scholarly journals Single-atom active sites on metal-organic frameworks

Author(s):  
Marco Ranocchiari ◽  
Christian Lothschütz ◽  
Daniel Grolimund ◽  
Jeroen Anton van Bokhoven

Single-site heterogeneous catalysis has been recently accepted as a novel branch of heterogeneous catalysis. Catalysts with single-atom active sites (SAHCs) allow the design and fine-tuning of the active moiety, and can potentially combine the advantages of heterogeneous and homogeneous catalysis. This study illustrates how porous metal-organic frameworks (MOFs) can be synthesized with homogeneous distribution of SAHCs. The catalytic potential of MIXMOFs is shown. A short overview of catalysis with mesoporous silica materials is described to demonstrate their importance in SAHC.

Author(s):  
Feijie Song ◽  
Teng Zhang ◽  
Cheng Wang ◽  
Wenbin Lin

Metal-organic frameworks (MOFs) are a class of organic–inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. They have received much attention in recent years owing to the ability to tune their properties for potential applications in various areas. Properly designed MOFs with uniform, periodically aligned active sites have shown great promise in catalysing shape-, size-, chemo-, regio- and stereo-selective organic transformations. This study reports the synthesis and characterization of two chiral MOFs (CMOFs 1 and 2 ) that are constructed from Mn-salen-derived dicarboxylic acids [salen is ( R , R )- N , N ′-bis(5- tert -butylsalicylidene)-1,2-cyclohexanediamine], bis(4-vinylbenzoic acid)-salen manganese(III) chloride (H 2 L 4 ) or bis(benzoic acid)-salen manganese(III) chloride (H 2 L 3 ) and [Zn 4 (μ 4 -O)(O 2 CR) 6 ] or [Zn 5 (H 2 O) 2 (μ 3 -OH) 2 (O 2 CR) 8 ] secondary building units (SBUs), respectively. The SBUs in CMOF- 1 are connected by the linear ditopic Mn-salen-derived linkers to construct a fourfold interpenetrated isoreticular MOF (IRMOF) structure with pcu topology. In CMOF- 2 , the Mn-salen centres dimerize in a cross-linking way to form a diamondoid structure with threefold interpenetration. CMOF- 1 was examined for highly regio- and stereo-selective tandem alkene epoxidation/epoxide ring-opening reactions by using the Mn-salen andZn 4 (μ 4 -O)(carboxylate) 6 active sites, respectively. Our work demonstrated the potential utility of chiral MOFs with multiple active sites in the efficient synthesis of complex molecules with excellent regio- and stereo-controls


2014 ◽  
Vol 1 (10) ◽  
pp. 721-734 ◽  
Author(s):  
Sha Ou ◽  
Chuan-De Wu

The recently developed strategies on designed synthesis of porous metal–organic framework catalysts and their interesting catalytic properties are summarized in this short review.


ChemInform ◽  
2012 ◽  
Vol 43 (48) ◽  
pp. no-no
Author(s):  
Marco Ranocchiari ◽  
Christian Lothschuetz ◽  
Daniel Grolimund ◽  
Jeroen Anton van Bokhoven

2019 ◽  
Vol 7 (11) ◽  
pp. 1743-1758 ◽  
Author(s):  
Liang Feng ◽  
Kun-Yu Wang ◽  
Xiu-Liang Lv ◽  
Tian-Hao Yan ◽  
Hong-Cai Zhou

Abstract Despite numerous advantages, applications of conventional microporous metal–organic frameworks (MOFs) are hampered by their limited pore sizes, such as in heterogeneous catalysis and guest delivery, which usually involve large molecules. Construction of hierarchically porous MOFs (HP-MOFs) is vital to achieve the controllable augmentation of MOF pore size to mesopores or even macropores, which can enhance the diffusion kinetics of guests and improve the storage capacity. This review article focuses on recent advances in the methodology of HP-MOF synthesis, covering preparation of HP-MOFs with intrinsic hierarchical pores, and modulated, templated and template-free synthetic strategies for HP-MOFs. The key factors which affect the formation of HP-MOF architectures are summarized and discussed, followed by a brief review of their applications in heterogeneous catalysis and guest encapsulation. Overall, this review presents a roadmap that will guide the future design and development of HP-MOF materials with molecular precision and mesoscopic complexity.


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