The coordinatively unsaturated sites in MIL‐101, Cr3(F,OH)(H2O)2O[(O2C)‐C6H4‐(CO2)]3⋅n H2O (n≈25), having zeotypic giant pores can be selectively functionalized in a way differing from that of mesoporous silica. Metal–organic frameworks, grafted with ethylenediamine or diethylenetriamine on the unsaturated CrIII sites of MIL‐101, exhibit remarkably high activities in the Knoevenagel condensation relative to that of the mesophase.
The acid sites on γ-Al2O3 were characterized
using FTIR spectroscopy of adsorbed pyridine and temperature programmed
desorption (TPD) of 2-propanamine, ethanol, 1-propanol, 2-propanol,
and 2-methyl-2-propanol, together with density functional theory (DFT)
calculations. Following room-temperature adsorption and evacuation,
the surface coverages of the adsorbed alcohols were between 2 and
3.2 × 1018 molecules/m2. For each of the
adsorbed alcohols, reaction to olefin and water products occurred
in a narrow peak that indicated reaction is a first-order process
with a well-defined activation energy, which in turn depended strongly
on the particular alcohol. DFT calculations on an Al8O12 cluster are in excellent agreement with the experimental
observations and show that the transition states for dehydration had
carbenium-ion character. The carbenium ion stability in terms of proton
affinity (of alkenes) matches well with the activation energy of the
dehydration reaction. Adsorption of water on the γ-Al2O3, followed by evacuation at 373 K, demonstrated that
water simply blocks sites for the alcohols without affecting the reaction
activation energy. There was no evidence for Brønsted sites on
the γ-Al2O3 based on FTIR of pyridine
or TPD of 2-propanamine.
Molecular simulations have largely contributed to the emergence of Metal Organic Frameworks (MOFs) not only for the resolution of the crystal structures of the most complex and poorly crystallized solids but also to enumerate all the plausible structures constructed by the assembly of a large diversity of inorganic and organic building blocks. Besides this in silico design of novel MOFs which has been only rarely validated so far by the post-synthesis of the desired material, a computational effort has been deployed to modulate the chemical and topological features of existing architectures specifically targeted for societally-relevant applications. Molecular modelling has been also frequently used to guide interpretation of the experimental data by providing a deep understanding of the microscopic adsorption/separation mechanism with the objective to drive the synthesis effort towards tuned materials with the required features for an optimization of their properties. This presentation will highlight the invaluable contribution of the computational approaches from the birth of novel MOFs and their structure elucidations to the characterization and understanding of their properties, throughout recent advances our groups have made in this field. A special emphasizes will be devoted to a series of recent MOFs that show promising adsorption/separation performances for natural gas upgrading, carbon capture and interesting features for mechanical energy storage and proton conduction.
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