolution of the carbon dioxide into the aqueous phase. We have also carried out both reactions in the gas phase. Both proceed at a higher rate in the gas phase, and for methanol reforming, there is some CO evolution. In H₂ + CO₂ reactions, there is little sign of the reverse WGS reaction, but some photo-methanation does occur. Of the three catalysts Pd is the best for the methanol reforming reaction, while Au is best for the water–gas shift. Nonetheless, Cu works reasonably well for methanol reforming and makes a much cheaper, earth-abundant catalyst.