Catalytic Performance of Zr‐Based Metal–Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H 2 O 2

The catalytic performance of Zr‐abtc and MIP‐200 metal–organic frameworks consisting of 8‐connected Zr 6 clusters and tetratopic linkers was investigated in H 2 O 2 ‐based selective oxidations and compared with that of 12‐coordinated UiO‐66 and UiO‐67. Zr‐abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron‐deficient C=C bonds in α,β‐unsaturated ketones. The significant predominance of 1,2‐epoxide in carvone epoxidation, coupled with high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr‐abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr‐abtc. Electrophilic activation of H 2 O 2 can also be realized, as evidenced by the high activity of Zr‐abtc in epoxidation of the electron‐rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr‐abtc structure after the catalysis. The low activity of MIP‐200 in H 2 O 2 ‐based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H 2 O 2 .