A novel one-pot approach selects a hydrothermally synthesized Cu/SiO catalyst (consisting of CuO·SiO and Cu surface species) to catalyze the reduction of a series of fatty esters, fatty acids, and coconut oil to fatty alcohols at 240 °C in methanol without extraneous hydrogen, attaining around 85% conversion and 100% selectivity.
Hydrogen is an important sustainable resource, and here we report a catalytic route for the direct production of hydrogen (with a purity of 95 %) and dimethoxylmethane (DMM) from supercritical methanol over a Cu/SiO2 catalyst prepared by deposition–precipitation with ammonia (DPA) at 240°C in a one‐pot process. The procedure starts with methanol dehydrogenation to hydrogen and formaldehyde at the interface of the Cu2O⋅SiO2–Cu0 particle mixture, and subsequently, the formaldehyde intermediate condenses with substantial methanol to form DMM in the liquid phase. The Cu0, CuO, and chrysocolla species are inactive for hydrogen generation from methanol, and the intrinsic active species for methanol decomposition is the Cu2O⋅SiO2–Cu0 nanoparticle interface, which is produced from the hydrogen reduction of Cu2Si2O5(OH)2 or from the methanol reduction of Cu−O−Si moieties. A correlation between the structure and activity on reduced Cu/SiO2 (DPA) suggested that only Cu0 was not active, but the combined Cu0 and Cu+ sites with interfaces on SiO2 with an optimal Cu+/Cu0 ratio of 1.56 were highly active for methanol dehydrogenation and subsequent condensation steps. The developed new catalytic system offers a facile and atom‐economical way to generate pure hydrogen (almost CO free) from liquid methanol that can be used in fuel cell and hydrogen‐involved biomass reactions.
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