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91.
以过渡金属为催化衬底的化学气相沉积法(Chemical Vapor Deposition,CVD)已经可以制备与机械剥离样品相媲美的石墨烯,是实现石墨烯工业应用的关键技术之一。原子尺度理论研究能够帮助我们深刻理解石墨烯生长机理,为实验现象提供合理的解释,并有可能成为将来实验设计的理论指导。本文从理论计算的角度,总结了各种金属衬底在石墨烯CVD生长过程中的各种作用与相应的机理,包括在催化碳源裂解、降低石墨烯成核密度等,催化加快石墨烯快速生长,修复石墨烯生长过程中产生的缺陷,控制外延生长石墨烯的晶格取向,以及在降温过程中石墨烯褶皱与金属表面台阶束的形成过程等。在本文最后,我们对当前石墨烯生长领域中亟需解决的理论问题进行了深入探讨与展望。 相似文献
92.
Steven M. Swick Tim Gebraad Dr. Leighton Jones Dr. Bo Fu Dr. Thomas J. Aldrich Prof. Kevin L. Kohlstedt Prof. George C. Schatz Prof. Antonio Facchetti Prof. Tobin J. Marks 《Chemphyschem》2019,20(20):2608-2626
Accurate single-crystal X-ray diffraction data offer a unique opportunity to compare and contrast the atomistic details of bulk heterojunction photovoltaic small-molecule acceptor structure and packing, as well as provide an essential starting point for computational electronic structure and charge transport analysis. Herein, we report diffraction-derived crystal structures and computational analyses on the n-type semiconductors which enable some of the highest efficiency organic solar cells produced to date, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC ) and seven derivatives (including three new crystal structures: 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-propylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C3 ), 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( m -ITIC-C6 ), and 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-butylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C4-4F ). IDTT acceptors typically pack in a face-to-face fashion with π–π distances ranging from 3.28–3.95 Å. Additionally, edge-to-face packing is observed with S⋯π interactions as short as 3.21–3.24 Å. Moreover, ITIC end group identities and side chain substituents influence the nature and strength of noncovalent interactions (e. g. H-bonding, π–π) and thus correlate with the observed packing motif, electronic structure, and charge transport properties of the crystals. Density functional theory (DFT) calculations reveal relatively large nearest-neighbor intermolecular π-π electronic couplings (5.85–56.8 meV) and correlate the nature of the band structure with the dispersion interactions in the single crystals and core–end group polarization effects. Overall, this combined experimental and theoretical work reveals key insights into crystal engineering strategies for indacenodithienothiophene (IDTT) acceptors, as well as general design rules for high-efficiency post-fullerene small molecule acceptors. 相似文献
93.
Aycha Jellali Slim Elleuch Besma Hamdi Ridha Zouari 《Journal of Saudi Chemical Society》2019,23(5):600-611
In this work, a new hybrid material (C5H6N2Cl)2[FeCl4].Cl abbreviated (CAP)2[FeCl4].Cl was prepared using room temperature slow evaporation technique. The X-ray diffraction analysis revealed that the compound is crystallized in the centrosymmetric space group P21/c of the monoclinic system. The crystallographic network consists of an Fe(III) ion located on an inversion center and coordinated by four chlorine, isolated Cl– and two (CAP)+ protonated cations linked by N–H...Cl and C–H...Cl hydrogen bonds to form a zero-dimensional network. Hirshfeld surface analysis was used to analyze intermolecular interactions present in the crystal structure. The vibrational properties were inspected by means of Infra-Red absorption and Raman diffusion spectroscopy techniques. In addition, theoretical calculations based on the DFT/B3LYP/LanL2DZ method and the time-dependent density functional theory (TD–DFT) were performed in order to gain more information and help in the examination of over-all properties of the title compound. Good and interesting experimental findings were presented and good consistency was found with the calculated results. 相似文献
94.
Dr. Yao-Yao Wang Dr. Hong-Hong Fan Zhi-Wei Wang Wan-Yue Diao Dr. Chao-Ying Fan Prof. Xing-Long Wu Prof. Jing-Ping Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(66):15173-15181
Owing to low ion/electron conductivity and large volume change, transitional metal dichalcogenides (TMDs) suffer from inferior cycle stability and rate capability when used as the anode of lithium-ion batteries (LIBs). To overcome these disadvantages, amorphous molybdenum sulfide (MoSx) nanospheres were prepared and coated with an ultrathin carbon layer through a simple one-pot reaction. Combining X-ray photoelectron spectroscopy (XPS) with theoretical calculations, MoSx was confirmed as having a special chain molecular structure with two forms of S bonding (S2− and S22−), the optimal adsorption sites of Li+ were located at S22−. As a result, the MoSx electrode exhibits superior cycle and rate capacities compared with crystalline 2H-MoS2 (e.g., delivering a high capacity of 612.4 mAh g−1 after 500 cycles at 1 A g−1). This is mainly attributed to more exposed active S22− sites for Li storage, more Li+ transfer pathways for improved ion conductivity, and suppressed electrode structure pulverization of MoSx derived from the inherent chain-like molecular structure. Quantitative charge storage analysis further demonstrates the improved pseudocapacitive contribution of amorphous MoSx induced by fast reaction kinetics. Moreover, the morphology contrast after cycling demonstrates the dispersion of active materials is more uniform for MoSx than 2H-MoS2, suggesting the MoSx can well accommodate the volume stress of the electrode during discharging. Through regulating the molecular structure, this work provides an effective targeted strategy to overcome the intrinsic issues of TMDs for high-performance LIBs. 相似文献
95.
Dr. Yago García-Rodeja Prof. Dr. Israel Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9771-9779
The influence of the replacement of C=C bonds by isoelectronic B−N moieties on the reactivity of π-curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels–Alder cycloaddition reactions of the parent corannulene and its BN-doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN-hemifullerene, BN-circumtrindene, and BN-fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN-curved systems cannot be used as dienes in Diels–Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state-of-the-art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations. 相似文献
96.
Rajan Kumar Subir Kumar Ray Dr. Saikat Mukherjee Sudipta Saha Dr. Arijit Bag Prof. Dr. Pradip Kr. Ghorai Prof. Dr. Nirmalya Ghosh Prof. Dr. Raja Shunmugam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(59):13514-13522
The development of organic photoluminescent materials, which show promising roles as catalysts, sensors, organic light-emitting diodes, logic gates, etc., is a major demand and challenge for the global scientific community. In this context, a photoclick polymerization method is adopted for the growth of a unique photoluminescent three-dimensional (3D) polymer film, E, as a model system that shows emission tunability over the range 350–650 nm against the excitation range 295–425 nm. The DFT analysis of energy calculations and π-stacking supports the spectroscopic observations for the material exhibiting a broad range of emission owing to newly formed chromophoric units within the film. Full polarization spectroscopic Mueller matrix studies were employed to extract and quantify the molecular orientational order of both the ground (excitation) and excited (emission) state anisotropies through a set of newly defined parameters, namely the fluorescence diattenuation and fluorescence polarizance. The information contained in the recorded fluorescence Mueller matrix of the organic polymer material provided a useful way to control the spectral intensity of emission by using pre- and post-selection of polarization states. The observation was based on the assumption that the longer lifetime of the excited dipolar orientation is attributed to the compactness of the film. 相似文献
97.
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
98.
99.
Stevo Stevi Bratislav Iri
anin Witold Kosmala Zdenk marda 《Mathematical Methods in the Applied Sciences》2019,42(5):1687-1701
Some formulas for well‐defined solutions to four very special cases of a nonlinear fifth‐order difference equation have been presented recently in this journal, where some of them were proved by the method of induction, some are only quoted, and no any theory behind the formulas was given. Here, we show in an elegant constructive way how the general solution to the difference equation can be obtained, from which the special cases very easily follow, which is also demonstrated here. We also give some comments on the local stability results on the special cases of the nonlinear fifth‐order difference equation previously publish in this journal. 相似文献
100.
Roser Pons Cristina Ibez Ana B. Buades Antonio Franconetti Angel Garcia‐Raso Juan J. Fiol Angel Terrn Elies Molins Antonio Frontera 《应用有机金属化学》2019,33(6)
We report the synthesis and X‐ray characterization of the N6‐benzyl‐N6‐methyladenine ligand (L) and three metal complexes, namely [Zn(HL)Cl3]·H2O ( 1 ), [Cd(HL)2Cl4] ( 2 ) and [H2L]2[Cd3(μ‐L)2(μ‐Cl)4Cl6]·3H2O ( 3 ). Complex 1 consists of the 7H‐adenine tautomer protonated at N3 and coordinated to a tetrahedral Zn(II) metal centre through N9. The octahedral Cd(II) in complex 2 is N9‐coordinated to two N6‐benzyl‐N6‐methyladeninium ligands (7H‐tautomer protonated at N3) that occupy apical positions and four chlorido ligands form the basal plane. Compound 3 corresponds to a trinuclear Cd(II) complex, where the central Cd atom is six‐coordinated to two bridging μ‐L and four bridging μ‐Cl ligands. The other two Cd atoms are six‐coordinated to three terminal chlorido ligands, to two bridging μ‐Cl ligands and to the bridging μ‐L through N3. Essentially, the coordination patterns, degree of protonation and tautomeric forms of the nucleobase dominate the solid‐state architectures of 1 – 3 . Additionally, the hydrogen‐bonding interactions produced by the endocyclic N atoms and NH groups stabilize high‐dimensional‐order supramolecular assemblies. Moreover, energetically strong anion–π and lone pair (lp)–π interactions are important in constructing the final solid‐state architectures in 1 – 3 . We have studied the non‐covalent interactions energetically using density functional theory calculations and rationalized the interactions using molecular electrostatic potential surfaces and Bader's theory of atoms in molecules. We have particularly analysed cooperative lp–π and anion–π interactions in 1 and π+–π+ interactions in 3 . 相似文献