Single Atom Copper Catalysts on Sulfated Zirconia for the Catalytic Synthesis of Dimethoxymethane

The synthesis of dimethoxymethane via nonoxidative methanol dehydrogenation is an attractive route. However, it is still challenging to construct catalytic materials of high methanol conversion, high dimethoxymethane selectivity, and high stability for nonoxidative methanol dehydrogenation. In this work, we reported a facile strategy to prepare a series of single atom Cu catalysts by growing a sulfated zirconia thin film on SBA-15 to anchor Cu sites. The optimal catalytic performance can be obtained when the Cu loading is 10.98 wt %, which achieves high dimethoxymethane selectivity of 93.16% and high dimethoxymethane yield of 4.69% for nonoxidative methanol dehydrogenation, representing the top catalytic performance among the reported catalysts. Moreover, regeneration experiments, in situ DRIFT, and theoretical calculations demonstrated that the stability of the catalyst can be greatly improved by simply mixing with hydrophobic additives, which can selectively penetrate methanol molecules and hinder the penetration of H2O due to the charge sieving effect generated by the H atoms.