Recent Development on Controlled Synthesis of Metal Sulfides Hollow Nanostructures via Hard Template Engaged Strategy: A Mini-Review.

In this mini-review, we highlighted the recent progresses in the controlled synthesis of metal sulfides hollow nanostructures via hard template technique. After a brief introduction about the formation mechanism of the inorganic hollow nanostructures via hard template technique, the discussions primarily focused on the emerging development of metal sulfides hollow nanostructures. Various synthetic strategies were summarized concerning the use of the hard template engaged strategies to fabricate various metal sulfides hollow nanostructures, such as hydrothermal method, solvothermal method, ion-exchange, sulfidation or calcination etc. Finally, the perspectives and summaries have been presented to demonstrate that a facile synthetic technique would be widely used to fabricate metal sulfides hollow nanostructures with multi-shells and components.

Graphene Emerges as a Versatile Template for Materials Preparation.

Graphene and its derivatives are emerging as a class of novel but versatile templates for the controlled preparation and functionalization of materials. In this paper a conceptual review on graphene-based templates is given, highlighting their versatile roles in materials preparation. Graphene is capable of acting as a low-dimensional hard template, where its two-dimensional morphology directs the formation of novel nanostructures. Graphene oxide and other functionalized graphenes are amphiphilic and may be seen as soft templates for formatting the growth or inducing the controlled assembly of nanostructures. In addition, nanospaces in restacked graphene can be used for confining the growth of sheet-like nanostructures, and assemblies of interlinked graphenes can behave either as skeletons for the formation of composite materials or as sacrificial templates for novel materials with a controlled network structure. In summary, flexible graphene and its derivatives together with an increasing number of assembled structures show great potentials as templates for materials production. Many challenges remain, for example precise structural control of such novel templates and the removal of the non-functional remaining templates.

Multilevel hierarchically ordered artificial biomineral.

Living organisms are known for creating complex organic-inorganic hybrid materials such as bone, teeth, and shells, which possess outstanding functions as compared to their simple mineral forms. This has inspired many attempts to mimic such structures, but has yielded few practical advances. In this study, a multilevel hierarchically ordered artificial biomineral (a composite of hydroxyapatite and gelatine) with favorable nanomechanical properties is reported. A typical optimized HAp/gelatin hybrid material in the perpendicular direction of the HAp c-axis has a modulus of 25.91 + 1.78 GPa and hardness of 0.90 + 0.10 GPa, which well matches that of human cortical bone (modulus 24.3 + 1.4 GPa, hardness 0.69 + 0.05 GPa). The bottom-up crystal constructions (from nano- to micro- to macroscale) of this material are achieved through a hard template approach by the phase transformation from DCP to HAp. The structural biomimetic material shows another way to mimic the complex hierarchical designs of sclerous tissues which have potential value for application in hard tissue engineering.

Periodically Arranged Arrays of Dendritic Pt Nanospheres Using Cage-Type Mesoporous Silica as a Hard Template.

Dendritic Pt nanospheres of 20 nm diameter are synthesized by using a highly concentrated surfactant assembly within the large-sized cage-type mesopores of mesoporous silica (LP-FDU-12). After diluting the surfactant solution with ethanol, the lower viscosity leads to an improved penetration inside the mesopores. After Pt deposition followed by template removal, the arrangement of the Pt nanospheres is a replication from that of the mesopores in the original LP-FDU-12 template. Although it is well known that ordered LLCs can form on flat substrates, the confined space inside the mesopores hinders surfactant self-organization. Therefore, the Pt nanospheres possess a dendritic porous structure over the entire area. The distortion observed in some nanospheres is attributed to the close proximity existing between neighboring cage-type mesopores. This new type of nanoporous metal with a hierarchical architecture holds potential to enhance substance diffusivity/accessibility for further improvement of catalytic activity.

Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions.

Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are utilized as sacrificial hard templates to prepare single- and multi-shell hollow spheres of metal oxides and other inorganic compounds and filters, as well as in adsorption and catalysis processes, drug delivery systems, and other minority applications (e.g., lubricants, black pigment in e-papers, and microwave absorber).