Metal‐Organic Frameworks as a New Platform to Construct Ordered Mesoporous Ce‐Based Oxides for Efficient CO2 Fixation under Ambient Conditions

Metal-organic frameworks (MOFs) are proved to be good precursors to derive various nanomaterials with desirable functions, but so far the controllable synthesis of ordered mesoporous derivatives from MOFs has not been achieved. Herein, this work reports, for the first time, the construction of MOF-derived ordered mesoporous (OM) derivatives by developing a facile mesopore-inherited pyrolysis-oxidation strategy. This work demonstrates a particularly elegant example of this strategy, which involves the mesopore-inherited pyrolysis of OM-CeMOF into a OM-CeO₂ @C composite, followed by the oxidation removal of its residual carbon, affording the corresponding OM-CeO₂ . Furthermore, the good tunability of MOFs helps to allodially introduce zirconium into OM-CeO₂ to regulate its acid-base property, thus boosting its catalytic activity for CO₂ fixation. Impressively, the optimized Zr-doped OM-CeO₂ can achieve above 16 times higher catalytic activity than its solid CeO₂ counterpart, representing the first metal oxide-based catalyst to realize the complete cycloaddition of epichlorohydrin with CO₂ under ambient temperature and pressure. This study not only develops a new MOF-based platform for enriching the family of ordered mesoporous nanomaterials, but also demonstrates an ambient catalytic system for CO₂ fixation.