Assembly of the Molecular Catalysts in Nanoreactors

The traditional methods, such as hydrothermal synthesis, impregnation, and chemical vapor deposition (CVD), can be employed to incorporate heteroatom and metal/metal oxide nanoparticles as catalysts into the nanopores of MSs. The advances in this area have been well summarized in recent reviews [35 - 38]. Herein, we will mainly focus on the assembly of molecular catalysts in the nanopore of MSs and MOFs. Using the molecular chiral catalyst as a model, we will address the general strategies for incorporating molecular catalysts in the nanoreactor, including the covalent and noncovalent bonding methods. 

Incorporating Chiral Molecular Catalysts In Nanoreactors through Covalent-Bonding Methods 

Post-synthetic modification can also be used for the synthesis of chiral MOFs via introducing chiral catalysts into the open coordination site of metal nodes of achiral MOFs [4S]. After the removal of the coordinated water molecules, two 

Immobilizing Chiral Molecular Catalysts in Nanoreactors through Noncovalent 

1 Introduction oTMolecular Catalysts into Nanoreactors through Noncovalent Bonding Methods 

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In this chapter, we summarize the recent advances in the development of nanaoreactors based on porous solid materials for chemical reactions, including the general methods for the fabrication of typical porous materials, (mesoporous silicas (MSs), carbon nanotubes (CNTs), and the MOFs), the assembly of the molecular catalysts in the cavities and pores of the porous materials, the chemical reactions in the porous-material-based nanoreactors, and some important issues concerning the porous-material-based nanoreactor, such as the pore confinement effect, the isolation effect, and the cooperative activation effect We close this chapter with an outlook of the future development of the nanoreactors. 

Later, more sophisticated supramolecular complexes capable of improved molecular recognition started to be studied. New supramolecular approaches to constmct synthetic biohybrid catalysts were developed [190]. An example is the giant amphi-philes, formed by a (hydrophilic) enzyme headgroup and a synthetic apolar tail. These biohybrid amphiphilic compounds self-assemble in water to yield enzyme fibers and enzyme reaction vessels (nanoreactors [202]). 

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