Synergized Molecular Oxygen Activation in an Enzyme-Mimicking Metal-Organic Framework for Boosted C-H Bond Oxidation

被引:4
作者
Fan, Tao [1 ]
Gou, Gaozhang [1 ]
Wang, Man [1 ]
Fang, Lei [1 ]
Liang, Gan [1 ]
Yin, Ying [1 ]
Liu, Mingxian [1 ]
Ma, Yunsheng [2 ,3 ]
Matsuda, Ryotaro [2 ,3 ]
Wang, Tianqi [4 ]
Shang, Jin [4 ]
Gu, Qinfen [5 ]
Li, Liangchun [1 ]
机构
[1] Tongji Univ, Sch Chem Sci & Engn, Shanghai Key Lab Chem Assessment & Sustainabil, Shanghai 200092, Peoples R China
[2] Nagoya Univ, Grad Sch Engn, Sch Engn, Dept Chem & Biotechnol, Nagoya 4648603, Japan
[3] Nagoya Univ, Grad Sch Engn, Dept Mat Chem, Nagoya 4648603, Japan
[4] City Univ Hong Kong, Sch Energy & Environm, Kowloon, Tat Chee Ave, Hong Kong 999077, Peoples R China
[5] Australian Synchrotron ANSTO, Clayton, Vic 3168, Australia
基金
中国国家自然科学基金;
关键词
POROUS COORDINATION POLYMERS; AEROBIC OXIDATION; SELECTIVE OXIDATION; CATALYSIS; COPPER; EFFICIENT; IRON; GENERATION; ALCOHOLS; DIOXYGEN;
D O I
10.1021/acs.chemmater.4c01683
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Metal-organic frameworks (MOFs) have experienced significant progress and advancement in recent decades due to the multifarious modifications and functionalization of their inherent structures. However, the development of synergistic all-in-one MOF catalysts with functionalized organic linkers and metal nodes has posed formidable challenges. Here we construct an isostructural MOF, TJU-101-NHPI, using traditional Cu(II) paddle-wheel nodes as catalytic open metal sites (OMSs) and N-hydroxyphthalimide (NHPI) covalently embedded ligands as organocatalytic sites (OCSs) in spatial proximity. The TJU-101-NHPI catalyst, in combination with the cocatalyst t-butyl nitrite, can overcome the longstanding paradox to selectively oxidize primary alcohols to aldehydes or acids in a specific time-dependent manner. Moreover, the single TJU-101-NHPI MOF can directly activate O-2 to oxidize alkylarenes, resembling biomimetic enzymatic oxidation. The established catalytic systems use O-2 as the exclusive oxidant and yield H2O as the sole byproduct, achieving nearly complete conversion and 100% selectivity in the majority of the oxidations (62 examples). Control experiments and computational studies reveal that the synergistic activation of molecular oxygen and facilitated hydrogen atom transfer (HAT) between the OMSs and the OCSs lead to the generation of critical phthalimido N-oxyl radicals on the pore surface, thereby boosting the oxidation under mild conditions. This research offers a new concept of leveraging MOF organic linkers as cofactors and inorganic nodes as metal sites to mimic enzymes for superior catalysis.
引用
收藏
页码:9613 / 9624
页数:12
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