Project

Exploring the intrinsic dynamics of rigid Zr-based metal-organic frameworks as a potential route towards complex catalytic transformations including redox chemistry

Code
01P07618
Duration
01 October 2018 → 30 September 2021
Funding
Regional and community funding: Special Research Fund
Research disciplines
  • Engineering and technology
    • Catalysis and reacting systems engineering not elsewhere classified
    • Particle design and technology
    • General chemical and biochemical engineering not elsewhere classified
    • Process engineering not elsewhere classified
    • Separation and membrane technologies not elsewhere classified
    • Transport phenomena not elsewhere classified
    • Other (bio)chemical engineering not elsewhere classified
Keywords
redox chemistry
 
Project description

The general objective of this proposal is the exploration of the intrinsic dynamics of the metalligand (M-L) bond in a class of stable Zr-based metal-organic frameworks with the principal aim to tune the materials for complex catalytic transformations including redox chemistry. We intend to develop MOF-scaffolds which may be used in ligand-assisted catalysis for C-H bond activation of aromatic compounds, where the MOF itself takes the function of the ligand. Recent experimental and theoretical reports have shown that the stable UiO-66 material, is much more dynamic than originally believed. The M-L bond can temporarily break, without compromising the stability resulting in dynamic changes of the coordination number which offer the potential to modify the structure enabling dynamic proton shuttles, post synthetic cation exchange and ability to dock redox active cations. Herein, we will conduct a fundamental study on the intrinsic flexibility of a class of Zr6-based MOFs connected with variously shaped organic linkers and zirconium node connectivity ranging from 12 to 6. The materials are particularly interesting for catalysis, due to their stability, larger pores and internal surface area. State of the art molecular dynamics based simulations methods, allow to follow the system in situ during activation processes, which poses a huge challenge to realize experimentally. The project relies on a bilateral collaboration between a theoretical and experimental group.