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Inverse relationship of dimensionality and catalytic activity in CO2 transformation: a systematic investigation by comparing multidimensional metal-organic frameworks
- Inverse relationship of dimensionality and catalytic activity in CO2 transformation: a systematic investigation by comparing multidimensional metal-organic frameworks
- Babu, Robin; Roshan, Roshith; Gim, Yeongrok; Jang, Yun Hee; Kurisingal, Jintu Francis; Kim, Dong Woo; Park, Dae-Won
- DGIST Authors
- Gim, Yeongrok; Jang, Yun Hee
- Issue Date
- Journal of Materials Chemistry A, 5(30), 15961-15969
- Article Type
- Carbon Dioxide; Catalysis; Catalyst Activity; Catalysts; Catalytic Performance; Chemical Fixation; Conversion; Coordination Environment; Crystalline Materials; Cyclic Carbonate Synthesis; Cycloaddition; Cycloaddition Reaction; Density Functional Theory; Dioxide Capture; Epoxides; Highly Efficient; Indium; Inverse Relationship; Metal Organic Framework (MOF); Metal Testing; Organometallics; Photocatalyst; Propylene Oxide; Reduction; Solid Acid Catalysts; Structural Investigation; Unsaturated Metal Centers
- The correlation between dimensionality and active sites on deciding the catalytic performance of an MOF catalyst in CO2-epoxide cycloaddition reactions has been studied. Seven In(iii) based MOFs built from carboxylic and N-donor ligands possessing different dimensionalities and distinct coordination environments were chosen as solid acid catalysts for this study. The origin of the catalytic activity of an In3+/TBAB bifunctional system in a CO2-PO reaction was studied in detail by performing density functional theory (DFT) calculations at the M06/LACVP∗∗++ level. The energy barrier of the propylene oxide ring opening in the presence of In3+/Br- is 11.5 kcal mol-1, which is significantly lower than those of un-catalyzed (55-63 kcal mol-1) and Br--catalyzed (19.5 kcal mol-1) reactions, which confirms the importance of the In3+/Br- binary catalytic system in the CO2-epoxide cycloaddition reactions. The one-dimensional (1D) MOF with unsaturated metal centers exhibited higher catalytic activity (PO conversion: 91%, temperature: 50 °C, and time: 12 h) than the two- and three-dimensional MOFs. The roles of dimensionality and unsaturated metal centers in cycloaddition reactions were explained on the basis of the results of activity testing and structural investigations. In addition, a plausible reaction mechanism for the catalytic activity of the 1D MOF was proposed with reference to our structure-density functional theory correlations. © 2017 The Royal Society of Chemistry.
- Royal Society of Chemistry
- Related Researcher
Jang, Yun Hee
CMMM Lab(Curious Minds Molecular Modeling Laboratory)
Multiscale molecular modeling (quantum mechanics calculation; molecular dynamics simulation) : Supercomputer-assisted molecular-level understanding of materials and their chemistry; which leads to rational design of high-performance organic-inorganic-hybrid materials for clean and renewable energy as well as low-energy-consumption electronic devices
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- Department of Energy Science and EngineeringCMMM Lab(Curious Minds Molecular Modeling Laboratory)1. Journal Articles
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