The nanoporous structures of metal-organic frameworks (MOFs) can be functionally regulated according to specific targets of interest
and thus such types of solids can be considered as promising industrial catalytic materials. Since interface microenvironments and catalytic properties of MOFs might be affected by the solvents
it is necessary to study the influence of solvent effects on their catalytic activities. Although MOFs with coordinatively unsaturated metal sites (CUMs) have shown promising applications in liquid-phase catalysis
the related solvent effects on the Lewis acid catalytic performance of these CUMs are seldom investigated. In this work
density functional theory calculations were conducted to investigate the solvent effects on the properties of the Lewis acid sites in two typical MOFs
Cu-BTC and MOP-15
where the COSMO (conductor-like solvent model) was used to mimic the dielectric response of the solvent environments. Different relative dielectric constants were considered
including in vacuum
toluene
ethyl acetate
1
2-dichloroethane and acetonitrile. Using CO as the probe molecule
the solvent effects were examined by exploring the geometry parameters
the Mulliken charges
and the vibrational frequency as well as the adsorption energy of CO molecule around those CUMs. The strengths of Lewis acid sites could be enhanced with the increase of the dielectric constant. Further
the solvent effects became more evident in CUMs when the organic linkers had higher electronegativity. These observations provide fundamental insights into the regulation of the liquid-phase catalytic activity of MOFs using specific solvents.
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Synthesis of 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid in organic solvent systems
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Related Author
BO Xiaofan
WU Pingyi
MA Qintian
LAN Ling
GONG Xiang
LI Linsen
JIANG Zhao
Peng XIE
Related Institution
Petrochemical Research Institute, PetroChina
Department of Chemical Engineering, Xi’an Jiaotong University, Shaanxi Key Laboratory of Energy Chemical Process Intensification
State Key Laboratory of Chemical Engineering, East China University of Science and Technology
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University
Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology, Tianjin University