The fundamental role of halide anions in the seed-mediated synthesis of anisotropic noble metal nanostructures has been a subject of debate within the nanomaterials community. Herein, we systematically investigate the roles of chloride, bromide and iodide anions in mediating the growth of anisotropic Au nanostructures. A high-purity surfactant solution of hexadecyltrimethylammonium bromide (CTABr) is used to reliably probe the role of each halide anion without interference from impurities. Our investigation reveals that bromide anions are required for the formation of Au nanorods, while the controlled combination of both bromide and iodide anions are necessary for the production of high-quality Au nanoprisms. Chloride anions, however, are ineffective at promoting anisotropic architectures and are detrimental to nanorod and/or nanoprism growth at high concentrations. We examine the seed structure and propose a growth model based on facet-selective adsorption on low-index Au facets to rationalize the nanostructures obtained by these methods. Our approach provides a facile synthesis of anisotropic Au nanostructures by way of a single growth solution and yields the desired morphologies with high purity. These results demonstrate that appropriate combinations of halide anions provide a versatile paradigm for manipulating the morphological distribution of Au nanostructures.

limits the diffusion of chemical species and their interactions with active sites in MOFs. [ 10 ] One of successful strategy from zeolites, silica, and carbon is the fabrication of mesopore structure which has expanded a large variety of potential and existing commercial applications. [1][2][3] Hence, it is worthwhile to develop methods to fabricate MOFs with mesopores so as to enhance the molecular diffusion while preserving their molecular sieve properties.To date, two major synthetic strategies have been explored to synthesize mesoporous-MOFs (meso-MOFs). [ 11 ] One is through ligand extension, either to increase the length of organic ligands [ 12 ] or to use bulky organic scaffolds [ 13 ] to form mesopores inside MOFs. In this case, the largest pore size reported is 9.8 nm in MOF-74 by increasing the length of organic linker to 5 nm. [ 14 ] Besides the diffi culties in complex ligands synthesis, interpenetration, disintegration, and instability of frameworks almost inevitably occur in MOFs with extended organic linkers, which prevent this functionalization method from being generally adopted in the formation of meso-MOFs. Another approach, the surfactanttemplate method, [ 4d , 15 ] has been introduced to increase the pore size in MOFs. For example, the Zhou group has successfully used cetyltrimethylammonium bromide (CTAB) as soft template to build meso-MOFs. [ 16 ] In this system, surfactant mole cules fi rst self-assembled into micelles serving as a soft template for MOFs growth and were subsequently removed to generate mesopores. The pore diameter of the resulting MOFs could be tuned from 3.8 to 31.0 nm. Nevertheless, as is well known, small molecular micelles are usually unstable under the synthesis conditions of most MOFs, so that only a few series of MOFs (such as carboxylic acid ligands) can be obtained by the surfactant-template method. Recently, some new methods have been successively developed to prepare the meso-MOFs, such as the gelation process, [ 17 ] and switchable solvent. [ 18 ] Moreover, the above methods are suitable for preparation of intrinsic meso-MOFs, but lack of control over the shape, position, and space distribution of mesopores in MOFs makes it hard to meet the demand for the growing applications of MOFs. It is well known that the potential applications of MOFs can be further developed and extended by encapsulating various nanoparticles (NPs) within the frameworks matrix so that the functionalized MOFs can exhibit the novel chemical and physical properties endowed by NPs. [ 7b , 19 ] Thus, to the best of our knowledge, general and versatile strategies of synthesizing functionalized MOFs with size-, shape-, and space-distribution-controlled mesopores have been rarely reported, in spite of the need and the signifi cance in application of functionalized meso-MOFs.Herein, we report a facile strategy of crafting mesopores inside MOFs through encapsulation of NPs followed by etching. Especially, the mesopore morphology, hierarchical structure, and space Porous materials, such as sili...

This study reports a systematic approach to synthesize ultralong gold nanorods and nanowires using a seed-mediated growth approach. In the first series, the effect of growth solution pH on the lengths of nanorods prepared was investigated. Interestingly, although shorter rods (230-310 nm) were produced in a basic solution environment than in an acidic condition (330-410 nm), the nanorod yield is greatly improved with relatively few nanoplate byproducts formed. Nanorod growth proceeds quickly in a basic solution as evidenced by the fast solution color changes. By adjusting several experimental parameters with the aim to elongate the nanorod length in a tunable fashion, gold nanorods and nanowires with average lengths from 580 to 2850 nm can be synthesized by progressively increasing the HNO3 concentration in the final growth solution. Nanowire growth in a highly acidic solution is slower, and a substantially longer time is needed to reach long lengths. Further extension of the nanowire length can be achieved simply by reducing the volume of second growth solution transferred to the final growth solution. Nanorods and nanowires with lengths spanning from 700 nm to 4.5 μm were prepared in this series of experimental conditions. The longest nanowires can reach a length of up to 6 μm. The nanowires still maintain thin average diameters of 33-53 nm. The ability to make gold nanorods and nanowires over this exceptionally wide and useful length range is exciting because applications and demonstrations using ultralong gold nanorods and nanowires of most suitable lengths are now possible.

Anisotropic Au@SiO(2) core-shell nanostructures have been fabricated from CTABr-stabilized Au nanoparticles with a facile synthesis involving a single growth solution. This procedure circumvents tedious surface modification steps and allows for the SiO(2) shell thickness to be tuned from 5 to 20 nm by modulating the nanoparticle number density and concentration of silica precursor.

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