Computational screening of metal-substituted HKUST-1 catalysts for chemical fixation of carbon dioxide into epoxides

Abstract

This work would enrich the CO2–PO reaction catalyzed by M-HKUST-1/TBAX and provide a guideline for the design of more powerful catalysts.

Metal and Co‐Catalyst Free CO2 Conversion with a Bifunctional Covalent Organic Framework (COF)

“…As shown in entries 6 and 7 of Table 2, COF-TpPa-Py-Cl À or COF-TpPa-Py-I À (Figures S32-S33) has a significantly lower catalytic yield (57 � 1.8 % for COF-TpPa-Py-I À and 50 � 2.2 % for COF-TpPa-Py-Cl À ) than that of COF-TpPa-Py-Br À under the same reaction conditions. According to the previous work, [45][46][47][48] the low activity of COF-TpPa-Py-Cl À may be attributed to the poor nucleophilicity of Cl À anion. On the other hand, I À anion with a larger radius will restrict the diffusion of reactant and product in COF-TpPa-Py-I À and thus, reduce the conversion rate.…”

A more effective catalysis of the CO2 fixation with aziridines: computational screening of metal-substituted HKUST-1

“…For each stationary point, the intrinsic reaction coordinate (IRC) analysis was undertaken to confirm that it connected the desired minimal reactant and product on the potential energy surface [60]. Throughout the entire reaction pathways, we used the solvent Et 2 O to model this reaction and performed self-consistent reaction field calculations with the polarizable continuum model to consider the effects of solvent, as was completed in previous similar investigations [39]. Additionally, to obtain more reliable interaction energies, single-point energy calculations were conducted on the stationary points by using M06-2X functional with a larger basis set, i.e., SDD for transitionmetal atoms and Bromine atom, 6-311++G(2df,p) for the other elements…”

“…Open since for such thermally activated processes, the spin turnover (or intersystem crossing between different states) is usually unlikely to take place. Such a spin-selected methodologyhas been applied in previous studies [39,63].…”

“…It has proven quite applicable to design novel and powerful MOF-based catalysts simply by altering the metal centers while retaining the rigid framework of a MOF [39][40][41][42][43][44][45][46].The recently reported [Cu 30 ] nanocages [35]contain the Cu-HKUST-1 building units. As is well known, the HKUST-1 (HKUST = Hong Kong University of Science and Technology) (also known as Cu-BTC or MOF-199, BTC = 1,3,5-benzenetricarboxylate) MOF possesses a number of attractive features includingthe designability and stability [47].…”

Controllable Generation of Reactive Oxygen Species on Cyano-Group-Modified Carbon Nitride for Selective Epoxidation of Styrene

“…Selective epoxidation of styrene by reactive oxygen species (ROS) originating from dioxygen is an economically important atomic reaction, and the styrene oxide products are versatile intermediates for the synthesis of perfumes, drugs, epoxy resins, and sweeteners and even for the chemical fixation of CO 2 . [1][2][3] The ROS mainly include superoxide anion radical (O 2 ,À , Scheme 1, Equation 3), 4 hydrogen peroxide (H 2 O 2 , Equation 4, or the intermediate peroxyl species, -O-O-), 5 hydroxyl radical ( , OH, Equation 5), 6 and singlet oxygen ( 1 O 2 , Equations 8, 9, and 10, the energy transfer from the excited state of the sensitizer or O 2 ,À oxidation product). 7,8 Among all the ROS, -O-O-and 1 O 2 react with styrene via [2 + 2] photochemical cycloaddition and generate styrene oxide as the product.…”