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101.
To overcome the weak carbon dioxide (CO2) conversion ability of Zn‐Co double metal cyanide (DMC) catalyst, zinc glutarate (ZnGA) catalyst was introduced into the DMC catalytic system and applied for the synthesis of oligo (propylene‐carbonate) diols. The DMC/ZnGA composite catalyst (mass ratio = 10:1) exhibited an excellent synergistic effect which had enhanced CO2 activation ability, high yield and good selectivity. In copolymerization process, ZnGA catalyst not only provided activated CO2 for DMC catalyst, but also transferred the propagating chain with more alternating structures to DMC catalyst. Both of the two effects increased the carbonate content in the final products. Overall, DMC catalyst dedicated to the polymer chain growth, while the increased CO2 conversion mainly attributed to ZnGA catalyst. Oligo (propylene‐carbonate) diols with carbonate unit content of 45.1 mol%, Mn of 1228 g/mol, WPC of 4.3 wt% and high yield of 1689 g/g cat was obtained. 相似文献
102.
Sidra Jabeen Zhe Zeng Mohammednoor Altarawneh Xiangpeng Gao Anam Saeed Bogdan Z. Dlugogorski 《国际化学动力学杂志》2019,51(9):696-710
This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO2 and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH2 from α-carbon of leucine. The activation energies for direct elimination of CO2, NH3, and H2O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH3 over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase. 相似文献
103.
Lianghao Song Tiantian Xu Daowei Gao Prof. Xun Hu Prof. Cuncheng Li Prof. Shun Li Prof. Guozhu Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6621-6627
CeO2-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO2 and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO4 to synthesize CeO2−MnO2, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO2 crystallites under a high calcination temperature and, more importantly, intimate contact within CeO2/C is conveyed to CeO2/MnO2 after the interfacial reaction; this is responsible for the high catalytic activity of CeO2−MnO2 towards CO oxidation. 相似文献
104.
Ethan M. Cunningham Alexander S. Gentleman Peter W. Beardsmore 《Molecular physics》2019,117(21):2990-3000
ABSTRACTWe present the results of a combined experimental and computational study of the structures of gas-phase M+(N2O)n (M?=?Li, Al) complexes. Infrared spectra were recorded in the region of the N2O asymmetric (N?=?N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M+(N2O)n (M?=?Cu, Ag, Au and M?=?Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li+ complexes, there is, however, evidence for the presence of bound N2 moieties, indicating the presence of inserted, OLi+N2(N2O)n–type structures. The weak N2 band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al+(N2O)n complexes whose infrared spectra can be understood on the basis of molecularly-bound N2O ligands. The differences in M+(N2O)n structures observed for these closed–shell, ns2, metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. 相似文献
105.
Dr. Chao Zhao Dr. Louise Male Dr. Tzu-Yu Chen Joseph A. Barker Dr. Ian J. Shannon Dr. Paul A. Anderson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13865-13868
(NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K+ as an exemplar are studied in detail, and its unusual structure-reviving property reported. 相似文献
106.
Xin Cheng Dr. Zi-Yu Li Li-Hui Mou Yi Ren Dr. Qing-Yu Liu Prof. Dr. Xun-Lei Ding Prof. Dr. Sheng-Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16523-16527
The side-on-end-on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V5N5]−) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV). 相似文献
107.
A variety of heterobiaryl compounds have been synthesized by the Suzuki‐Miyaura coupling reactions of heteroaryl halides with potassium aryltrifluoroborates. Pd (OAc)2 was found to be highly efficient for the Suzuki‐Miyaura coupling reactions of various heteroaryl halides with potassium aryltrifluoroborates in aqueous systems, delivering the corresponding heterobiaryl compounds in good to excellent yields. 相似文献
108.
Three multinuclear Cu (II), Zn (II) and Cd (II) complexes, [Cu2(L)(μ‐OAc)]·CHCl2 ( 1 ), [Zn2(L)(μ‐OAc)(H2O)]·3CHCl3 ( 2 ) and [{Cd2(L)(OAc)(CH3CH2OH)}2]·2CH3CH2OH ( 3 ) with a single‐armed salamo‐like dioxime ligand H3L have been synthesized, and characterized by FT‐IR, UV–vis, X‐ray crystallography and Hirshfeld surfaces analyses. The ligand H3L has a linear structure and C‐H···π interactions between the two molecules. The complex 1 is a dinuclear Cu (II) complex, Cu1 and Cu2 are all five‐coordinate possessing distorted square pyramidal geometries. The complex 2 also forms a dinuclear Zn (II) structure, and Zn1 and Zn2 are all five‐coordinate bearing distorted trigonal bipyramidal geometries. The complex 3 is a symmetrical tetranuclear Cd (II) complex, and Cd1 is a hexa‐coordinate having octahedral configuration and Cd2 is hepta‐coordinate with a pentagonal bipyramidal geometry, and it has π···π interactions inside the molecule. In addition, fluorescence properties of the ligand and its complexes 1 – 3 have also been discussed. 相似文献
109.
110.
Viko Ladelta George Zapsas Yves Gnanou Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2450-2456
New tricrystalline triblock terpolymers, polyethylene‐block‐poly(ε‐caprolactone)‐block‐poly(L‐lactide) (PE‐b‐PCL‐b‐PLLA), were synthesized by ROP of ε‐caprolactone (CL) and L‐lactide (LLA) from linear ω‐hydroxyl polyethylene (PE‐OH) macroinitiators. The linear PE‐OH macroinitiators were prepared by C1 polymerization of methylsulfoxonium methylide (polyhomologation). Tin(II) 2‐ethylhexanoate was used as the catalyst for the sequential ROP of CL and LLA in one‐pot polymerization at 85 °C in toluene (PE‐OH macroinitiators are soluble in toluene at 80 °C). 1H NMR spectra confirmed the formation of PE‐b‐PCL‐b‐PLLA triblock terpolymers through the appearance of the characteristic proton peaks of each block. GPC traces showed the increase in the number average molecular weight from PE‐OH macroinitiator to PE‐b‐PCL, and PE‐b‐PCL‐b‐PLLA corroborating the successful synthesis. The existence of three crystalline blocks was proved by DSC and XRD spectroscopy. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2450–2456 相似文献