85023-51-4Relevant articles and documents
Carbon Dioxide Conversion Upgraded by Host-guest Cooperation between Nitrogen-Rich Covalent Organic Framework and Imidazolium-Based Ionic Polymer
Gao, Jinwei,Sa, Rongjian,Wang, Ruihu,Wu, Zhicheng,Yang, Shuailong,Zhong, Hong
, (2020)
The chemical conversion of CO2 into value-added chemicals is one promising approach for CO2 utilization. It is crucial to explore highly efficient catalysts containing task-specific components for CO2 fixation. Here, a host-guest catalytic system was developed by integrating nitrogen-rich covalent organic framework (TT-COF) and imidazolium-based ionic polymer (ImIP), which serve as hydrogen-bonding donor and nucleophilic agent, respectively, for cooperatively facilitating the activation of the epoxides and subsequent CO2 cycloaddition. The catalytic activity of the host-guest system was remarkably superior to those of ImIP, TT-COF, and their physical mixture. Furthermore, selective adsorption for CO2 over N2 rendered this catalytic system effective for the cycloaddition reaction of the simulated flue gas. The protocols for the unification of two catalytically active components provide new opportunities for the development of composite systems in multiple applications.
Experimental and theoretical study for CO2 activation and chemical fixation with epoxides
Gao, Jinwei,Li, Liuyi,Cui, Caiyan,Ziaee, Muhammad Asad,Gong, Yaqiong,Sa, Rongjian,Zhong, Hong
, p. 13122 - 13127 (2019)
The synthesis of five-membered cyclic carbonates via catalytic cycloaddition reaction of CO2 with epoxides is considered to be an effective technology for alleviation of the energy crisis and global warming. Various commercial organic bases and ionic salts were used as catalysts, while the relationship of catalytic activity and compound structure has been seldom explored. Herein, a facilely obtained binary catalytic system based on triethylamine/NBu4Br was developed for CO2 activation and chemical fixation. The highly efficient catalytic system showed outstanding conversion and above 99% selectivity under metal-free mild reaction conditions (100 °C, 1 atm) in one hour. The detailed process of CO2 activation and chemical fixation was investigated at the molecular level by a series of experiments and theoretical calculation, which provided a mode for the design and synthesis of a highly efficient catalytic system for conversion of CO2 under mild conditions.
Synthesis of organic cyclic carbonates assisted by macroporous polystyrene-based catalyst
Chowdhury, B.,Davankov, V. A.,Lyubimov, S. E.,Pestrikova, A. A.,Tyutyunov, A. A.,Zvinchuk, A. A.
, p. 2345 - 2348 (2020)
An easy-to-prepare recyclable catalyst of quaternary ammonium nature and based on commercially available and inexpensive macroporous polymeric sorbent Purolite A103 resin has been devised for the carbon dioxide addition to epoxides. The catalyst can be ea
Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
Hu, Yuya,Wei, Zhihong,Frey, Anna,Kubis, Christoph,Ren, Chang-Yue,Spannenberg, Anke,Jiao, Haijun,Werner, Thomas
, p. 363 - 372 (2020/11/30)
A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea=39.6 kJ mol?1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol?1 for the bromide and 72 kJ mol?1 for the iodide salt, which explains the difference in activity.
Iodine as an efficient and available activator of sodium and potassium halides in carbon dioxide addition to epoxides
Chowdhury, B.,Lyubimov, S. E.,Zvinchuk, A. A.
, p. 1324 - 1327 (2021/08/10)
Sodium and potassium halides in combination with molecular iodine are efficient catalysts for the solvent-free addition of CO2 (10–56 atm) to epoxides giving organic carbonates.
