A quantum-chemical insight on chemical fixation carbon dioxide with epoxides co-catalyzed by MIL-101 and tetrabutylammonium bromide

Mechanism for CO2 Fixation with Aziridines Synergistically Catalyzed by HKUST-1 and TBAB: A DFT Study

“…Thus, here, the Br – is used to simulate the bulky TBAB. This methodology has been widely used in investigating the cycloaddition mechanism of CO 2 and propylene epoxide, which is an analogue of aziridine. , Similar to the noncatalyzed and HKUST-1-catalyzed reactions, the binary HKUST-1/TBAB system involves two different pathways: i.e., path-α and path-β. Figures and show the Gibbs free energy profiles for path-α and path-β, respectively.…”

“…Thus, considering the computational cost, we established a truncated cluster model (i.e., the model of dicopper tetraformate Cu 2 (HCOO) 4 ) by cutting the periodic structure and saturating it with protons (see A in Figure ). In fact, this methodology has been very often applied in previous calculations on adsorption and catalysis by MOFs. − To mimic the constraints imposed by the surrounding MOF structure, the terminal H atoms in the framework were fixed but the remaining atoms were relaxed. Additionally, the validity of the Cu 2 (HCOO) 4 model was tested by a larger Cu 2 (C 6 H 5 COO) 4 model with four benzenecarboxylate ligands, which could much better describe the chemical environment of HKUST-1.…”

On the Role of Alkali‐Metal‐Like Superatom Al12P in Reduction and Conversion of Carbon Dioxide

“…The cycloaddition of CO 2 with epoxides to produce cyclic carbonates, as one of the most successful strategies to transform CO 2 into value‐added chemicals has been the ongoing hot topic throughout the past years [2, 3] . Without catalysts, such a cycloaddition reaction undergoes only one elementary step with a very high energy barrier [3b, e] . Differently, the formation of cyclic carbonates can be achieved through three consecutive steps with the help of catalysts and co‐catalysts, namely the ring‐opening of epoxide, insertion of CO 2 , and ring‐closure of cyclic carbonate [3] .…”

Electrochemical Potential of the Metal Organic Framework MIL-101(Fe) as Cathode Material in Li-Ion Batteries

“…The electronic structure calculations were performed on a simplified cluster model of the large MIL-101(Fe) unit cell adapted from the family of trimetallic [M 3 O(OOCR) 6 L 3 ] + n paddlewheel complexes (M=Fe, R=H, n = 1; no L ligands), representing the SBU of the MOF shown in Figure 1. This model with/without the axial anions/molecules has been successfully applied in many earlier MIL-101 studies [23][24][25][26][27]. Notably, in order to understand various magnetic orders present in the MOF, the system could be treated also with a periodic approach using a very large supercell containing several cluster models, as shown by Trepte et al [34] in the case of DUT-8(Ni).…”

“…Since the secondary building units (SBUs) are quite well separated and known to be the active sites in MIL-101 [23], it is reasonable to replace the extended periodic structure of the solid with a non-periodic cluster model that can capture the binding properties near the active site. Such an approach has been used in previous studies of MIL-101 materials [23][24][25][26][27] and other Fe-containing organometallics [20][21][22]. Beyond the van der Waals materials, cluster models have been successfully applied for the optimization of reduction activity of covalently bonded Fe-N4@graphene for fuel-cell fabrication [28][29][30].…”