The Activity of Ultrafine Cu Clusters Encapsulated in Nano-Zeolite for Selective Hydrogenation of CO2 to Methanol

Narrowly dispersed ultrafine Cu clusters of sizes smaller than 2.0 nm have been encapsulated in nanosized silicalite-1 zeolite through direct crystallization in the presence of Cu(en)22+ complex ions as the metal precursor. The growing silicalite-1 crystals are rich in vacancy defects and connectivity defects on the grain boundaries, where the terminating silanols promote the decomposition of Cu(en)22+, thus the deposition of ultrafine Cu species. The obtained composite material as a model catalyst is active for CO2 activation and hydrogenation to methanol. The preliminary in situ FTIR study recognizes a series of surface-adsorbed carbonyl, formyl, carbonate, and formate species when the material is exposed to CO2 and H2. Among others, the adsorbed formate decays most rapidly upon cofeeding CO2 and H2, implying that the most probable pathway toward methanol formation over this material is via the formate-mediated mechanism.