CO(x) hydrogenation to methanol and other hydrocarbons under mild conditions with Mo(3)S(4)@ZSM-5

The hydrogenation of CO(2) or CO to single organic product has received widespread attentions. Here we show a highly efficient and selective catalyst, Mo(3)S(4)@ions-ZSM-5, with molybdenum sulfide clusters ([Mo(3)S(4)](n+)) confined in zeolitic cages of ZSM-5 molecular sieve for the reactions. Using continuous fixed bed reactor, for CO(2) hydrogenation to methanol, the catalyst Mo(3)S(4)@NaZSM-5 shows methanol selectivity larger than 98% at 10.2% of carbon dioxide conversion at 180 °C and maintains the catalytic performance without any degeneration during continuous reaction of 1000 h. For CO hydrogenation, the catalyst Mo(3)S(4)@HZSM-5 exhibits a selectivity to C(2) and C(3) hydrocarbons stably larger than 98% in organics at 260 °C. The structure of the catalysts and the mechanism of CO(x) hydrogenation over the catalysts are fully characterized experimentally and theorectically. Based on the results, we envision that the Mo(3)S(4)@ions-ZSM-5 catalysts display the importance of active clusters surrounded by permeable materials as mesocatalysts for discovery of new reactions.