Room temperature stable CO_x-free H₂ production from methanol with magnesium oxide nanophotocatalysts

Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at room temperature. However, by releasing the hydrogen, undesirable CO and/or CO₂ byproducts are formed during catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable photocatalytic activity for CO/CO₂-free H₂ production from liquid methanol at room temperature. The performance of MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 mmol g⁻¹ hour⁻¹ after a 2-day photocatalytic reaction. The CO_x-free H₂ production is attributed to methanol photodecomposition to formaldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol.