The alloying-induced electrical conductivity of metal-chalcogenolate nanowires.

Alloying is one of the most effective strategies to change the properties of inorganic-organic hybrid materials, but there are few reports of the alloying of one-dimensional nanowires with precise atomic structure due to the difficulties in obtaining the single crystals of nanowires themselves. Herein, we describe the synthesis and characterization of an alloyed one-dimensional Ag-Cu nanowire [Ag2.5Cu1.5(S-Adm)4]n. Compared with the unalloyed [Ag4(S-Adm)4]n, our novel alloyed nanowire exhibits good conductivity, and its resistivity (as a powder) was determined to be 107 Ω m by impedance analysis-consistent with that of a semiconductor. Accordingly, based on these properties combined with its excellent thermal stability and high-yielding, gram-scale synthesis, [Ag2.5Cu1.5(S-Adm)4]n is proposed for electronic-device applications.

[Au7(SR)7] Ring as a New Type of Protection Ligand in a New Atomic Structure of Au15(SR)13 Nanocluster.

We present a [Au7(SR)7] ring as a new type of protection ligand in a new atomic structure of Au15(SR)13 nanocluster for the first time based on the ring model developed to understand how interfacial interaction dictates the structures of protection motifs and gold cores in thiolate-protected gold nanoclusters. This new Au15(SR)13 model shows a tetrahedral Au4 core protected by one [Au7(SR)7] ring and two [Au2(SR)3] "staple" motifs. Density functional theory (DFT) calculations show that the newly predicted Au15(SR)13 (R = CH3/Ph) has a lower energy of 0.24/0.68 eV than previously proposed isomers. By comparing calculated optical absorption spectra (UV), circular dichroism (CD) spectra, and powder X-ray diffraction (XRD) patterns with related experimental spectra, the calculated CD spectra of the newly predicted Au15(SR)13 (R = CH3/Ph) cannot reproduce the experimental results, indicating that the newly predicted Au15(SR)13 is a new structure that needs to be confirmed by experiment. In addition, DFT calculations also show that the newly predicted Au15(SR)13 (R = CH3/Ph) exhibits a large HOMO-LUMO gap, suggesting its high chemical stability. The proposition of the [Au7(SR)7] ring as a protection ligand in the newly predicted Au15(SR)13 not only enriches the types of protection ligands in thiolate-protected gold nanoclusters but also further confirms the effectiveness and rationality of the ring model for understanding the interfacial interaction between the protection motifs and gold cores in thiolate-protected gold nanoclusters.

Unraveling the Atomic Structures of 10-Electron (10e) Thiolate-Protected Gold Nanoclusters: Three Au32(SR)22 Isomers, One Au28(SR)18, and One Au33(SR)23.

The atomic structures of 10-electron (10e) thiolate-protected gold nanoclusters have not received extensive attention both experimentally and theoretically. In this paper, five new atomic structures of 10e thiolate-protected gold nanoclusters, including three Au32(SR)22 isomers, one Au28(SR)18, and one Au33(SR)23, are theoretically predicted. Based on grand unified model (GUM), four Au17 cores with different morphologies can be obtained via three different packing modes of five tetrahedral Au4 units. Then, five complete structures of three Au32(SR)22 isomers, one Au28(SR)18, and one Au33(SR)23 isomers can be formed by adding the thiolate ligands to three Au17 cores based on the interfacial interaction between thiolate ligands and gold core in known gold nanoclusters. Density functional theory calculations show that the relative energies of three newly predicted Au32(SR)22 isomers are quite close to two previously reported isomers. In addition, five new 10e gold nanoclusters have large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps and all-positive harmonic vibration frequencies, indicating their high stabilities.

Ring Model for Understanding How Interfacial Interaction Dictates the Structures of Protection Motifs and Gold Cores in Thiolate-Protected Gold Nanoclusters.

Understanding the effect of interfacial interactions between the protection motifs and gold cores on the stabilities of thiolate-protected gold nanoclusters is still a challenging task. Based on analyses of 95 experimentally crystallized and theoretically predicted thiolate-protected gold nanoclusters, we present a ring model to offer a deeper insight into the interfacial interactions for this class of nanoclusters. In the ring model, all the gold nanoclusters can be generically viewed as a fusion or interlocking of several [Aum(SR)n] (m = 4-8, 10, and 12 and 0 ≤ n ≤ m) rings. Guided by the ring model and the grand unified model, a new Au42(SR)26 isomer is predicted, whose total energy is lower than those of two previously crystallized isomers. The ring model offers a mechanistic understanding of the interactions between the protection ligands and gold cores and practical guidance on predicting new gold nanoclusters for future experimental synthesis and confirmation.

Synthesis of Ethylenediaminetetraacetic Acid Disodium Salt Functionalized Magnetite/Chitosan Nanospheres for the Highly Efficient Removal of Methylene Blue.

In this paper, novel Ethylenediaminetetraacetic acid disodium salt (EDTA) functionalized magnetite/ chitosan nanospheres (Fe3O4/CS-EDTA) are synthesized by combining solvothermal method and chemical modification, and they are further applied as a kind of adsorbent to eliminate dye of methylene blue (MB) from wastewater. The properties as well as structure exhibited by the fabricated adsorbent are characterized through FTIR, XRD, TG and TEM, together with VSM. The impact exerted by sorption parameters (time of contact, initial dye concentration, temperature, etc.) on the adsorptions were evaluated in batch system. These results demonstrated that our magnetic materials held the adsorption capacity for MB of 256 mg g-1 (pH = 11), and the kinetic model of pseudo-second-order and the Langmuir model could make an effective simulation regarding the adsorption kinetics and isotherm, respectively. Besides, the external magnetic field can assist in easily separating dye adsorbed Fe3O4/CS-EDTA from solution for regeneration. The removal efficiency of recycled adsorbents remained above 92% in the 5th adsorption/desorption cycle. These superioritiesmake Fe3O4/CS-EDTA a high-efficientmultifunctional adsorbent for removing dyes from wastewater.

Two-dimensional growth mode of thiolate-protected gold nanoclusters Au28+4n(SR)20+2n (n = 0-8): compared with their one-dimensional growth mode.

In this paper, six new atomic structures of thiolate-protected gold nanoclusters, i.e. Au32(SR)20, Au40(SR)26, Au48(SR)30, two Au56(SR)34, and Au60(SR)36, are predicted. Considering these six newly predicted structures and six previously predicted or crystallized Au28(SR)20, Au36(SR)24, Au44(SR)28, Au52(SR)32, and Au60(SR)36 altogether, the two-dimensional (2D) growth mode of Au28+4n(SR)20+2n (n = 0-8) nanoclusters is completely presented to compare with their one-dimensional (1D) growth mode. In Au28+4n(SR)20+2n (n = 0-8) nanoclusters with both 1D and 2D growth modes, the same number of gold-core atoms with different morphologies can be seen. Furthermore, the growth of the gold cores occurs via sequential fusion of one tetrahedral Au4 unit by sharing one gold atom. In addition, density functional theory calculations show that these six newly predicted gold nanoclusters following the 2D growth mode have relative energies very close to those of their isomeric structures following the 1D growth mode, large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, and all-positive harmonic vibration frequencies, indicating their high stabilities. Therefore, the complete presentation of the 2D growth mode of Au28+4n(SR)20+2n (n = 0-8) is beneficial not only for a better understanding of the structural growth of gold nanoclusters, but also for a theoretical guidance on the prediction of new stable structures for experimental confirmation.

Structural predictions of thiolate-protected gold nanoclusters via the redistribution of Au-S "staple" motifs on known cores.

Four new atomic structures of thiolate-protected gold nanoclusters, namely, Au27(SR)20-, Au32(SR)21-, Au34(SR)23-, and Au36(SR)25-, were predicted via the redistribution of Au-S "staple" motifs on the known Au13 core from experimentally determined Au23(SR)16- and the Au20 core from crystallized Au30(SR)18. Density functional theory calculations show that these structures have large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps and positive vibrational frequencies, indicating their high stabilities. Furthermore, a series of more stable theoretical structures were predicted by introducing triply coordinated µ3-sulfido (µ3-S) motifs to the cores of Au27(SR)20-, Au32(SR)21-, Au34(SR)23-, and Au36(SR)25-. These predicted structures can further confirm the effectiveness and rationality of the ligand-binding strategy for the structural prediction of thiolate-protected gold nanoclusters by redistributing the Au-S "staple" motifs on known cores.