Neighboring Zn–Zr Sites in a Metal–Organic Framework for CO₂ Hydrogenation

Abstract

ZrZnO_<i>x</i> is active in catalyzing carbon dioxide (CO₂) hydrogenation to methanol (MeOH) via a synergy between ZnO_<i>x</i> and ZrO_<i>x</i>. Here we report the construction of Zn²⁺-O-Zr⁴⁺ sites in a metal-organic framework (MOF) to reveal insights into the structural requirement for MeOH production. The Zn²⁺-O-Zr⁴⁺ sites are obtained by postsynthetic treatment of Zr₆(μ₃-O)₄(μ₃-OH)₄ nodes of MOF-808 by ZnEt₂ and a mild thermal treatment to remove capping ligands and afford exposed metal sites for catalysis. The resultant MOF-808-Zn catalyst exhibits >99% MeOH selectivity in CO₂ hydrogenation at 250 °C and a high space-time yield of up to 190.7 mg_MeOH g_Zn^-1 h^-1. The catalytic activity is stable for at least 100 h. X-ray absorption spectroscopy (XAS) analyses indicate the presence of Zn²⁺-O-Zr⁴⁺ centers instead of Zn_<i>m</i>O_<i>n</i> clusters. Temperature-programmed desorption (TPD) of hydrogen and H/D exchange tests show the activation of H₂ by Zn²⁺ centers. Open Zr⁴⁺ sites are also critical, as Zn²⁺ centers supported on Zr-based nodes of other MOFs without open Zr⁴⁺ sites fail to produce MeOH. TPD of CO₂ reveals the importance of bicarbonate decomposition under reaction conditions in generating open Zr⁴⁺ sites for CO₂ activation. The well-defined local structures of metal-oxo nodes in MOFs provide a unique opportunity to elucidate structural details of bifunctional catalytic centers.