Ionic liquid induced structural transformation in a copper-based MOF synthesis: Experimental and DFT investigations
Abstract
The development of advanced materials for carbon management has driven significant interest in hybrid systems based on metal–organic frameworks (MOFs) and ionic liquids (ILs), owing to their tunable structures and enhanced affinity for CO2. In this study, we demonstrate that the IL [BMIm][BF4], employed as an ionothermal medium, plays a dual role as both solvent and structure-directing agent, enabling the formation of a two-dimensional copper–terephthalate network (Cu-BDC-2), which differs from the material obtained via conventional solvothermal synthesis (Cu-BDC-1). Structural and spectroscopic analyses reveal that IL-derived species remain associated with the framework surface, directly influencing its physicochemical properties. CO2 adsorption measurements at 85 °C show that Cu-BDC-2 exhibits enhanced interactions with CO2, attributed to the effect of IL-derived species. In contrast, theoretical calculations indicate that, in Cu-BDC-1, van der Waals interactions between CO2 and the aromatic linkers dominate the adsorption process. Furthermore, the GFN1 − xTB method shows good agreement with DFT + U results, highlighting its potential as a computationally efficient approach for screening such systems. These findings demonstrate that ionothermal synthesis is an effective strategy for modulating both the structure and surface functionality of MOF-based materials, opening new perspectives for their applications.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (12)
Jarede S. Martins
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,
Carolina B. P. Ligieiro
Centro Brasileiro de Pesquisas Físicas 2 , Rua Dr. Xavier Sigaud, 150—Urca, 2290-180 Rio de Janeiro, RJ,
Rodrigo S. Bitzer
Instituto de Química, Universidade Federal do Rio de Janeiro 3 , 21941-909 Rio de Janeiro, RJ,
Yann Maia
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,
Odivaldo C. Alves
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,
Sara S. Vieira
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,
Paulo Henrique M. Toledo
Departamento de Química, Universidade Federal de Juiz de Fora 4 , 36036-330 Juiz de Fora, MG,
Gustavo F. S. Andrade
Departamento de Química, Universidade Federal de Juiz de Fora 4 , 36036-330 Juiz de Fora, MG,
Thiago M. Rossi
Departamento de Processos Inorgânicos, Escola de Química, Universidade Federal do Rio de Janeiro 5 , 21941-909 Rio de Janeiro, RJ,
Mariana M. V. M. Souza
Departamento de Processos Inorgânicos, Escola de Química, Universidade Federal do Rio de Janeiro 5 , 21941-909 Rio de Janeiro, RJ,
Célia M. Ronconi
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,
Luciano T. Costa
Instituto de Química, Universidade Federal Fluminense 1 , Outeiro de São João Batista, 24020-141 Niterói, RJ,