4437-69-8Relevant articles and documents
Chemical fixation of CO2 to cyclic carbonate catalyzed by new environmental- friendly bifunctional bis-Β-cyclodextrin derivatives
Peng, Jing,Wang, Sheng,Yang, Hai-Jian,Ban, Binru,Wei, Zidong,Wang, Lihua,Bo, Lei
, p. 76 - 84 (2019)
In present work, three amino-bridged biomass bis-β-cyclodextrins (bis-β-CDs) and eight bifunctionalized bis-β-CDs derivatives were designed and synthesized as environmental friendly catalysts to fix CO2. Both the bridged bis-β-CDs 1a-3a/potassium halide and haloalkane functionalized bis-β-CDs 1b-8b were poven to be efficient catalytic systems for the solvent-free coupling reaction of CO2 and epoxides. After systematic investigation, the optimized conditions of (120 °C, 4 MPa, 0.14mol% 1a, 1.25mol% KI, 2 h) have been established for dual catalytic system 1a/KI and the excellent yield (94%) with high selectivity (99%) can be achieved for the cycloaddition of CO2 and propylene oxide. Furthermore, after functionalization with alkyl halides, bis-β-CD derivative 1b-8b as sigle bifunctional catalyst exhibited better activity under milder optimal conditions of (110 °C, 2 MPa, 0.125mol% 1b and 4 h). Moreover, these bifunctional catalysts are also applicable to a variety of epoxides (including diepoxides) and good catalytic performances were abtained for producing the corresponding cyclic carbonates in most cases. Furthermore, this catalyst can be reused at least for five times without significant activity decrease. Finally, a possible mechanism including the activation of both epoxide and CO2 was proposed based on the literatures and experimental results.
Crosslinked Resin-Supported Bifunctional Organocatalyst for Conversion of CO2 into Cyclic Carbonates
Dong, Tongfeng,Li, Bo,Wu, Guang-Peng,Yang, Guan-Wen,Zhang, Yao-Yao,Zheng, Yu-Jia
, (2020)
The development of solvent-free, metal-free, recyclable organic catalysts is required for the current chemical fixation of carbon dioxide converted into cyclic carbonates. With the goal of reducing the cost, time, and energy consumption for the coupling reaction of CO2 and epoxides, a series of highly active heterogeneous catalysts, based on a thiourea and quaternary ammonium salt system, are synthesized by using a thiol-ene click reaction under ultraviolet light. Benefitting from synergistic interactions of the electrophilic center (thiourea) and the nucleophilic site (ammonium bromide), the catalysts exhibit excellent catalytic selectivity (99 %) for the cycloaddition of carbon dioxide with a diverse range of epoxides under mild conditions (1.2 MPa, 100 °C). Moreover, the catalyst can be easily recycled by facile filtration and reused for 5 times without noticeable loss of activity and selectivity. This work provides a potential heterogeneous catalyst for the conversion of carbon dioxide into high value-added chemicals with the combined advantages of low cost, easy recovery, and satisfactory catalytic properties.
Metal-Organic Frameworks with Tb4 Clusters as Nodes: Luminescent Detection of Chromium(VI) and Chemical Fixation of CO2
Dong, Jie,Xu, Hang,Hou, Sheng-Li,Wu, Zhi-Lei,Zhao, Bin
, p. 6244 - 6250 (2017)
Two multifunctional metal-organic frameworks based on cubane-like tetrahedron Tb4 clusters as nodes have been synthesized and characterized. Compound 1 exhibits a 2D lanthanide-organic framework with Tb4 clusters as nodes, and compound 2 possesses a 3D framework with Tb4 clusters and Mn2+ as nodes. Interestingly, luminescent investigations on them reveal that the two compounds can act as recyclable luminescent probes for chromium(VI) anion species and the corresponding detection limit can reach 10-7 mol/L. Furthermore, 1 and 2 own efficient catalytic activity for the chemical fixation of CO2 with epoxides under mild conditions. Importantly, they both can be recycled at least three times without compromising the activity.
Zeolitic Tetrazolate-Imidazolate Frameworks with SOD Topology for Room Temperature Fixation of CO2 to Cyclic Carbonates
Li, Min-Yu,Wang, Fei,Zhang, Jian
, p. 2866 - 2870 (2020)
Presented here is an SOD-type zeolitic tetrazolate-imidazolate framework (ZTIF-8) based on 5-methyltetrazole (5-Hmtz) and 2-methyimidazole (2-Hmim) ligands. Owing to the uncoordinated N-sites on the framework, ZTIF-8 has shown high chemical fixation of CO2 to cyclic carbonates at room temperature and ambient pressure.
New lanthanide(iii) coordination polymers: Synthesis, structural features, and catalytic activity in CO2 fixation
Xu, Cong,Liu, Yan,Wang, Li,Ma, Jingxin,Yang, Lizi,Pan, Fu-Xin,Kirillov, Alexander M.,Liu, Weisheng
, p. 16426 - 16431 (2017)
A new series of lanthanide coordination polymers formulated as [Ln(μ-L)(μ3-L)(H2O)]nXn (Ln/X = Er/Cl (1), Er/Br (2), Tm/Cl (3), Tm/Br (4), Yb/Cl (5), and Yb/Br (6); L = 1,3-bis(4-carboxyphenyl) imidazolium carboxylate(1+)) were solvothermally generated and fully characterized. Single-crystal X-ray diffraction analysis shows that all products possess isomorphous structures that are composed of cationic 1D double chains with encapsulated halide anions. From a topological perspective, such 1D chains can be classified as a binodal 3,5-connected net with a unique topology defined by the point symbol of (3·42)(32·42·53·62·7). All products 1-6 feature a remarkable thermal stability and were applied as highly active heterogeneous catalysts for the coupling reactions between halogenated propylene oxides and CO2 to give the corresponding cyclic carbonates. The reaction conditions, substrate and catalyst scope, and mechanistic features of this catalytic transformation were investigated. High products yields (up to 98%), elevated TONs (up to 3920) or TOFs (up to 326 h-1) were attained under mild reaction conditions. In addition, catalyst 6 can be recycled at least eight times with no loss of catalytic activity.
Robust multivariate metal-porphyrin frameworks for efficient ambient fixation of CO2 to cyclic carbonates
He, Liang,Nath, Jayanta Kumar,Lin, Qipu
, p. 412 - 415 (2019)
A family of multivariate metal-organic frameworks (MOFs) with three-kinds of orderly distributed metals were designed and successfully synthesized by combining metalloporphyrin sheets and pentafluoride (NbOF5)2? pillars. Benefiting from the cooperative nature of open-metal-sites (OMSs) within porphyrins, specific pore-sizes, coupled with fluorine-rich electrostatic environments, the fabricated materials demonstrated high affinity toward CO2, and good catalytic performance, structural robustness, and good recyclability for the conversion of epoxides and CO2 to cyclic carbonates at room temperature and 1 atm pressure.
Synthesis of carbonates from CO2 and epoxides catalyzed by the system of N-heterocyclic carbene, hydrogen bond donor, CrCl2, and tetrabutylammonium bromide
Zhang, Kuikui,Liu, Zhenbang,Liu, Ning
, (2021)
A three-component catalytic system including pyridine-bridged benzimidazolium salts, CrCl2, and tetrabutylammonium bromide (TBAB) was developed. Based on the control experiments and spectroscopic measurements, the role of the three components in the catalytic process was clarified, in which benzimidazolium salts were used as N-heterocyclic carbene precursor, a new Cr complex generating from the coordination of CrCl2 with pyridine nitrogen and pyrazole nitrogen bearing benzimidazolium salts was employed as hydrogen bond donor, TBAB was used as nucleophilic reagent, respectively. Under mild conditions (50°C and 1?bar CO2), the terminal epoxides displayed high reactivity in the three-component catalytic system. The catalytic system showed also high catalytic activity for the internal epoxides by increasing the temperature and CO2 pressure and/or prolonging the reaction time.
Aluminium based binary catalytic system for the solvent free conversion of CO2 to carbonates with high activity and selectivity
Ma, Ran,Sun, Haojie,Cui, Yuanzhi
, p. 11145 - 11149 (2018)
An easily prepared and low-cost aluminium based metal complex catalyst was prepared using kojic acid (Hkoj) as a ligand, and this developed oxo-coordinated Al(koj)3 complex showed high activity and selectivity for the CO2 fixation reaction with epoxides under mild conditions without any organic solvents. Various cyclic carbonates were obtained in excellent yields (up to 99%). This stable catalytically active Al(koj)3 has strong Lewis acidity for the activation of epoxides, and meanwhile the hydroxy group in Al(koj)3 may play a role in boosting the catalytic activity through possible hydrogen bonding interactions with the epoxide.
A Mechanochemical-Assisted Synthesis of Boron, Nitrogen Co-Doped Porous Carbons as Metal-Free Catalysts
Zhao, Li-Yuan,Dong, Xiao-Ling,Chen, Jun-Yue,Lu, An-Hui
, p. 2041 - 2050 (2020)
A green and convenient solid-state method assisted by mechanical energy is employed for the synthesis of boron (B) and nitrogen (N) co-doped porous carbons (B,N-Cs). Glutamic acid (Glu) and boric acid (H3BO3) are used as the N-containing carbon precursor and boron source, respectively. This method is easy to perform and proved to be efficient towards co-doping B and N into the carbon matrix with high contents of B (7 atom %) and N (10 atom %). By adjusting the molar ratio of H3BO3 to Glu, the surface chemical states of B and N could be readily modulated. When increasing H3BO3 dosage, the pore size of B,N-Cs could be tuned ranging from micropores to mesopores with a Brunauer–Emmett–Teller (BET) surface area up to 940 m2 g?1. Finally, the B,N-Cs were applied as metal-free catalysts for the cycloaddition of CO2 to epoxides, which outperform the N-doped carbon catalyst (NC-900) and the physically mixed catalyst of NC-900/B4C. The enhanced activity is attributed to the cooperative effect between B and N sites. X-ray photoelectron spectroscopy (XPS) analysis reveals that BN3 in the B,N-Cs serves as a critical active site for the cooperative catalysis.
Amino acids/superbases as eco-friendly catalyst system for the synthesis of cyclic carbonates under metal-free and halide-free conditions
Qi, Yaqiong,Cheng, Weiguo,Xu, Fei,Chen, Shengli,Zhang, Suojiang
, p. 876 - 886 (2018)
An eco-friendly and efficient binary catalyst system of superbases and amino acids was developed for the synthesis of cyclic carbonates from epoxides and CO2 under metal-free and halide-free conditions. Among the various amino acids and superbases systems tested, the L-histidine/1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) system achieved the highest conversion of propylene oxide and selectivity of propylene carbonate. The effect of various reaction parameters was evaluated. A possible catalyst mechanism for L-histidine synergized with DBU in the ring opening of epoxide and DBU introduced CO2 activation. The process herein represents a green, simple, and cost-effective route for the chemical fixation of CO2 into cyclic carbonates.
