ABSTRACT
We have developed an original synthetic pathway for the conversion of a MIL-68(In)-NH(2) metal-organic framework into its corresponding isocyanate (-NCO) derivative. This two-step soft post-modification technique leads to highly porous isostructural materials.
ABSTRACT
We successively introduce new catalytic centers through click reaction into MOFs and modify their environment by addition of lipophilic groups. The resulting bifunctionalized MOF provides an optimized balance between basicity and lipophilicity and shows outstanding performance for the transesterification reaction.
ABSTRACT
Carbon dioxide capture from processes is one of the strategies adopted to decrease anthropogenic greenhouse gas emissions. To lower the cost associated with the regeneration of amine-based scrubber systems, one of the envisaged strategies is the grafting of amines onto high-surface-area supports and, in particular, onto metal-organic frameworks (MOFs). In this study, the interaction between CO(2) and aliphatic and aromatic amines has been characterized by quantum mechanical methods (MP2), focusing attention both on species already reported in MOFs and on new amine-based linkers, to inspire the rational synthesis of new high-capacity MOFs. The calculations highlight binding-site requisites and indicate that CO(2) vibrations are independent of the adsorption energy and monitoring them in probe-molecule experiments is not a suitable marker of efficient adsorption.
Subject(s)
Amines/chemistry , Carbon Dioxide/chemistry , Carbon Dioxide/isolation & purification , Carbon Sequestration , Organometallic Compounds/chemistry , Models, Molecular , Molecular Conformation , Static Electricity , Thermodynamics , VibrationABSTRACT
This study deals with the development of a soft, generic, one-pot postfunctionalization method for metal-organic frameworks (MOFs) starting from compounds with an amino group on the linker. The first step consists of transforming the amino group into azide (N(3)) by an unconventional route using tBuONO and TMSN(3). In the same vessel, the desired functionalized MOF then is obtained by the Huisgen 1,3-dipolar cycloaddition of azides to alkynes, otherwise known as the "click" reaction. The method was applied to DMOF-NH(2) and MIL-68(In)-NH(2), which represent two distinct and important classes of MOF. For both, the functionalization was complete (>90% grafting) and the crystallinity was maintained. Thanks to the large diversity and availability of cyano- and acetylene-based chemicals, this method opens the door to tailor-made functionalized MOFs.
