Coordinatively Unsaturated Aluminum Enables Methanol‐Selective CO ₂ Hydrogenation With Zeolite‐Supported Copper Catalysts

We demonstrate the synthesis of Cu(AlO x ) a (SiO y ) b clusters under the confines of MER zeolite, which hydrogenate CO 2 to methanol and dimethyl ether with 96% selectivity and a space time yield of 15.0 mmol C g Cu −1 h −1 at 250 °C (4:1 H 2 :CO 2 and 5 MPa). A crucial aspect of the synthesis involves MER zeolite calcination, leading to framework dealumination and loss of long‐range order. These Cu(AlO x ) a (SiO y ) b clusters consist of a high density of coordinatively unsaturated aluminum sites, which are lacking in conventional copper catalysts with similar stoichiometry, and stabilize copper in a more oxidic form that is characterized by higher reduction temperatures. Other copper‐containing zeolites consisting of stable frameworks that do not dealuminate upon calcination (Cu‐Li‐FAU and Cu‐Li‐RHO zeolites) exhibit 99% selectivity to CO under the same reaction conditions. When compared with these catalysts and an industrial CuZnAl catalyst, kinetic analysis shows the Cu(AlO x ) a (SiO y ) b clusters are more intrinsically selective for methanol over the reverse water gas shift reaction at low CO 2 converions.