949-97-3Relevant articles and documents
A Calix[4]resorcinarene-Based [Co12] Coordination Cage for Highly Efficient Cycloaddition of CO2 to Epoxides
Guo, Ting-Ting,Su, Xiao-Fang,Xu, Xianxiu,Yang, Jin,Yan, Li-Kai,Ma, Jian-Fang
, p. 16518 - 16523 (2019)
The design and synthesis of polynuclear metal cluster-based coordination cages is of considerable interest due to their appealing structural characteristics and potential applications. Herein, we report a calix[4]resorcinarene-based [Co12] coordination cage, [Co12(TPC4R-I)2(1,3-BDC)10(μ3-OH)4(H2O)10(DMF)2]·7DMF·23H2O (1), assembled with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3-benzenedicarboxylates (1,3-BDC), and 12 Co(II) cations. Remarkably, it is shown to be a highly efficient recyclable heterogeneous catalyst for CO2 conversion due to its exposed Co(II) Lewis acid sites.
A Porphyrin-Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO2to Epoxides
Jiang, Wei,Yang, Jin,Liu, Ying-Ying,Song, Shu-Yan,Ma, Jian-Fang
, p. 16991 - 16997 (2016)
A porous rtl metal–organic framework (MOF) [Mn5L(H2O)6?(DMA)2]?5DMA?4C2H5OH (1?Mn) (H10L=5,10,15,20-tetra(4-(3,5-dicarboxylphenoxy)phenyl)porphyrin; DMA=N,N′-dimethylacetamide) was synthesized by employing a new porphyrin-based octacarboxylic acid ligand. 1?Mn exhibits high MnIIdensity in the porous framework, providing it great Lewis-acid heterogeneous catalytic capability for the cycloaddition of CO2with epoxides. Strikingly, 1?Mn features excellent catalytic activity to the cycloaddition of CO2to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As-synthesized 1?Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO2make 1?Mn a promising heterogeneous catalyst for fixation and utilization of CO2.
Shape-persistent octanuclear zinc salen clusters: Synthesis, characterization, and catalysis
Haak, Robert M.,Decortes, Antonello,Escudero-Adan, Eduardo C.,Belmonte, Marta Martinez,Martin, Eddy,Benet-Buchholz, Jordi,Kleij, Arjan W.
, p. 7934 - 7936 (2011)
We describe a selective and template-controlled synthesis of a series of Zn8 metal complexes based on a bis-nucleating salen ligand scaffold. Our results, a combination of X-ray analysis and solution studies, show that discrete, shape-persistent metal clusters can be prepared in high yield. Their activity in organic carbonate catalysis is a function of the metal-connecting fragment present in the exterior of the cluster complex. The high stability of the clusters has been confirmed by 1H, 13C (DEPTQ) and DOSY NMR, gel permeation chromatography, high-performance liquid chromatography, and mass spectrometry.
In situcleavage and rearrangement synthesis of an easy-to-obtain and highly stable Cu(ii)-based MOF for efficient heterogeneous catalysis of carbon dioxide conversion
Qin, Lan,Pan, Yu,Yu, Lei,Huai, Ranran,Yang, Lu,Dou, Yong,Zhou, Zhen
, p. 6307 - 6314 (2021)
Cycloaddition of carbon dioxide (CO2) with epoxides into cyclic carbonates has been attracted substantial attentions for metal-organic frameworks based catalysis of CO2chemical fixation, not only due to the contributions that solving the environmental issue of the excessive emission CO2, but also providing an effective pathway for the production of value-added fine chemicals. Herein, a Cu(ii)-based metal-organic framework (1) was synthesized by thein situcleavage and rearrangement of theN,N′-bis(4-picolinoyl)hydrazine ligand into an isonicotinate (INA) moiety as a connected nodeviasolvothermal synthesis in high yields. This three-dimensional framework possesses infinite one-dimensional Cu-O double chains in a ladder-like arrangement with exposed metal centres, and can be highly stable up to at least 240 °C and in various solvents. Gas adsorption experiments reveal the good adsorption ability of1towards CO2with a high value ofQst. Cycloaddition of CO2with epoxides could successfully occur by using1as an efficient heterogeneous catalyst, affording almost complete conversion and selectivity under solvent free conditions.
High Uptake of ReO4? and CO2 Conversion by a Radiation-Resistant Thorium–Nickle [Th48Ni6] Nanocage-Based Metal–Organic Framework
Xu, Hang,Cao, Chun-Shuai,Hu, Han-Shi,Wang, Shi-Bin,Liu, Jin-Cheng,Cheng, Peng,Kaltsoyannis, Nikolas,Li, Jun,Zhao, Bin
, p. 6022 - 6027 (2019)
Assembled from [Th48Ni6] nanocages, the first transition-metal (TM)-thorium metal–organic framework (MOF, 1) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO4? (an analogue of radioactive 99TcO4?, a key species in nuclear wastes) with a maximum capacity of 807 mg g?1, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO2 fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus-independent chemical shifts and natural bond orbital analysis reveal that the [Th6O8] clusters in 1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising 1′s stability.
Highly efficient CO2 fixation into cyclic carbonate by hydroxyl-functionalized protic ionic liquids at atmospheric pressure
Chen, Peng,Chen, Teng,Gu, Jiarui,Li, Cheng,Liu, Fei,Zhao, Tianxiang
, (2021)
We report an efficient strategy for CO2 fixation into cyclic carbonates catalyzed by hydroxyl-functionalized protic ionic liquids (PILs) without any solvent and additive. Excellent yields of cyclic carbonates are obtained for the varied substrates under mild conditions (1 bar and 60°C). Mechanism studies have shown that hydroxyl promoted the activation of epoxide molecules through hydrogen bonding interaction, so that CO2 can be easily converted into the desired product of cyclic carbonates. In addition, the hydroxyl-functionalized PILs can also be recycled repeatedly. This hydroxyl-functionalized PILs-catalyzed process is proved to be a promising scheme for the chemical conversion of CO2.
Method for preparing cyclic carbonate by immobilizing CO2 under catalysis of organic boric acid
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Paragraph 0137-0142, (2021/06/22)
The invention discloses a synthesis method for synergistically catalyzing carbon dioxide immobilization through weak Lewis acid phenylboronic acid and tetrabutylammonium bromide. According to the method, CO2 is immobilized by epoxide, and a cyclic carbonate product is generated. The method comprises the following step: under the concerted catalysis of phenylboronic acid and tetrabutylammonium bromide, performing reaction on epoxide as shown in a formula IV, a formula V or a formula VI and carbon dioxide to respectively obtain a cyclic carbonate product as shown in a formula I, a formula II or a formula III. According to the method, raw materials are convenient and easy to obtain, reaction conditions are mild, operation is easy and convenient, and the yield can reach 97%.
High yield room temperature conversion of carbon dioxide into cyclic carbonates catalyzed by mixed metal oxide (CuO-ZnO) nano-flakes/micro-flakes (Cozi-nmf)
Velpuri, Venkateswara Rao,Muralidharan, Krishnamurthi
, (2021/03/06)
Capturing and converting carbon dioxide (CO2) into useful organic molecules and polymers is the best way of alleviating excessive release of it from industrial sources to the environment. Cyclic carbonate synthesis by cycloaddition from CO
