Yuan Kuo, Song Tianqun, Wang Dawei, Zhang Xiaotao, Gao Xiong, Zou Ye, Dong Huanli, Tang Zhiyong, Hu Wenping
Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Sciences, Tianjin University & Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, China.
Chinese Academy of Sciences (CAS), Key Laboratory of Nanosystem and Hierarchy Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, China.
Angew Chem Int Ed Engl. 2018 May 14;57(20):5708-5713. doi: 10.1002/anie.201801289. Epub 2018 Mar 23.
Metal-organic frameworks (MOFs) as selectivity regulators for catalytic reactions have attracted much attention, especially MOFs and metal nanoparticle (NP) shelled structures, e.g., MOFs@NPs@MOFs. Nevertheless, making hydrophilic MOF shells for gathering hydrophobic reactants is challenging. Described here is a new and viable approach employing conjugated micro- and mesoporous polymers with iron(III) porphyrin (FeP-CMPs) as a new shell to fabricate MIL-101@Pt@FeP-CMP. It is not only hydrophobic and porous for enriching reactants, but also possesses iron sites to activate C=O bonds, thereby regulating the selectivity for cinnamyl alcohol in the hydrogenation of cinnamaldehyde. Interestingly, MIL-101@Pt@FeP-CMP can achieve a high turnover frequency ( 1516.1 h ), with 97.3 % selectivity for cinnamyl alcohol at 97.6 % conversion.
金属有机框架材料（MOFs）作为催化反应的选择性调节剂已引起广泛关注，尤其是MOFs与金属纳米颗粒（NP）壳层结构，例如MOFs@NPs@MOFs。然而，制备用于聚集疏水性反应物的亲水性MOF壳层具有挑战性。本文描述了一种新的可行方法，即采用具有铁（III）卟啉（FeP-CMPs）的共轭微孔和介孔聚合物作为新的壳层来制备MIL-101@Pt@FeP-CMP。它不仅具有疏水性和多孔性以富集反应物，还拥有铁位点来活化C=O键，从而调节肉桂醛加氢反应中肉桂醇的选择性。有趣的是，MIL-101@Pt@FeP-CMP能够实现高周转频率（1516.1 h⁻¹），在97.6%的转化率下对肉桂醇的选择性为97.3%。
