The design of nanostructured materials and their corresponding morphologies has attracted intense attention because of their effectiveness in tuning electronic, optical, magnetic, and catalytic properties, as well as mechanical properties. Although many technologies have been explored to fabricate nanostructured materials, templated synthesis is one of the most important approaches to fabricate nanostructured materials with precisely controlled structures and morphologies from their constituent components. In this review article, we aim to highlight the use of the self-assembly of block copolymers as an emerging and powerful tool to fabricate well-defined nanomaterials with precise control over the structural dimensions and shape, as well as over the composition and corresponding spatial arrangement. After providing a brief introduction to the synthesis of regular porous materials, including silica- and carbon-based mesoporous materials, the review focuses on the fabrication of well-ordered nanoporous polymers from the selfassembly of degradable block copolymers, in particular with gyroid-forming network morphologies, as templates for the syntheses of various materials with different entities. We highlight the principles of different templated syntheses, from the fundamentals to their practical uses in the fabrication of nanohybrids and nanoporous materials; moreover, we provide an introduction to templates, precursors, solvents, and processing. Finally, some recent examples using block copolymer structure-directed nanomaterials for applications, such as solar cells, catalysis, and drug delivery, are presented. In particular, by taking advantage of the "well-ordered" structural characteristics of the gyroid texture, the properties and applications of 3D regular nanostructures, such as the photonic behavior and optical properties of gyroid-forming nanostructures, as well as of gyroid-forming metamaterials, will be emphasized. Special attention is also given to present new developments and future perspectives in this field.

Nanoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. A well-defined nanohybrid material with SiO2 gyroid nanostructure in a PS matrix can be obtained using the nanoporous PS as a template for sol-gel reaction. After subsequent UV degradation of the PS matrix, a highly porous inorganic gyroid network remains, yielding a single-component material with an exceptionally low refractive index (as low as 1.1).

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Mesoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by hydrolysis of PLLA block. Well-defined polymer/ceramic nanohybrid materials with inorganic gyroid nanostructures in a PS matrix can be obtained by using the mesoporous PS as a template for sol-gel reaction. Titanium tetraisopropoxide (TTIP) is used as a precursor to give a model system for the fabrication of metal oxide nanostructures from reactive transition metal alkoxides. By controlling the rates of capillary-driven pore filling and sol-gel reaction, the templated synthesis can be well-developed. Also, by taking advantage of calcination, bicontinuous TiO(2) with controlled crystalline phase (i.e., anatase phase) can be fabricated after removal of the PS template and crystallization of TiO(2) by calcination leading to high photocatalytic efficiency. This new approach provides an easy way to fabricate high-surface-area and high-porosity ceramics with self-supporting structure and controlled crystalline phase for practical applications. As a result, a platform technology to fabricate precisely controlled polymer/ceramic nanohybrids and mesoporous ceramic materials can be established.

A simple method for the preparation of nanomaterials with new functionality by physical displacement of a network phase is suggested, giving a change in space group symmetry and hence properties. A double gyroid structure made by the self-assembly of block copolymers is used as a model system for the demonstration of shifting networks to achieve single gyroid-like scattering properties. Free-standing single gyroid-like network materials can be fabricated to give nanophotonic properties, similar to the photonic properties of a butterfly wing structure.

Well-defined multibranched gold (Au) in polymers, both as bulk or continuous thin films, can be fabricated by using a nanoporous polymer with gyroid nanochannels as a template. The nanoporous polymer template is obtained from the self-assembly of a degradable block copolymer, polystyrene-b-poly (L-lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. Templated seeding growth approach can be conducted to create precisely controlled nanostructured Au giving remarkable surface plasmon resonance (SPR) in (branched Au with uniform distribution in PS matrix) near-infrared (NIR) region. Controlled growth conditions allow the fabrication of three-dimensionally ordered nanoporous Au particles that possess NIR SPR. Double gyroid Au with dual networks in the PS matrix is obtained after completing the seeding growth at which the NIR SPR diminishes resulting from the reduction in the density of nanostructured edge.

Nanoporous platinum (Pt) with a gyroid nanostructure was fabricated using a nanoporous polymer with gyroid nanochannels as a template. The nanoporous polymer template was obtained from the self-assembly of the degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by the hydrolysis of the PLLA blocks. Templated electroless plating can be conducted under ambient conditions to create a precisely controlled Pt gyroid nanostructure with high crystallinity in a PS matrix. After removal of the PS matrix, the well-interconnected nanoporous gyroid Pt can be successfully fabricated. Compared with commercially available catalysts, the nanoporous Pt possesses superior macroscopic stability and peak specific activity, benefiting from the well-defined network structure with robust texture and the growth of the low-index crystalline facets of Pt.

An order−order phase transition of chiral block copolymers (BCPs*) from single helix to double gyroid (H* → G) through a nucleation and growth process was demonstrated. The H* and G phases can be obtained by solution casting from fast and slow solvent evaporation, respectively, suggesting that the H* phase is a metastable phase. Consequently, the coexistence of H* and G phases can be found in the solution-cast samples from intermediate solvent evaporation. To truly examine the transition mechanism of the H* → G, electron tomography was carried out to directly visualize the morphological evolution in real space, in particular, the transition zone at interface. Unlike the mechanisms for the transitions of block copolymers (BCPs) by considering the interdomain spacing matching, a significant mismatch in the lattices for the H* → G was found. Consequently, the transition may require an adjustment on the geometric dimensions to justify corresponding lattice mismatch. As a result, the morphological observations from electron tomography offer new insights into BCP phase transitions.