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41.
采用密度泛函理论的B3LYP, B3P86, B1B95, P3PW91和PBE1PBE方法结合SDD, LANL2DZ和CEP-121G基组计算了d~(10)组态二聚物MN(M=Ga, Ge, In, Sn和Sb; N=M和Al)的几何结构.采用B3P86/SDD进一步研究了MN@H_2O团簇的几何结构及吸附能.结果表明,水分子结合在二聚物M_2上时,对二聚物影响较大,对水分子自身影响较小.将M_2中Ga, Ge, In, Sn或Sb替换一个原子为Al时,水分子在GeAl和SnAl上的吸附能变化较大,而在GaAl, InAl和SbAl上吸附能变化较小.另外, H_2O吸附在Ga, Ge, In, Sn和Sb上时,与吸附在Al上时,吸附能的变化不大. 相似文献
42.
Nonlinear Dynamics - To better understand the dynamic behaviors of cable-stayed bridges, this study investigates the dynamic behaviors of a cable-stayed shallow arch subjected to two external... 相似文献
43.
Nonlinear Dynamics - Gaussian spatial soliton solutions of both the constant-coefficient and variable-coefficient (2 + 1)-dimensional nonlinear Schrödinger equations in... 相似文献
44.
45.
Dr. Yuan Liu Dr. Jin-Cheng Liu Teng-Hao Li Zeng-Hui Duan Dr. Tian-Yu Zhang Ming Yan Dr. Wan-Lu Li Prof. Dr. Hai Xiao Prof. Dr. Yang-Gang Wang Prof. Dr. Chun-Ran Chang Prof. Dr. Jun Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18745-18749
The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe1©SiC2), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH2 intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe1©SiO2 and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism. 相似文献
46.
Guangrui Chen Yuxing Yan Dr. Jie Wang Prof. Yong Sik Ok Guiyuan Zhong Prof. Bu Yuan Guan Prof. Yusuke Yamauchi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19831-19836
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献
47.
Dr. Ming-Hui Sun Prof. Dr. Li-Hua Chen Shen Yu Prof. Dr. Yu Li Xian-Gang Zhou Dr. Zhi-Yi Hu Prof. Dr. Yu-Han Sun Prof. Dr. Yan Xu Prof. Dr. Bao-Lian Su 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19750-19759
Zeolite Beta single crystals with intracrystalline hierarchical porosity at macro-, meso-, and micro-length scales can effectively overcome the diffusion limitations in the conversion of bulky molecules. However, the construction of large zeolite Beta single crystals with such porosity is a challenge. We report herein the synthesis of hierarchically ordered macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta) with a rare micron-scale crystal size by an in situ bottom-up confined zeolite crystallization strategy. The fully interconnected intracrystalline macro-meso-microporous hierarchy and the micron-sized single-crystalline nature of OMMS-Beta lead to improved accessibility to active sites and outstanding (hydro)thermal stability. Higher catalytic performances in gas-phase and liquid-phase acid-catalyzed reactions involving bulky molecules are obtained compared to commercial Beta and nanosized Beta zeolites. The strategy has been extended to the synthesis of other zeolitic materials, including ZSM-5, TS-1, and SAPO-34. 相似文献
48.
Dr. Yong-Sheng Wei Dr. Liming Sun Miao Wang Dr. Jinhua Hong Dr. Lianli Zou Hongwen Liu Dr. Yu Wang Dr. Mei Zhang Dr. Zheng Liu Prof. Yinwei Li Prof. Satoshi Horike Prof. Kazu Suenaga Prof. Qiang Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16147-16156
Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear FeIII2FeII complex (denoted as Fe3) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of FeII by other metal(II) ions (e.g., ZnII/CoII) via synthesizing isostructural trinuclear-complex precursors (Fe2Zn/Fe2Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities. 相似文献
49.
Dr. Si-Yong Qin Yan Jiang Dr. Han Sun Han Liu Prof. Ai-Qing Zhang Prof. Xinxiang Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17245-17251
Residual dipolar coupling (RDC), a robust anisotropic NMR parameter for structural elucidation of organic molecules, is only accessible in an anisotropic environment. Herein, we introduce a novel alignment medium based on the molecular self-assembly of oligopeptide amphiphile (OPA). This medium is compatible with different intermediate and polar solvent systems, such as CD3OD, [D6]DMSO, and D2O. The preparation of the OPA-based medium is simple and rapid, while only very weak background signals were observed from OPAs. Furthermore, we show that the purity of OPA has only a minor influence on the quality of the RDC data. These advantages allow RDC measurements of organic molecules with different polarities and solubilities with high efficiency and accuracy. 相似文献
50.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献