4.8 Review

Rational Design of Catalytic Centers in Crystalline Frameworks

Journal

ADVANCED MATERIALS
Volume 30, Issue 33, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adma.201707582

Keywords

covalent organic frameworks; metal organic frameworks; molecular solid catalysts; reaction pathways; single catalytic sites

Funding

  1. Ministry of Education, Singapore (AcRF Tier 1) [RG116/16]
  2. Nanyang Technological University
  3. Cambridge Centre for Carbon Reduction in Chemical Technology CREATE Programmes [C4T]

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Crystalline frameworks including primarily metal organic frameworks (MOF) and covalent organic frameworks (COF) have received much attention in the field of heterogeneous catalysts recently. Beyond providing large surface area and spatial confinement, these crystalline frameworks can be designed to either directly act as or influence the catalytic sites at molecular level. This approach offers a unique advantage to gain deeper insights of structure-activity correlations in solid materials, leading to new guiding principles for rational design of advanced solid catalysts for potential important applications related to energy and fine chemical synthesis. In this review, recent key progress achieved in designing MOF- and COF-based molecular solid catalysts and the mechanistic understanding of the catalytic centers and associated reaction pathways are summarized. The state-of-the-art rational design of MOF- and COF-based solid catalysts in this review is grouped into seven different areas: (i) metalated linkers, (ii) metalated moieties anchored on linkers, (iii) organic moieties anchored on linkers, (iv) encapsulated single sites in pores, and (v) metal-mode-based active sites in MOFs. Along with this, some attention is paid to theoretical studies about the reaction mechanisms. Finally, technical challenges and possible solutions in applying these catalysts for practical applications are also presented.

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