Selectivity Control in the Direct CO Esterification over Pd@UiO‐66: The Pd Location Matters

The selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal–organic frameworks (MOFs), namely UiO‐66‐X (X=‐H, ‐NO2, ‐NH2), affording Pd@UiO‐66‐X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO‐66, displays high selectivity (89 %) to DMO as always reported with Pd NPs. Both experimental and DFT calculation results prove that the Pd location relative to UiO‐66 gives rise to discriminated microenvironment of different amounts of interface between Zr‐oxo clusters and Pd NPs in Pd@UiO‐66 and Pd/UiO‐66, resulting in their distinctly different selectivity. This is an unprecedented finding on the production of DMC by Pd NPs, which was previously achieved by Pd(II) only, in the direct CO esterification. Incorporating Pd nanoparticles into metal–organic frameworks (MOFs) exhibits high selectivity for dimethyl carbonate (DMC), while Pd nanoparticles on MOFs and other supports give high selectivity for dimethyl oxalate (DMO) in the direct CO esterification with methyl nitrite. The Lewis acid microenvironment surrounding Pd NPs is responsible for the reversed product selectivity.