College of Chemistry and Chemical Engineering, iCHEM, PCOSS Xiamen University, Xiamen, 361005, China.
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
Angew Chem Int Ed Engl. 2017 Aug 7;56(33):9704-9709. doi: 10.1002/anie.201703675. Epub 2017 Jun 5.
Microenvironments in enzymes play crucial roles in controlling the activities and selectivities of reaction centers. Herein we report the tuning of the catalytic microenvironments of metal-organic layers (MOLs), a two-dimensional version of metal-organic frameworks (MOFs) with thickness down to a monolayer, to control product selectivities. By modifying the secondary building units (SBUs) of MOLs with monocarboxylic acids, such as gluconic acid, we changed the hydrophobicity/hydrophilicity around the active sites and fine-tuned the selectivity in photocatalytic oxidation of tetrahydrofuran (THF) to exclusively afford butyrolactone (BTL), likely a result of prolonging the residence time of reaction intermediates in the hydrophilic microenvironment of catalytic centers. Our work highlights new opportunities in using functional MOLs as highly tunable and selective two-dimensional catalytic materials.
酶中的微环境在控制反应中心的活性和选择性方面起着至关重要的作用。在此，我们报告了金属-有机层（MOLs）的催化微环境的调节，MOLs 是金属-有机骨架（MOFs）的二维版本，厚度可达单层，以控制产物选择性。通过用单羧酸（如葡萄糖酸）修饰 MOL 的次级建筑单元（SBUs），我们改变了活性位点周围的疏水性/亲水性，并在四氢呋喃（THF）的光催化氧化中精细调节选择性，以专一地得到丁内酯（BTL），这可能是由于反应中间体在亲水催化中心微环境中的停留时间延长的结果。我们的工作强调了使用功能化 MOL 作为高度可调谐和选择性二维催化材料的新机会。
