Surface‐Deactivated Core–Shell Metal–Organic Framework by Simple Ligand Exchange for Enhanced Size Discrimination in Aerobic Oxidation of Alcohols. Issue 34 (15th May 2020)

• Record Type: Journal Article
• Authors: Kim, Seongwoo; Lee, Jooyeon; Jeoung, Sungeun; Moon, Hoi Ri; Kim, Min
• Is Part Of: Chemistry. Volume 26:Issue 34(2020)
• Page Start: 7568
• Page End: 7572
• Publication Date: 2020-05-15
• Subjects: aerobic oxidation -- ligand exchange -- metal–organic frameworks -- post-synthetic modifications -- TEMPO; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202000933
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Metal–organic frameworks (MOFs) are an attractive catalyst support for stable immobilization of the active sites in their scaffold due to the high tunability of organic ligands. The active site‐functionalized ligands can be easily employed to construct MOFs as porous heterogeneous catalysts. However, the existence of active sites on the external surfaces as well as internal pores of MOFs seriously impedes the selective reaction in the pore. Herein, through a simple post‐synthetic ligand exchange (PSE) method we synthesized surface‐deactivated (only core‐active) core–shell‐type MOF catalysts, which contain 2, 2, 6, 6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) groups on the ligand as active sites for aerobic oxidation of alcohols. The porous but catalytically inactive shell ensured the size‐selective permeability by sieving effects and induced all reactions to take place in the pores of the catalytically active core. Because PSE is a facile and universal approach, this can be rapidly applied to a variety of MOF‐based catalysts for enhancing reaction selectivity. Abstract : Site control : Removing catalytic sites near the surface of the MOF crystal allowed for enhanced size discrimination of the reactants thus improving selectivity.