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1.
The concise synthesis of sulfur-enriched graphene for battery applications is reported. The direct treatment of graphene oxide (GO) with the commercially available Lawesson's reagent produced sulfur-enriched-reduced GO (S-rGO). Various techniques, such as X-ray photoelectron spectroscopy (XPS), confirmed the occurrence of both sulfur functionalization and GO reduction. Also fabricated was a nanohybrid material by using S-rGO with polyoxometalate (POM) as a cathode-active material for a rechargeable battery. Transmission electron microscopy (TEM) revealed that POM clusters were individually immobilized on the S-rGO surface. This battery, based on a POM/S-rGO complex, exhibited greater cycling stability for the charge-discharge process than a battery with nanohybrid materials positioned between the POM and nonenriched rGO. These results demonstrate that the use of sulfur-containing groups on a graphene surface can be extended to applications such as the catalysis of electrochemical reactions and electrodes in other battery systems.  相似文献   

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The first systematic access to molecular cerium vanadium oxides is presented. A family of structurally related, di‐cerium‐functionalized vanadium oxide clusters and their use as visible‐light‐driven photooxidation catalysts is reported. Comparative analyses show that photocatalytic activity is controlled by the cluster architecture. Increased photoreactivity of the cerium vanadium oxides in the visible range compared with nonfunctionalized vanadates is observed. Based on the recent discovery of the first molecular cerium vanadate cluster, (nBu4N)2[(Ce(dmso)3)2V12O33Cl] ? 2 DMSO ( 1 ), two new di‐cerium‐containing vanadium oxide clusters [(Ce(dmso)4)2V11O30Cl] ? DMSO ( 2 ) and [(Ce(nmp)4)2V12O32Cl] ? NMP ? Me2CO ( 3 ; NMP=N‐methyl‐2‐pyrrolidone) were obtained by using a novel fragmentation and reassembly route. Pentagonal building units {(V)M5} (M=V, Ce) reminiscent of “Müller‐type” pentagons are observed in 2 and 3 . Compounds 1 – 3 feature high visible‐light photooxidative activity, and quantum efficiencies >10 % for indigo photooxidation are observed. Photocatalytic performance increases in the order 1 < 3 < 2 . Mechanistic studies show that the irradiation wavelength and the presence of oxygen strongly affect photoreactivity. Initial findings suggest that the photooxidation mechanism proceeds by intermediate formation of hydroxyl radicals. The findings open new avenues for the bottom‐up design of sunlight‐driven photocatalysts.  相似文献   

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Under hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed‐valent Mn6 sandwiched silicotungstate [(B‐α‐SiW9O34)2MnIII4MnII2O4(H2O)4]12? ( 1 a ) with organic N ligands led to the isolation of five organic–inorganic hybrid, Mn6‐substituted polyoxometalates (POMs) 2 – 6 . They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse‐reflectance spectroscopy, and powder and single‐crystal X‐ray diffraction. Compounds 2 – 6 represent the first series of mixed‐valent {MnIII4MnII2O4(H2O)4?n(L)n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1 – 6 not only indicates that the double‐cubane {MnIII4MnII2O4(H2O)4?n(L)n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed‐valent POMs substituted with transition‐metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single‐molecule magnet behavior.  相似文献   

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《化学:亚洲杂志》2017,12(20):2763-2769
A series of seven new complexes including silver‐thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag2C2 using a C22− pre‐templated approach. Herein, two prototype clusters Ag14(SR)6 and CO3@Agm (SR)10 (R=isopropyl, cyclohexyl or tert ‐butyl; m= 18 or 20) are employed to construct cluster‐based metal–organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag14(S‐i Pr)6(CO2CF3)8⋅(DMSO)6 (two polymorphic forms 1 , 2 ) and [Ag14(S‐Cy)6(CO2CF3)8(DMSO)4]⋅(DMSO)3 ( 3 ), and a cluster‐based metal–organic framework {Ag3[Ag14(S‐i Pr)6(CO2CF3)11(H2O)3CH3OH]⋅(H2O)2.5}n ( 4 ) have been isolated and structurally characterized. Furthermore, increased acidity of the reaction mixture afforded three carboxylate‐templated cluster based frameworks: a chain‐like compound {[HN(CH3)2CO]⋅[CO3@Ag18(S‐t Bu)10(NO3)7(DMF)4]⋅DMF}n ( 5 ), as well as two layer‐type compounds, namely, {Ag[CO3@Ag20(S‐i Pr)10(CO2CF3)9(CO2HCF3)(CH3OH)2]}n ( 6 ) and {Ag2[CO3@Ag20(S‐Cy)10(CO2CF3)10(CO2HCF3)2(H2O)2]⋅(H2O)3⋅(CH3OH)3}n ( 7 ) exhibiting sql ‐net characteristics. It is demonstrated that the C≡C2− pre‐template, which draws several Ag+ ions together to form the C2@Agn entity, plays an indispensable role in the syntheses of these compounds. Furthermore, covalent linkage of these nano‐sized silver thiolate clusters from one‐ to three‐dimensions revealed enormous potential for the future development of silver cluster‐based frameworks.  相似文献   

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Crystallization of [Ag14(C?CtBu)12Cl][BF4] and different polyoxometalates in organic solvents yields a series of new intercluster compounds: [Ag14(C?CtBu)12Cl(CH3CN)]2[W6O19] ( 1 ), (nBu4N)[Ag14(C?CtBu)12Cl(CH3CN)]2[PW12O40] ( 2 ), and [Ag14(C?CtBu)12Cl]2[Ag14(C?CtBu)12Cl(CH3CN)]2[SiMo12O40] ( 3 ). Applying the same technique to a system starting from polymeric {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n and the polyoxometalate (nBu4N)2[W6O19] results in the formation of [Ag14(C?CtBu)12(CH3CN)2][W6O19] ( 4 ). Here, the Ag14 cluster is generated from polymeric {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n during crystallization. In a similar way, [Ag15(C?CtBu)12(CH3CN)5][PW12O40] ( 5 ) has been obtained from {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n and (nBu4N)3[PW12O40]. The use of charged building blocks was intentional, because at these conditions the contribution of long‐range Coulomb interactions would benefit most from full periodicity of the intercluster compound, thus favoring formation of well‐crystalline materials. The latter has been achieved, indeed. However, as a most conspicuous feature, equally charged species aggregate, which demonstrates that the short‐range interactions between the “surfaces” of the clusters represent the more powerful structure direction forces than the long‐range Coulomb bonding. This observation is of significant importance for understanding the mechanisms underlying self‐organization of monodisperse and structurally well‐defined particles of nanometer size.  相似文献   

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The direct microwave‐mediated condensation between 3‐oxetanone and primary amides and thioamides has delivered moderate to good yields of (hydroxymethyl)oxazoles and (hydroxymethyl)thiazoles. The reactions use a sustainable solvent and only require short reaction times. These are highly competitive methods for the construction of two classes of valuable heteroarenes, which bear a useful locus for further elaboration. Electronic structure calculations have shown that the order of events involves chalcogen atom attack at sp3 carbon and alkyl–oxygen cleavage. The critical role of acid catalysis was shown clearly, and the importance of acid strength was demonstrated. The calculated barriers were also fully consistent with the observed order of thioamide and amide reactivity. Spontaneous ring opening involves a modest degree of C? O cleavage, moderating the extent of strain relief. On the acid‐catalysed pathway, C? O cleavage is less extensive still, but proton transfer to the nucleofuge is well advanced with the carboxylic acid catalysts, and essentially complete with methanesulfonic acid.  相似文献   

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The simultaneous polymer functionalization and exfoliation of graphene sheets by using mild bath sonication and heat treatment at low temperature is described. In particular, free‐radical polymerization of three different vinyl monomers takes place in the presence of graphite flakes. The polymerization procedure leads to the exfoliation of graphene sheets and at the same time the growing polymer chains are attached onto the graphene lattice, which gives solubility and stability to the final graphene‐based hybrid material. The polymer‐functionalized graphene sheets possess fewer defects as compared with previously reported polymer‐functionalized graphene. The success of the covalent functionalization and exfoliation of graphene was confirmed by using a variety of complementary spectroscopic, thermal, and microscopy techniques, including Raman, IR and UV/Vis spectroscopy, thermogravimetric analysis, and transmission electron microscopy.  相似文献   

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A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8]17? heterometallic anions ( Ln3M2 ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce3Co2 derivative.  相似文献   

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We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}‐in‐{W76} cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO32?, Cl?, and Ag+ play in the self‐assembly of compounds 1 – 3 .  相似文献   

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The integration of 2D covalent organic frameworks (COFs) with atomic thickness with graphene will lead to intriguing two‐dimensional materials. A surface‐confined covalently bonded Schiff base network was prepared on single‐layer graphene grown on copper foil and the dynamic reaction process was investigated with scanning tunneling microscopy. DFT simulations provide an understanding of the electronic structures and the interactions between the surface COF and graphene. Strong coupling between the surface COF and graphene was confirmed by the dispersive bands of the surface COF after interaction with graphene, and also by the experimental observation of tunneling condition dependent contrast of the surface COF.  相似文献   

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Heteroatom‐doped carbon materials have been extensively investigated as metal‐free electrocatalysts to replace commercial Pt/C catalysts in oxygen reduction reactions in fuel cells and Li–air batteries. However, the synthesis of such materials usually involves high temperature or complicated equipment. Graphene‐based sulfur composites have been recently developed to prolong the cycling life of Li–S batteries, one of the most attractive energy‐storage devices. Given the high cost of graphene, there is significant demand to recycle and reuse graphene from Li–S batteries. Herein, we report a green and cost‐effective method to prepare sulfur‐doped graphene, achieved by the continuous charge/discharge cycling of graphene–sulfur composites in Li–S batteries. This material was used as a metal‐free electrocatalyst for the oxygen reduction reaction and shows better electrocatalytic activity than pristine graphene and better methanol tolerance durability than Pt/C.  相似文献   

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石墨烯的制备、功能化及在化学中的应用   总被引:11,自引:0,他引:11  
石墨烯是最近发现的一种具有二维平面结构的碳纳米材料,它的特殊单原子层结构使其具有许多独特的物理化学性质.有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一.本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述,重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展,并对石墨烯在相关领域的应用前景作了展望.  相似文献   

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