Templated Synthesis for Nanoarchitectured Porous

Award Accounts

The Chemical Society of Japan Award for Young Chemists for 2013

Templated Synthesis for Nanoarchitectured Porous Materials Victor Malgras,1 Qingmin Ji,1 Yuichiro Kamachi,1 Taizo Mori,1,2 Fa-Kuen Shieh,3 Kevin C.-W. Wu,4 Katsuhiko Ariga,*1 and Yusuke Yamauchi*1 World Premier International (WPI) Research Center for Materials Nanoarchitechtonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 1

2

Liquid Crystal Institute, Chemical Physics Interdisciplinary Program, Kent State University, Kent, Ohio 44242, United States 3

Department of Chemistry, National Central University, Chung-Li 32001, Taiwan

4

Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan

E-mail: [email protected], [email protected] Received: April 21, 2015; Accepted: June 28, 2015; Web Released: July 22, 2015

1. Introductions Controlling a structure with a nanometer scale precision is critical to create nanoporous materials with innovative functions. However, single-component nanomaterials and monotonous nanostructures cannot satisfy demands from advanced and more elaborated applications any more. Instead of simple nanostructures, highly sophisticated and wisely combined assemblies of nanomaterials now became necessary for further developments. The strategies for constructing functional nanomaterials have to step up from “nanofabrication” to “nanoarchitectonics”.1­12 Nanoarchitectonics was recently proposed as an advanced concept for the assembly of structural materials at the nanoscale level.13,14 Based on a deep understanding of the mutual interactions between the individual nanostructures and their arbitrary arrangements, including atoms and molecules manipulation, functional materials with sophisticated internal architectures can be elaborated. Nanoarchitectonics is expected to achieve an effective guidance in fabricating functional nanoporous materials. We can find relevant specimens of nanoarchitectonic guidance in naturally occurring systems. In living cells for example, various kinds of molecules and ions in softly organized assemblies can operate synergistically to render incredibly high efficiency and selectivity. Interestingly, most of their components are rather fragile and deformable soft-materials which have the potential to form highly harmonized structures with specific functions due to their flexibility during the assembling process. It would be therefore useful to transcript the structural information of soft-materials assemblies into rigid inorganic materials in order to design harder components.15,16 This structural transcription approach of soft-assemblies would be a breakthrough in the development of nanomaterials science and technology. ProtoBull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

typical strategies of this concept have been indeed researched for the last few decades under the name of “templated synthesis”.17­19 The fabrication of inorganic nanomaterials from soft assemblies would be an attractive way to benefit from the advantages and characteristics of both hard- and soft-materials. The general route for the templated synthesis of nanostructured materials includes the following steps: (1) template preparation, (2) template-directed synthesis of target materials, and (3) template removal (if necessary). Alternative ways, such as hardtemplating methods, have been proposed, in which the targeted material is deposited into the confined spaces of the template. Hard-templating is a facile synthetic method for fabricating nanoporous materials with a stable porous structure derived from inverse replica of an original template. Thus, nowadays a wide variety of synthesis techniques are utilized to produce nanoporous materials. Here, we summarize the general principles behind various types of templated-synthesis and cover recent developments in this area (Scheme 1). This review is organized according to the types of templates reported so far: namely the soft-, hard-, and sacrificial templates. The concept of templated synthesis can be utilized to prepare nearly all types of nanoarchitectured materials with different compositions (i.e., metal oxides, metals, semiconductors, and ceramics) and various structures/shapes (zero-dimensional (0D) nanoparticles, one-dimensional (1D) nanowires and two- and threedimensional (2D and 3D) hierarchical nanostructures). 2. Soft-Templates 2.1 Self-Assembled Lipid Template. The hybridization of inorganic structures into soft-organic templates possesses several advantages such as fine-structuring inorganic materials and mechanically strengthening organic functional structures. In the following section, lipid-based hybridization approaches © 2015 The Chemical Society of Japan | 1171

Scheme 1. Historical development of various templated synthesis.

in their initiation period are briefly summarized. The approaches based on the functional transcription from softtemplates into inorganic materials can be categorized into two strategies: (i) the hybrid formation between rigid materials and soft-templating assemblies and (ii) the structural transcription of the soft-template into a rigid material. Here, research developments on these strategies as well as some pioneering examples are briefly described. 2.1.1 Soft-Assembly with Inorganic Support: Amphiphilic lipid molecules can self-assemble into various kinds of structures, including monolayers, bilayers, or multilayers architectures. Among them, the lipid monolayer can be regarded as a unit, or a building block. Because it is usually not strong enough to maintain its structure by itself, the lipid monolayer is often immobilized on solid supports as a self-assembled monolayer (SAM) through the formation of strong Si­O­Si,20,21 S­Au,22,23 and Si­Si24,25 bonds. The formation of conjugate hybrids based on the SAM approach allows the preparation of nanoscale surface coating and patterning, which are important processes in nanofabrication. On the other hand, the Langmuir­Blodgett (LB) method26­30 is known to be a powerful method to achieve well-organized thin films. Approaches combining SAM and LB with nanoporous inorganic support led to the successful synthesis of nanostructured materials with promising transport properties using only a single lipid monolayer. In later 1980s, Ariga, Okahata, and co-workers accomplished the permeation control of aqueous solute through a single lipid monolayer by combining SAM and LB.31,32 In this work, a fragile lipid monolayer was mechanically strengthened by forming a single silicate layer in the neighborhood of the polar region of the Langmuir film through in situ polymerization of organosilane at the air­ water interface (Figure 1). Upon addition of acid into the water 1172 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 1. Langmuir­Blodgett film of silica-layer-baring monolayer at the air­water interface.

sub-phase, in situ polymerization could be confirmed by the following three methods: 1) variations of the surface pressure; 2) molecular area isotherms of dialkylsilane monolayer with the formation of a condensed monolayer phase and without the formation of an expanded state; 3) FT-IR spectroscopy upon transferring the films (30 monolayers) on CaF2 plates. The quasi-2D osmotic pressure analysis revealed that the degree of polymerization at pH 2 becomes ca. 300. The resulting single 2D hybrid gives a covalently linked surface area covering the nanopores of the glass substrate. Transferring the single monolayer onto a porous glass plate (5 nm pore) clearly suppresses the permeability to the aqueous fluorescent probe and to sodium chloride compared with a bare glass plate. In addition, permeation through the polymerized monolayer increased © 2015 The Chemical Society of Japan

Figure 2. A “cerasome” lipid bilayer vesicle with silica network.

significantly when the sample was heated up to the phase transition temperature. It is the first time that permeation control through a single lipid monolayer structure was demonstrated. A similar hybrid lipid conjugate soft monolayer was employed in sensing application based on the permeability control of an electrochemical probe ([Fe(CN)6]4¹/[Fe(CN)6]3¹)33 and on the mimic of vitamin function using electrodes modified with a vitamin B12 derivative with the aid of organosilane monolayers.34,35 The concept of hybrid lipid conjugate soft-assembly is not limited to hybrid sheet-like morphologies and can be applied to 3D hierarchical structures. In order to develop cell-like spherical shapes with mechanically strong inorganic frameworks, several approaches have been proposed. Katagiri et al. proposed to covalently link a siloxane framework onto the membrane surface of a lipid bilayer vesicle (Figure 2).36,37 The resulting structure was named “cerasome”, from the combination of “ceramics” and “soma”. The dispersion of certain kinds of alkoxysilane-bearing amphiphiles induces the spontaneous formation of vesicular structures by promoting silica-like inorganic linkage at the surface. Transmission electron microscopy (TEM) imaging confirmed the presence of multi-lamellar cerasomes with a bilayer thickness of ca. 4 nm and a vesicular diameter of 150 nm. In addition, multi-vesicular aggregates maintaining the characteristic spherical morphology were also observed, even upon suppression of the cerasome, probably due to the formation of intra- and intermembrane siloxane network strengthening the overall structure. This approach was extended to the formation of 3D structures by depositing cerasomes through a layer-by-layer (LbL) process.38­50 The LbL assembly of a cationic polyelectrolyte (e.g., poly(diallyldimethylammonium chloride), PDDA) with anionic vesicles allowed the film to grow uniformly.51 Furthermore, this method can also be applied to cationic and anionic cerasomes without using intermediate polyelectrolytes.52 Atomic force microscopy imaging of the resulting films showed closely packed particles for both the cationic and anionic cerasomes, similar to a layered stone pavement. The obtained structure can be regarded as the mimic of multi-cellular tissues rather than independent cells. 2.1.2 Nanostructure Formation with 2D Multilayer Assembly: More advanced approaches for the formation of nanostructures include the structure transcription from organized soft-templates into inorganic materials. Kunitake and coBull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 3. Preparation of 2D polymer nanosheets using lipid multilayer templates of synthetic double-alkyl cationic lipids.

workers have achieved pioneering works in both organic and inorganic nanostructure formation using lipid multilayer systems through lipid cast films. Although lipid assemblies can form spontaneously in solution medium, such as liposomes and vesicles, thin film materials containing lipid bilayer units can be obtained upon gradually evaporating solvents after casting the lipid solution on a solid support. The obtained thin films are often detachable from the substrate, thus resulting in freestanding films. In these structures, 2D lipid bilayer sheets are stacked on top of each other, providing an anisotropic template medium for material synthesis. Hydrophilic source materials, such as monomeric precursors, can be selectively condensed in the hydrophilic interlayer nanospaces of the lipid films. Solid formation processes, including polymerization and sol­gel reaction, followed by the extraction of the bilayer soft-template component, result in 2D ultrathin sheet-like materials. The preparation of 2D sheet-like structures with highly oriented assemblies of organic components was reported. Polymerization with crosslinked processes resulted in stable and highly anisotropic 2D polymer sheets. For example, Kunitake and co-workers introduced hydrophilic oligoethylene glycol bis-acrylate molecules in the interlayer spaces of a synthetic multilayered double-alkyl cationic lipid templates (Figure 3).53,54 Crosslinking polymerization within the template nanospaces upon the irradiation of an ultrahigh pressure Hg lamp in the presence of a photoinitiator resulted in highly oriented hybrids. Extracting the template components by immersing the hybrid film in methanol led to the formation of self-standing transparent films within which 2 nm thick 2D © 2015 The Chemical Society of Japan | 1173

Figure 4. Formation of various 2D silica nanostructures using lipid multilayer templates.

polymer nanosheets are stacked together. X-ray diffraction and X-ray photoelectron spectroscopy analysis on the prepared films confirmed that their crystal structure and composition were highly uniform. A distinct advantage of this approach is the availability of a wide range of guest monomer components. Incorporating guest monomer molecules in the interlayer nanospaces do not induce any significant destruction of the soft-template structure because the supramolecular interactions between the template and the guest molecules are weak at the surface of the lipid bilayer. This characteristic makes it possible to prepare various kinds of polymers, including poly(stearyl acrylate)55 and poly(tetraallylammonium bromide).56 Similar strategies were also reported to synthesize 2D polymer sheets using LB films as soft-templates.57,58 The same research group also used a sol­gel reaction with a multi-bilayer template medium to produce ultrathin 2D silica nanosheets (Figure 4).59­61 Methyl trimethoxysilane as silica precursor was dispersed with the lipid bilayers under sonication in order to form cationic amphiphiles. The resulting dispersion was cast on a solid support, followed by exposing the film to gaseous ammonia in order to complete the sol­gel reaction. Extracting the lipid template from the hybrids resulted in highly oriented silica thin films. Interestingly, various morphologies, such as rod, sheets, and spheres with porous structures, were obtained upon appropriate selection of amphipihiles and after optimizing the synthesis conditions (e.g., precursor-totemplate ratio). Similarly, multilayered alumina films with crystalline anisotoropy and high surface area were prepared using multi-bilayer soft-template films.62 Here, an aqueous dispersion of cationic amphiphiles was first prepared, to which alumina sol was added under sonication. The mixed dispersion was cast on a solid support followed by calcination in air at high temperature. Scanning electron micrograph (SEM) imaging indicated that ca. 10 nm thick multilayered structures grew 1174 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

in parallel to the film plane. Increasing the calcination temperature resulted in increasing the anisotropy of the alumina crystalline structure. The surface area of the synthesized films became significantly high (ca. 100 m2 g¹1) when the calcination temperature reached 1300 °C. Kunitake et al. also reported the preparation of various inorganic nanomaterials within the soft multi-bilayer template. For example, the formation of iron oxide particles distributed in an oriented fashion was demonstrated using lipid cast films as a synthetic method.63 The oriented iron oxide particles had a magnetic anisotropy. CdS clusters were synthesized using highly ordered multilayer films of amphiphiles containing ethylenediamine,64,65 where regulated amounts of CdCl2 or CdBr2 were incorporated by dipping the templates into an aqueous solution of cadmium halide. The obtained hybrid films were exposed to H2S gas to form Q-state CdS particles. A supramolecular assembly of a halogen-bridged platinum complex was shown to form a molecular wire using a soft-template of double-chained phosphates or sulfonates lipids.66 The complex exhibited intervalence charge transfer absorption bands in the crystalline state which could be maintained in organic media because of their amphiphilic stable superstructure. This strategy might be widely applicable to the preparation of soluble, low-dimensional inorganic materials. A multilayer template approach was employed to synthesize graphitic carbon films using montmorillonite clay.67 The incorporation of acrylonitrile copolymers and methacryloyloxyethyltrimethylammonium chloride into the nanospaces between the clay plates, followed by carbonization, resulted in graphitic films. Heat treatment at 700 °C converted the copolymer into amorphous carbon although the montmorillonite template remained intact. Dissolving the montmorillonite template with hydrofluoric acid (HF) and further heat treating at 2200 °C led to the formation of a highly oriented graphite film. 2.1.3 Nanostructure Formation with Non-2D Assembly: The structure transcription of 3D soft-templates, such as fibrous molecular assemblies, can be used to synthesize rather complicated rigid nanoarchitectures. Shinkai and co-workers firstly reported the successful utilization of a cholesterol-based organogelator as template in order to synthesize 3D networks of nanometer-sized hollow silica fibrils through sol­gel transcription.68 During the process, the cationic groups on the fibrils allowed the adsorption of the anionic silica oligomers, giving appropriate reaction sites for the polymerization to occur. Based on electrostatic or hydrogen-bonding interactions between the organic superstructure and the inorganic precursors, a variety of morphologies, including spheres, tubes, and helical ribbons with well-defined dimensions, could be transcribed.69­73 The inorganic structures obtained from the sol­gel transcription process are not always an exact copy of their self-assembled template. For example, rod-shaped molecular assemblies produce tubular morphologies of metal oxide. Shimizu et al. reported a close reproduction of a nanotube shape by using the molecular assembly of synthetic peptidic lipids into a single-bilayer wall as a template (Figure 5).74 A relatively small population of positive charges and mild catalytic sites on the organic template are crucial for the formation of nanotubes with smooth and ultrathin (ca. 8 nm) silica walls. The unique process using the mild catalytic function of the ter© 2015 The Chemical Society of Japan

Figure 5. Preparation of a nanotube using the molecular assembly of a synthetic peptidic lipid with a single-bilayer wall as a template.

minal head group enables a fine control over the wall thickness of the obtained silica nanotubes within 4 nm precision.75 The importance of these design does not only relies on the porosity of their structures, but also on their tunable functionalities. The combination of self-assembled templates and other functional additives opens a new route to form inorganic or hybrid materials with specific purposes for promising applications. Huang et al. reported a rational design of artificial silica nanohelices by supramolecular self-assembly of a synthetic sugar-lipid C4AG.76 The double-stranded helical assembled structures of C4AG served as a template for the formation of silica double-stranded nanohelices. Through the addition of ionic surfactants, which introduces interchain repulsion, the double-stranded nanohelices can transform into single-stranded silica nanohelices or nanotubes. The unwinding of double helixes into single-stranded fibers can be viewed as a good example of building tunable hierarchical architectures via chemical self-assembly. Marr and Evans employed a poly(9,9di-n-octylfluorenyl-2,7-diyl) (PFO) conjugated polymer (CP) added to a 5-di-O-methanesulfonyl-1,4:3,6-dianhydro-D-sorbitol organogelator.77 The sugar-based gelator self-assembled into a fibrous network in ethanol. The addition of the tetraethyl orthosilicate (TEOS) silica precursor led to the transcription into micrometer scale silica tubes. In this process, the PFO additive is expected to be immiscible in both the organogel and the hydrophilic sol­gel phase and thus preferentially segregates at the organogel/silica interface. After removing the organogel template, the resulting uniform CP-silica microtubes retained the photoluminescence properties of the parent, showcasing their promising potential in applications such as optoelectronic and photovoltaic devices. 2.2 Biopolymer Templates. Since nature presents great evidences of many well-defined and structured inorganic or hybrid materials, the usage of the biotemplates or biomolecular superstructures seems to be a direct, facile, and intuitive choice to fabricate inorganic materials in a wide range of scales and Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 6. Preparation of various silica nanostructures using DNA templates.

highly ordered hierarchical morphologies. The complexity of the structures from biotemplates is generally difficult to reach through synthesized templates. In 1991, Mann et al. successfully used supramolecular protein cages as template for different metal nanophase materials (e.g., FeS and MgO).78 Later, the group also reported using the well-known tobacco mosaic virus (TMV) as a template to synthesize inorganic metal nanotubes (silica, iron oxides, CdS, and PbS),79,80 as well as particles with more complicated structure (with radially patterned interiors and threadlike mesostructures). The surface amino acid residues on the TMV tube facilitate the adsorption of the precursors and the formation of an inorganic layer around the template. Moreover, the self-assembly capability of the TMV structure itself resulted in a highly faithful superstructural transcription.81 Helical structures represent one of the most common structural motifs for high order architectures performing several functions in biology. The double helical structure of DNA is a brilliant natural strategy by which genetic material can be stored and copied. Shinkai et al. reported using DNA as a template to form inorganic materials.82 As DNA is anionic, they treated it with cationic n-octyl-1,8-diammonium dibromide or didodecyldimethylammonium bromide to form cationic DNA complexes. The resulting superstructure was found to act as an ideal template from which silica can faithfully inherit rod-like (inside coiled coils shapes) and circular morphologies (Figure 6). Che et al. described the formation of a DNA­silica complex with a tunable mesoporosity based on the co-structure directing effect of N-trimethoxy silylpropyl-N,N,N trimethylammonium chloride (TMAPS).83 After introducing various alkaline earth metal ions into the systems, DNA chiral packing and the corresponding macroscopic silica-DNA helical morphologies can be tuned by controlling the reaction temperature, pH, and the molar ratio of the quaternary ammonium/ phosphate groups. They suggested that the interaction strength between DNA and the quaternary ammonium/phosphate

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Figure 7. Preparation of nanostructured TiO2 materials using biotemplates.

groups dictates the chiral conformation of the DNA­silica complex, the left- and right-handedness having a direct dependence on their molar ratio. Besides using those relatively small biomaterials, “giant” natural materials, like cotton or insect wings, have also been successfully used as templates for inorganic nanostructures.84­86 Boury et al. employed cotton wool and terula communis (an umbelliferous plant) for the synthesis of nanostructured TiO2 microfibers or microcellular materials through non-hydrolytic reaction of TiCl4 (Figure 7).87 The hydroxy and ether groups in the cellulose of the biotemplates can react with TiCl4, leading to the intermediate formation of a titanium alkoxide network. Different from the most common surface sol­gel approaches in which the template is only a mold over which an oxide layer is deposited, here the biotemplate is a reactant which is gradually replaced by the oxide phase, similar to fossilization processes. Xia and co-workers reported the synthesis of porous metal oxide/carbon (LiFePO4/C and NiO/C) composite microstructures in which native spirulina and lotus pollen grains acted both as a template and as a carbon source.88 Owing to their unique hierarchical microstructures, the porous composite materials exhibited remarkable electrochemical performances. 2.3 Self-Assembly of Amphiphilic Molecules for Mesoporous Materials. Amphiphilic molecules, including surfactants and block copolymers, contain both hydrophilic and hydrophobic groups, which tend to reduce locally the surface tension of a medium and are widely used as detergents, emulsifiers, foaming agents, and dispersants. According to the nature of the hydrophilic moieties, they can be classified as nonionic, anionic, cationic, or amphoteric types. Amphiphilic molecules are spontaneously self-assembled into aggregates with various morphologies, such as spherical or rod-like micelles. By increasing their concentration, periodic liquid crystal mesophases can also be obtained. Self-assembled substances can 1176 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 8. Systematic presentation of the synthesis of mesoporous materials: (a) cooperative self-assembly route, (b) lyotropic liquid crystal templating route.

ultimately be used as structure-directing agents (SDAs) for mesoporous materials. The first example of ordered mesoporous silica was reported in 1992.89,90 At high concentration, the surfactants preliminarily form a liquid crystal phase. Then, the inorganic source is introduced on the surface of the micelles to form a mesostructured composite. Subsequent studies have shown that the wellordered mesostructured composites can also be prepared when the surfactant concentration is much lower than that required for the formation of a liquid crystal. Cooperative self-assembly is generally known as the most common method (Figure 8a), in which both the surfactant and the framework undergo conformational changes to form an ordered mesophase. Considering the interactions between both components is critical to obtain highly ordered mesostructured materials. Several interactions such as electrostatic, van der Waals, hydrogen or coordination bonding, were previously reported.91 For instance, in basic conditions, where the surface of the silica species is negatively charged, a cationic surfactant is favored as a template. The selection of the template removal process should be carefully considered in the preparation of mesoporous materials. Various removal methods have been developed, such as conventional calcination, solvent extraction, ozone treatment,92 supercritical CO2 fluid extraction,93 and H2SO4 treatment.94 The suitable process must be selected depending on the nature of the framework compositions. The reaction of layered silicates with organoammonium surfactants is also useful for the preparation of ordered mesoporous silica.95 FSM-16-type ( p6mm) mesoporous silica is formed from layered intermediates composed of fragmented silicate sheets and alkyltrimethylammonium cations.96 KSW-2-type (c2mm) mesoporous silica can be prepared through the bending of individual silicate © 2015 The Chemical Society of Japan

sheets with intra- and interlayer condensation.97 The structural units originating from the silicate sheets (kanemite) are partially retained in the frameworks, showcasing the unique capabilities of layered silicate which cannot be attained by MCM-type mesoporous silica.98 In the past two decades, many efforts have been made to synthesize nanoporous materials with well-controlled pore size, shape, composition, and spatial arrangement. Porous materials can generally be classified as macroporous (>50 nm), mesoporous (2­50 nm), and microporous materials (50%) of 3-aminopropyltriethoxysilane without any loss of the ordered mesostructure.216 From the viewpoint of environmental remediation applications, organically modified mesoporous silica materials have been utilized for the removal of toxic metal ions from aqueous solutions.217 Mercaptopropyl-functionalized mesoporous silica218,219 has a strong ability to absorb mercury ions due to their effective interactions with thiol sites. Amine-functionalized MCM-41 has been exploited for the selective extraction of precious metals. Only gold (Au(III)) ions can be collected from binary mixtures (with Cu2+ or Ni2+) by adjusting the solution pH in which the Cu2+ and Ni2+ ions have less interaction with the protonated amine groups than the Au3+ ions.220 Bridged silsesquioxanes ((RO)3Si­R¤­Si(OR)3),221 which are synthe© 2015 The Chemical Society of Japan | 1183

sized by bridging two organo-alkoxysilanes, are promising silica sources because they possess a variety of interesting chemical and physical properties. Inagaki et al. reported the synthesis of 2D- and 3D-hexagonal mesoporous organosilica by using 1,2-bis(trimethoxysilyl)ethane.222 Guan et al.,223 Kapoor et al.,224 and Sayari et al.225 reported various mesoporous organosilicas with ethylene units. A spray-drying process was also employed to prepare mesoporous organosilica particles with ethane and benzene fragments by using 1,2bis(triethoxysilyl)ethane or 1,4-bis(triethoxysilyl)benzene in conjunction with TEOS.226 The organic contents in the frameworks can be tuned by simply controlling the molar ratio of the initial precursor solutions. The synthesis of phenylenebridged mesoporous organosilica with a crystalline framework was also achieved by the hydrolysis and condensation of 1,4bis(triethoxysilyl)phenylene.227 TEM images clearly showed periodic fringes, derived from stacked benzene units, formed parallel to the 1D mesochannels. The crystalline-like structure in the framework was probably due to the stacking of phenylene units. Optoelectronic applications, such as photovoltaic devices, have been reported using periodic mesoporous organosilica materials with strong light absorption due to the densely packed organic chromophores within the pore walls.228 It is worth noticing that the energy from the photons is first absorbed by 125 biphenyl groups inside the framework and then funneled into a single coumarin site located at the mesochannel center with almost 100% quantum efficiency, thus enhancing drastically the emission from a single coumarin molecule. A hole-transporting framework can be also formed by using an electroactive phenylenevinylene-based organosilane precursor.229 The molecular geometry of the three-armed precursor contributes to both the formation of the periodic mesostructure and the introduction of hole conductivity in the organosilica hybrid. The electroactive organosilicas with mesopores and large surface areas have great potential for novel photovoltaic and photocatalytic systems. Incorporating metals in the functionalized organosilica framework provides many opportunities for accelerating the catalytic reactions by enhancing the physical and chemical properties of guest molecules and clusters.230 A large number of mesoporous organosilicas with several organic bridging groups, such as aliphatic, aromatic, and metal complexes, have been synthesized in various forms (e.g., powders, thin films, and monoliths, including self-standing films).231 Mesoporous organosilica films can be synthesized by either hydrothermal or solvent-evaporation methods. In both cases, the precursor solutions normally have a low pH, so the frameworks usually do not show molecular periodicity. Under basic conditions, a crystalline framework can be formed by hydrothermal process through the hydrolysis and condensation of organosilanes (e.g., 1,4-bis(triethoxysilyl)benzene).232 The organosilica frameworks, with both organic and inorganic properties, have various functions and find applications as lowdielectric-constant (low-k) material which are in high demand in modern semiconductor chemistry. Many types of mesoporous organosilica films with highly ordered mesostructures have been prepared by using various bridged organosilane precursors via casting, spin-coating, or dip-coating.233­235 Such 1184 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

films have good thermal stability and hydrophobicity, showcasing their potential as low-k films. The organic content can be tuned by varying the amount of silica source added in the precursor solutions. Increasing the organic content normally leads to the decrease of the dielectric constant. 2.4 Microemulsion Templates. Water-in-oil or oil-in-water microemulsions are naturally formed by mixing water with an immiscible alkane (e.g., hexane, n-octane, and isooctane) and one or more amphiphilic surfactants which will tend to orient in a way to maintain their hydrophobic tail in the oil phase and their hydrophobic head in the water phase. Once stable, the resulting system comprises micelles (reverse or not) whose size and shape will depend on several factors such as the nature of the surfactant and the water/oil/surfactant ratio. The candidate surfactants can be anionic, such as sodium dodecyl sulfate (SDS) or sodium sodium bis(2-ethylhexyl) sulfosuccinate (AOT), cationic, such as cetyltrimethylammonium chloride (CTAC) or bromide (CTAB), zwitterionic, such as α-phosphatidylcholine (lecithin), or nonionic, such as polyoxyethylene glycol alkyl ethers (Brij). Pileni first revealed the potential of these systems to build nano- and microreactors for the synthesis of metal nanoparticles by functionalizing AOT with copper or silver.236­238 Other reviews were then published, describing the mechanisms involved in microemulsion colloidal synthesis.239,240 For example, it was established that combining AOT and lecithin in an optimized content would lead to a stable system of hexagonally arranged water columns (HII) in isooctane.241 Following this discovery, CdS nanorods242 and channeled porous TiO2 could be synthesized.243 A microemulsion combining water, decane, undecylic acid, decyl amine with barium and chromate ions was used to produce 1.2­1.5 ¯m BaCrO4 nanowires with a diameter of 6 nm.244 Serrà et al. succeeded to synthesize NiCo nanoparticles with good magnetic properties. The system comprised water, Triton-X and diisopropyl adipate and was carried at room temperature.245 The creation of a monolithic nanoporous (100 nm pores) ternary polymer blend inheriting the interpenetrating channels from a typical bicontinuous microemulsion was also reported.246 This can be then used as an ideal template for the synthesis of nanoporous polymeric thermosets, conducting polymers, block copolymers, ceramics and silica, showcasing promising potential in catalytic and battery applications. Nie et al. recently reported the synthesis Au(I)-3-mercaptopropionic acid with controllable morphology, including rectangular/square nanosheets, nanobelts, nanostrings, and nanoships.247 The system consisted of a quaternary emulsion of CTAB, water, cyclohexane and 1-pentanol. With a facile reverse micelle assembly comprising xylene as oil and oleylamine as surfactant, Sim et al. successfully produced Ni-Mn layered double hydroxides.248 3. Hard-Templates The hard-templating method (i.e., nanocasting) is widely used and is a promising strategy for the synthesis of nanoporous carbons, metals, and metal oxides. This procedure, which is similar to the casting method used in metallurgy, can generally be conceptually adapted to the nanometer scale and applied to the synthesis of nanostructured materials using various hard-templates. Hard-templating is a facile synthetic method for fabricating porous materials with a stable porous © 2015 The Chemical Society of Japan

Figure 17. Selective preparation of nanotubes and nanowires prepared from AAO. Reproduced from http://research.chem.psu.edu/axsgroup/Ran/research/ templatesynthesis.html.

structure by depositing the targeted materials into the confined spaces of the template resulting in a reverse replica. It is known that porous anodic aluminum oxide (AAO) presents unique structural features such as well-ordered 1D metal oxide arrays.249 The composition of the electrolyte, the anodization time and the applied voltage can be adjust to control the porosity as well as the tube diameter and length. Because of its tunability and stability, AAO has been widely used as template to fabricate porous materials (Figure 17),250 although it can also act as supporting material. In a standard procedure, target precursors or materials (e.g. carbon,251 titania,252 hematite (Fe3O4),253 perovskite PbBi2Nb2O9 (PBON),254 metal,255 or polymer 256) are deposited inside the AAO arrays. The template is then removed to form nanotube or nanorod structures. These moulded materials have received a lot of attention in various fields owing to their outstanding physical and chemical properties. Similar concepts were rapidly extended to synthesize a wide range of nanoporous materials through hardtemplating process. 3.1 Colloidal Templates. There have been several methods for fabricating periodic macroporous structures by colloidal crystal templating (Figure 18).257 The first step of fabrication consists in preparing the hard-template with an appropriate composition. Inorganic silica and organic polymer are common candidates for template materials, both having their own advantages and drawbacks. During the impregnation and the conversion of the targeting precursor, silica templates provide a more stable structure even under critical conditions such as vacuum, high temperature and strongly acidic environment. Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 18. Three methods of preparing periodic macroporous structures by colloidal crystal templating. (left) A preformed colloidal crystal is infiltrated with the precursor material which is processed to form the 3DOM structure after removal of the template, (middle) uniform spheres and nanoparticles (NPs) are codeposited to form a 3DOM structure after template removal, and (right) core­shell structures are assembled into periodic arrays, forming close packed hollow shells. Reproduced from ref 257.

The removal of the silica template requires, however, the use of hydrogen fluoride etchants, which are highly corrosive and toxic. On the other hand, polymer templates can be easily removed by calcination or chemical extraction, but it is difficult to maintain their integrity under critical environment. Colloidal templates have been prepared using different methods such as sedimentation, centrifugation, filtration, or capillary force.258 In the sedimentation method, colloidal silica or polymer particles settle at the bottom of the flask. This process is driven by gravity and long periods of time are necessary to complete the fabrication (from several days to few weeks). To shorten the preparation time from days to a few hours, the driving force can be enhanced by centrifugation or suction. During this process, colloidal particles assemble in a tightly-packed manner. Recently, a new emulsion method has been reported to generate colloidal particles with a microspherical morphology. For example, based on the self-assembling character of emulsive systems, Li et al. synthesized PS balls with an opal structure as template to further obtain ordered macroporous TiO2 photonic balls with a reverse opal structure.259 In order to extend the morphology of a single pore to a hierarchical structure (e.g., bimodal macropore/mesopores), a PS-based hard-template needs to be further processed with additional mesopore-guiding agents. For example, Yu et al. controlled the sol­gel reaction of TEOS guided in the internal voids of the template in order to form silica nanoparticles with a size of 10 nm.260 After removing the PS by calcination, the obtained silica material possessed a bimodal pore size distri-

© 2015 The Chemical Society of Japan | 1185

bution: macropores with a size of 260 nm converted from the PS particle size and mesopores with a size of around 7 nm. Furthermore, by using such silica template, multimodal porous carbons with a high surface area of 1120 m2 g¹1 were prepared. Multimodal porous carbon is an attractive candidate to support Pt-Ru catalyst and demonstrated higher power density toward hydrogen oxidation than commercial carbon (Vulcan XC-72). Regarding the applications of porous materials in sorption and controlled release, macroporous materials, rather than micro- or mesoporous materials, provide higher pore interconnectivity and more surface accessibility. These advantages lead to a better mass transfer and faster uptake of large guests such as biomolecules, heavy metal ions,261 oils, etc. For examples, Pan et al. investigated a magnetic macroporous Fe/C nanocomposite to separate oils from the water surface.262 The ability of macropores to remove oil were compared according to their average diameters and the results indicated that larger pores led to a better removal efficiency. In addition, macroporous carbon-based functional magnets can easily collect pollutants from oil and thus, are promising recycling absorbents. Stein and co-workers synthesized macroporous hydroxyapatite as a host material suitable for the controlled release of antibiotic norfloxacin.263 The size of the pores of the host material had a direct impact on the release rate and extending to a macro- or mesoporous hierarchical structure led to an improved regulation of the kinetics of release and a longer release period. Ordered macroporous architectures derived from inverse opal components also show great potential in sensors,264 and catalyst supports,265 owing to their high surface area, large pore volume and unique optical properties. In addition, because of their well-arranged structure, these materials can selectively guide the penetrating direction of light due to the trapping of photons with a specific wavelength. Based on this optical phenomenon, TiO2 with ordered macroporous structure could be used as both optical element and current collector when applied to dye-sensitized solar cells (DSSCs).266,267 Macroporous TiO2 skeleton exhibits highly accessible surface, thus improving the contact with the electrolyte, the adsorption of the dyes and the charge transfer across the interface, while its optical properties can enhance the efficiency of DSSCs by expanding the absorption spectrum. In order to further functionalize the system, colloidal templates can usually co-assemble with other nanospheres. For example, Zhao et al. created magnetic 3D ordered macroporous siliceous materials, in which magnetic Fe3O4 nanoparticles were guided into the internal voids of the polymer template during the co-sedimentation process.268 The Fe3O4 was then further embedded in a silica framework after infiltrating the precursor. This magnetic macroporous silica demonstrated good affinity and high separation efficiency for biomacromolecules (microcystins), and could be easily recycled. The co-assembly between colloidal templates and functional particles is another promising approach. Cong and co-workers have employed this method to prepare superparamagnetic macroporous Fe3O4.269 To prevent the structure from collapsing, an organic polymer template was chemically extracted from Fe3O4/polymer hybrid with THF. After further oxidization and reduction treatments, the macroporous Fe3O4 could be 1186 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 19. Preparation of hollow silica vesicles through LbL assembly of polyelectrolytes and silica particles on colloidal templates.

converted into Fe2O3 or Fe. Caruso, Möhwald, and co-workers reported the formation of hollow silica vesicles through LbL assembly of polyelectrolytes and silica particles on PS-latex colloids (Figure 19).270 The subsequent destruction of the core template particles led to the formation of hollow silica/polymer hybrid spheres, and further calcination resulted in pure silica hollow spheres. The latter concept is now widely used to prepare various kinds of capsular shell objects. Sasaki et al. reported the synthesis of titania hollow particles via LbL selfassembly approach using exfoliated unilamellar titania nanosheets as inorganic shell building blocks.271 PS and poly(methyl methacrylate) spheres with different diameters were employed as colloidal templates, and polyethylenimine was utilized to modify the surface charge of the polymers. The ultrathin nature (0.75 nm) of the 2D nanosheets enabled the tailoring of the shell thickness at the nanometer scale level by varying the number of coating cycles. Miyamoto et al. also reported the synthesis of macroporous solids with a variety of structures from colloidal mixtures of PS spheres and inorganic nanosheets.272 The relative size differences between the spheres and the nanosheets strongly affected the structure. 3.2 Zeolite Templates. Zeolites are microporous crystalline aluminosilicates with cages and channels of molecular size ranging from 2 to 15 ¡ in diameter. The framework typically consists of tetrahedrally coordinated aluminum and silicon. The spatially periodic porous structure of zeolites as templates can be utilized to control the nanostructure of microporous carbon materials at the nanometer scale (Figure 20). Firstly, the zeolite channels are filled with a carbon precursor such as furfuryl alcohol (FA) and then carbonized. After removing the zeolite template, nanoporous carbon with a replicated structure from the zeolite framework is obtained. So far, several types of zeolite-templated carbons (ZTCs) with high specific surface areas, large pore volumes, and various morphologies, have been synthesized using zeolite Y/X, zeolite β, ZSM-5-type zeolite, and EMT-type zeolite.273­279 In addition, N-doped ZTCs279 and BN-doped ZTCs273 have also been prepared. ZTCs are ordered microporous carbons consisting of 3D ordered frameworks of buckybowl-like nanographenes with © 2015 The Chemical Society of Japan

Figure 20. Synthesis procedure of the zeolite-templated carbon (ZTC). (a) Crystal structure of the zeolite Y template. (b) Illustration of zeolite/carbon composite. Impregnated carbon is shown by a black framework. (c) Framework structure of the liberated ZTC after HF washing. Reproduced from ref 280.

several sp2-based carbon sites.280 Moreover, they have a high surface areas together with a uniform micropore size of about 1.6 nm, making ZTCs very attractive absorbents, especially for energy storage applications such as hydrogen storage and electric double-layer capacitors.281­291 Since ZTCs have no meso- or macropores, they have a higher particle density, and thus higher surface area (around 3000 m2 g¹1).274 The gravimetric and volumetric surface areas of ZTCs are the highest among all the carbon materials, therefore they exhibit a superior capacity for energy storage. Along with their unique structural properties, ZTCs can be seen as a new generation of 3D graphene-based architecture after the fullerenes (0D), the carbon nanotubes (1D), and the graphene (2D). The introduction of zeolite templates in the synthesis of nanoporous carbons has been reported by several groups. A two-step synthetic approach (impregnation followed by chemical vapor deposition) was developed, leading to the successful synthesis of microporous carbons using zeolite Y as template.292 In this initial study, propylene, acrylonitrile or FA, were employed as carbon precursors. Carbonization followed by the removal of the zeolite template produced microporous carbon materials with a specific surface areas of 1320­2260 m2 g¹1, and a total pore volume ranging from 0.96 to 1.87 cm3 g¹1. Mallouk and co-workers employed zeolites Y, L, and β as templates to synthesize microporous carbons with a specific surface area as high as 1580 m2 g¹1.293 It was found that the zeolite templates have a direct relationship with the structural and topological properties of the obtained carbons. Rodriguez-Mirasol et al. also reported the preparation of microporous carbons with a wide pore size distribution and well-developed porosity using zeolite Y as template.294 A chemical vapor deposition (CVD) method was employed for infiltrating a carbon source into the pores of the zeolite template. They found that the apparent specific surface area of the resulting microporous carbons increased with increasing the carbonization temperature. Furthermore, Meyers et al. synthesized porous carbon materials with a surface area of about 1000 m2 g¹1 using zeolites Y, β, and Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

ZSM-5 as well as Montmorillonite Clay (K10) as templates and acrylonitrile, FA, pyrene, and vinyl acetate as carbon precursors, followed by carbonization at 600 °C.295 Generally, filling small-sized zeolite nanochannels with infiltrated carbon source is much more difficult. Kyotani et al. developed a new two-step synthetic strategy to prepare ZTCs with a 3D periodicity using zeolite as a template.275,277 This strategy involves the thermal treatment of a zeolite/carbon composite, followed by the subsequent synthesis of microporous carbons through CVD. The infiltration of FA, followed by carbonization with CVD using propylene gas at 700 or 800 °C allows the ZTC to retain the periodicity of the zeolite Y template. The obtained carbon showed a surprisingly high BET specific surface area of 3600 m2 g¹1 and micropore volume of 1.52 cm3 g¹1. They reported ZTCs with narrower pore size distribution and extremely high BET surface area reaching 3730 m2 g¹1 under optimized synthetic conditions.296,297 Several efforts have been made for controlling the surface property of ZTC by changing the zeolite template compositions. For example, oxygen-containing groups can be formed on the interface between the carbon and the walls of the zeolite template.298 3.3 Mesoporous Templates. In this methodology, the mesopores of the hard templates (silica or carbon) are filled with precursors such as carbon sources or metal species (Figure 21a). Then, the desired compositions within the mesopores can be achieved through thermal conversion or chemical reduction. Finally, the desired mesoporous materials are obtained by removing the hard-template. Pioneering works were reported by Ryoo and co-workers in which they synthesized ordered mesoporous carbons “CMK-1”299 and “CMK-3”300 using MCM-48 and SBA-15 as template, respectively. Independently, Hyeon et al. proposed a similar approach to prepare well-ordered mesoporous carbons designated as the SNU series.301 The hybridization of mesoporous carbons with other substances is critical for developing new properties. The synthesis of well-ordered mesoporous carbon impregnated with In2O3 nanoparticles for supercapacitor electrodes was also reported, where the uniformly distributed In2O3 nanoparticles in the mesoporous carbon matrix are utilized for enhancing the capacitive performance.302 Mesoporous carbons with different concentration of fullerene cages were synthesized from a fullerenol-based precursor solution. The fullerene cages embedded in the framework are electrochemically active, showing their high potential as electrode material in electric doublelayer capacitors.303 Lin et al. prepared mesoporous carbon nanoparticles by using MCM-48-type mesoporous silica nanoparticles as hard template.304 However, the hard-templating strategy is complex and industrially unfeasible as the synthetic pathway involves several steps. The same concept was also applied to the preparation of novel nanoporous materials with different compositions, such as metal oxides and metals.305­308 A hard-templating route was extended to the synthesis of nanoporous metals by synthesizing a 3D framework consisting of interconnected Pt nanowires of 3 nm diameter obtained by impregnating tetraammineplatinum(II) nitrate into MCM-48 silica.309 The impregnated Pt species were reduced by H2 flow and finally the silica template was removed by HF treatment. By combining the electrochemical deposition of Pd salt with the hard-template method, Lu © 2015 The Chemical Society of Japan | 1187

Figure 21. (a) Illustration of hard-templating method using mesoporous silica. (b) Low- and (c) high-magnification SEM images of the obtained mesoporous Pt nanoparticles prepared with mesoporous silica KIT-6. Reproduced from ref 311.

and co-workers successfully synthesized a thin film consisting of ordered arrays of Pd nanowires.310 Pt single crystals with monodispersed polyhedral and olive-shaped morphologies were synthesized by using KIT-6 (double gyroid structure,
and SBA-15 (2D hexagonal structure, p6mm) mesopoIa3d) rous silica, respectively (Figures 21b and 21c).311 It is found that the reduction and growth kinetics play a critical role in the rational design of mesoporous crystals. Using mild reducing agents, like ascorbic acid, provides enough time for the reductants to access the inner regions of the mesoporous silica. Slow nucleation and growth of Pt can occur in the confined silica channels, thus leading to the formation of mesoporous nanocrystals. A variety of compositions including Pt-Ru, Pt-Co, and Pt-Ni have been reported by using this method with the appropriate metal precursors.312,313 In a successive template method, a silica replica (i.e., silica nanorods arranged periodically) is first prepared by using 2D hexagonally ordered mesoporous carbon as template. Then, the obtained silica replica is employed as a new template for the preparation of mesoporous ruthenium by introducing Ru species into the pores followed by their reduction using reducing agents. The silica template is ultimately removed to leave the mesoporous Ru free. By changing the metal species introduced into the silica replica, several mesoporous metals (such as Pd and Pt) can be synthesized.314 4. Sacrificial Templates 4.1 Metal Organic Frameworks. Nowadays, metal­ organic frameworks (MOFs) and porous coordination polymers (PCPs) have gained a considerable attention as they represent a novel class of nanoporous materials with attractive properties (Figure 22). These rationally designed framework structures 1188 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 22. Crystal structures and simplified framework structures of MOF-5 (Zn4O(1,4-benzenedicarboxylate)3), Al-PCP (Al(OH)(1,4-naphthalenedicarboxylate)), and ZIF8 (Zn(2-methylimidazolate)2).

are modularly built from metal clusters and organic ligands, hence, they can be tailored for specific applications. Inspired by their diverse structures, high BET surface area and large pore volume, MOFs or PCPs have been utilized as an alternative precursor for synthesizing nanostructured materials with controlled particle size and morphology under various conditions. Among others, the work of Sada et al. revealed that the transformation of MOF into polymer gel (PG) by crosslinking the organic ligands could preorganize the framework itself after the hydrolysis process. The obtained PG has the typical behavior of a polyelectrolyte gel due to its high content of ionic groups.315 4.1.1 Carbonization of MOFs in Inert Gas: Xu et al. reported for the first time the application of MOFs as sacrificial templates for the synthesis of nanoporous carbons (NPCs) (Figure 23)316 where FA was infiltrated into the micropores of MOF-5 (Zn4O(1,4-benzenedicarboxylate)3) by CVD. After carbonization at 1000 °C, a NPC showing a BET surface area as high as 2872 m2 g¹1 was successfully prepared. The same group further modified their synthesis strategy by using a wet impregnation method to infiltrate FA into the pores of MOF-5 for synthesizing NPCs with improved surface areas ranging from 1141 to 3040 m2 g¹1 at lower carbonization temperatures.317 The micro-/meso-/macropore ratio depends on the method employed to infiltrate FA into the pores (wet impregnation or CVD) and on the carbonization conditions. Besides FA, glycerol, carbon tetrachloride, ethylenediamine, and phenolic resin have been also employed as carbon sources with

© 2015 The Chemical Society of Japan

Figure 23. Schematic representation of construction of NPCs from MOFs with and without furfuryl alcohol as a carbon source.

MOF-5.318,319 A wide variety of MOFs, including MOF-5, Al-PCP, and zeolitic imidazolate frameworks-8 (ZIF-8), have been reported as promising carbon precursors for synthesizing high yielding NPCs, which showed promising properties for gas adsorption, electrochemical capacitance, sensing, and catalysis.320­324 Considering the large carbon content of organic components in MOFs or PCPs, additional carbon sources as additives are not always necessary. Yamauchi and co-workers prepared NPCs by direct carbonization of Al-based PCPs (Figure 23).325 By applying the appropriate carbonization temperature, both high surface area and large pore volume could be achieved. The obtained NPC showed a much higher porosity than other carbon materials (such as activated or mesoporous carbons). This new type of carbon material exhibits superior sensing capabilities toward toxic aromatic substances. Kurungot et al. prepared NPCs by direct carbonization of Zn-based MOF-5 and the impact of the constituting MOF ligands on the properties of the obtained carbons was studied as well.326 MOFs with rigid benzene-based ligands resulted in high surface area carbons of 2184 m2 g¹1. As another example, after direct thermal treatment of core­shell ZIF-8@ZIF-67 crystals, selectively functionalized nanoporous hybrid carbon materials with a nitrogen-doped carbon (NC) core and a highly graphitic carbon (GC) shell were obtained. Core­shell ZIF-8@ZIF-67 crystals were designed and prepared through a seed-mediated growth method. This is the first example of the integration of NC and GC in a single particle at the nanometer scale level. The obtained nanoporous hybrid carbon material combines the advantageous properties of NC and GC and exhibits a superior specific capacitance.327 Although the earlier attempts to synthesize NPCs were successfully realized by using MOF-5, control over porous Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

structures and particle morphologies was scarcely presented. It was demonstrated that porous carbon nanofibers can be synthesized through carbonization of fiber-shaped Al-PCP infiltrated with FA.328 After carbonization, NPC fibers were successfully obtained with embedded γ-alumina particles. Further treatment with HF allowed the complete removal of γ-alumina, thereby resulting in pure NPC with a BET surface area of 513 m2 g¹1. NPC particles with different sizes were also successfully synthesized by controlling the starting ZIF-8 crystals. QCM studies proved that the use of small-sized NPC particles can lead to large adsorption uptake and faster sensor response for toxic toluene molecules.329 Recently, a new type of extended MOF structure, the metal­ organic gels (MOGs), was reported.330,331 Compared to MOFs, MOGs suffers from a poor crystallinity and their structure remains difficult to determine. They show, however, great potential in catalysis, gas storage, and separation due to their abundant Lewis acid sites and porous gel structure. In this regard, Zou et al. reported a general way to prepare porous carbons from Al-based MOGs templates, an extended MOF structure.332 Unexpectedly, they found that the carbon product inherits the highly porous nature from the MOG and combines with the integrated character of the gel, thus resulting in a hierarchical porous architecture with ultrahigh surface area (3770 m2 g¹1) and a relatively large pore volume (2.62 cm3 g¹1). These porous carbon materials exhibited considerable hydrogen uptake and excellent electrochemical performances as cathode materials in lithium-sulfur battery applications. 4.1.2 Pyrolysis of MOFs in Air: Recently, researchers have attempted to perform the pyrolysis/thermolysis of MOFs to obtain various metal/metal oxide nanoparticles.333 Until now, many nanoscaled metal and metal oxide materials have been successfully obtained through the use of MOF as a starting template materials, such as Fe3O4,334 Co3O4,335 CoFe2O4,336 Al2O3,337 ZnO,338 and In2O3.339 A good example is the report of the calcination of [Cu3(BTC)2] MOF in a one-end closed horizontal tube furnace leading to the formation of coralloid microstructures with Cu nanoparticle clusters interspersed on the surface.340 However, the formation of porous or nanoporous metal oxides from MOFs has not yet been well understood. It is presumably due to the secondary agglomeration of the metal oxide nanocrystals during the thermolysis process. This strategy can be extended to other nanoporous monometallic and multimetallic oxides with a multitude of potential applications (Figure 24a).341 Remarkably, Kim et al. have recently reported a novel synthetic strategy that exploits a MOF-driven self-templated route toward nanoporous metal oxides, e.g., MgO and CeO2, via thermolysis under inert atmosphere (Figure 24b).342 Among the multitude of coordination polymers, Prussian blue (PB) is a compound with unique properties for practical applications. The general chemical formula of the PB analogues can be described as AlMn[M¤m(CN)6)]¢xH2O (A: alkali metal, M and M¤: transition metals) and are well known as cyano-bridged coordination polymers.343 One of the most promising applications for PB and its analogues is their conversion into nanoporous crystalline metals oxides after thermal treatment in air. In these materials, the metal centers are linked by cyano-groups ligands which can be removed after calcina© 2015 The Chemical Society of Japan | 1189

Figure 25. Polymeric nanofibers prepared by electrospinning process.

Figure 24. (a) SEM image of as-prepared MIL-88-Fe (left) and illustration of the fabrication of spindle-like porous α-Fe2O3 (right). Reproduced from ref 341. (b) Schematic view of the direct conversion from aliphatic carboxylate ligand-based MOF (aph-MOF) to nanoporous metal oxide (np-metal oxide) by heating under nitrogen atmosphere. Reproduced from ref 342.

tion, leading to the formation of nanoporous oxides with high surface area. Recently, a facile route was established to prepare well-organized nanoporous iron oxide hollow particles with various crystalline phases (e.g. α-Fe2O3, γ-Fe2O3) by thermal decomposition of hollow PB particles starting material.344,345 Single crystal-like nanoporous Fe­Co oxides were also prepared by using PB analogues containing Fe and Co.346 When both Fe and Co atoms are contained in the precursors, nanoporous Fe­Co oxide with a highly oriented crystalline framework can be obtained. On the other hand, the framework of the individual oxides obtained from the respective Co- and Fe-contacting precursors are amorphous or poorly crystallized. The obtained single crystal-like nanoporous Fe­Co oxide shows stable magnetic properties at room temperature compared to polycrystalline metal oxides. Recently, a 2D morphology of a cyano-bridged coordination polymer was also synthesized by controlling the reaction rates. The nanoflakes are well-dispersed in solution and have a high accessible surface area. Further thermal treatment leads to the formation of nanoporous metal oxides (e.g. NiO) with the retention of the original flake morphology.347 4.2 Nanostructured Carbon Materials Synthesized from Polymers. Carbon fibers made from polyacrylonitrile (PAN) have been widely used for sports equipment and aircrafts. In recent years, various carbon nanomaterials have been prepared by the carbonization of polymers. The final morphologies of the carbon materials can be controlled by selecting the structures of the polymers used as carbonization precursor. 1190 | Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Graphite sheets have been synthesized by carbonizing polyimide (PI) films at around 800 °C in a vacuum or inert gas and further heating over 2000 °C.348,349 There are three steps in the heat treatment process of polymers: (1) gas generation by depolymerization and decomposition of polymers, (2) carbonization via melting process, and (3) carbonization in solid states. Carbonized materials can be obtained via melting process, but the morphology of the original polymers is destroyed and does not transcript on the final structure. This is why thermosetting resins, such as PI and phenol resin, are good candidates as they can be carbonized in the solid state. 4.2.1 Carbon Nanofiber Prepared from Polymer: The development of spinning processes opened a new production range of polymeric nanofibers (Figure 25a). Carbon nanofibers (CNFs) are obtained from the carbonization of a polymeric nanofiber precursor. Many reports described the carbonization of PAN precursor nanofibers350 produced by electrospinning process.351 The electrospun PAN-based CNFs can be used in electrochemical energy storage such as supercapacitors352 and fuel lithium-ion batteries.353 The randomly oriented web structure is a common morphology obtained from electrospinning PAN-based CNFs. Aligned CNFs can be obtained through the carbonization of aligned PAN precursor nanofibers by using electrospinning processes with improved fibers collection methods.354­356 Core/shell polymer fibers are produced by using co-electrospinning process.357 Zussman et al. synthesized carbonized micro-/nanotubes from core/shell fibers which were obtained from poly(methyl methacrylate) (PMMA, core) and PAN (shell) by co-electrospinning process (Figures 25b­ 25e).358 The PMMA core is decomposed but the shell (PAN) is stabilized and carbonized during the heating process. Composite nanofibers containing carbonization catalysts or stabilization promoters can be prepared by using electrospinning processes in order to improve the characteristics of the CNFs. Park et al. synthesized graphitic CNFs with wellcrystallized graphite structure from electrospun PAN nanofibers containing iron(III) acetylacetonate as graphitization catalyst.359 Zhou et al. used aligned electrospun PAN nanofibers containing phosphoric acid as stabilization promoter to produce graphitic CNFs exhibiting a mechanical strength 62.3% higher than the graphitic CNFs made from the same precursor without phosphoric acid.360

© 2015 The Chemical Society of Japan

CNFs can be produced from a polymer blend technique. Polymer blends contain carbon precursor polymer (CPP) particles and a thermally decomposable polymer (TDP) as a matrix. The blend is extensively elongated during the spinning process which pulls the polymer blend out through a small hole. Therefore, CNFs are obtained after removing the TDP during the carbonization process. Oya et al. prepared CNFs with 200­300 nm diameter from phenol-formaldehyde resin and polyethylene used as CPP and TDP, respectively.361 Carbon nanotubes (CNTs) with 10­20 nm outer diameter were produced from threefold-layered core/shell particles consisting of PMMA as TDP and PAN as CPP. CNFs can also be produced from biopolymers. Kaburagi et al. reported the preparation of graphitic CNFs from bacteria cellulose362 and Kyotani et al. obtained carbon papers containing graphitic CNFs from iodinetreated Japanese paper which is mainly composed of cellulose microfibers.363 Nogi et al. reported that the external surface area of CNFs prepared from chitin nanofibers was three times that of CNFs prepared from wood cellulose nanofibers.364 4.2.2 Carbon Materials Made from Conjugated Polymers: It is expected that carbonization of conjugated polymers should lead to a high conversion yield as they contain many sp2 hybrid carbons. Polyacetylene (PA) being mostly composed of carbon (>92 wt %), it represents a good candidate for carbonization and graphitization.365 Polydiacetylene can be synthesized from diacetylenes by UV irradiation-assisted polymerization in a wide range of organized structures such as single crystals, self-assembling structures and solutions. The morphology of polydiacetylene replicates that of diacetylene structure. Luo et al. reported a room temperature carbonization of poly(diiododiacetylene) (PIDA) nanofibers which forms highly oriented nanofibers upon isolation of the cocrystals.366 They obtained CNFs with 300­500 nm diameter by adding Lewis bases (e.g. pyrrolidine) into a suspension of PIDA dispersed in methanol at room temperature. Polyaniline (PANI) nanotubes were prepared by a self-assembly process in the presence of carboxylic acids. The carbonized PANI nanotubes have outer diameters of 100­260 nm and lengths ranging from 0.5 to 5 ¯m.367­369 The electrical conductivity of the nanotubular PANI precursor increased upon carbonization. Stejskal et al. reported the carbonization of colloidal PANI particles stabilized with poly(N-vinylpyrrolidone) or silica nanoparticles370 leading to specific surface areas as high as 200 and 205 m2 g¹1, respectively. The structure and morphology of polypyrrole (PPy) can be controlled by template polymerization. The CNTs are synthesized from the carbonization of PPy nanotubes fabricated by using anodic aluminium oxide as template (Figures 26a and 26b).371 Dong et al. reported CNTs synthesized from PPy/ PMMA coaxial fibers where the sacrificial PMMA fibers obtained from electrospinning process were coated with PPy and decomposed during the carbonization process.372 Jang and co-workers synthesized 2 nm sized graphite nanoparticles through carbonization of PPy nanoparticles prepared by microemulsion polymerization.373 They also synthesized carbon nanocapsules,374 magnetic carbon nanoparticles,375 and reported a new method for the fabrication of fullerenes from carbonization of PPy nanoparticles.376 Graphite films could also be prepared from the carbonization of poly( p-phenylene vinylene) Bull. Chem. Soc. Jpn. 2015, 88, 1171–1200 | doi:10.1246/bcsj.20150143

Figure 26. SEM and TEM images of PPy nanotubes prepared using AAO membranes with pore diameters of (a) 20 nm and (b) 100 nm, at a fixed amount of monomer (0.05 mL). Reprinted with permission from ref 371.

(PPV) films.377,378 Ejima et al. obtained a long-range ordered hexagonal packing of porous carbons from the carbonization of PPV honeycomb films fabricated through breath figure method.379 Others reported the preparation of microporous carbons obtained from polythiophene-based polymer networks.380 4.2.3 Chiral Carbon-Based Materials: Chiral carbonbased materials with helical structures are expected to lead to novel chiroptical, electrical, and electromagnetic properties. They can also be used for asymmetric catalysis and chiral separation systems. Kyotani et al. prepared helical carbons and graphite films from iodine-doped helical PA films synthesized in a chiral nematic liquid crystal (N*-LC) under asymmetric reaction field (Figure 27).381­383 It was shown that the spiral morphology of the iodine-doped helical PA remains unchanged, even after carbonization and graphitization. They reported that a single helical graphitic fibril could be observed on SEM and TEM images and on selected-area electrondiffraction profiles. Matsushita et al. prepared helical carbons and graphite films from helical poly(3,4-ethylenedioxythiophene) films synthesized by electrochemical polymerization in N*-LCs.384 Shopsowitz et al. synthesized N* mesoporous carbon from the pyrolysis of nanocrystalline cellulose (NCC).385 The mixture between NCC and tetramethyl orthosilicate was slowly evaporated to form N* NCC-silica composite films which were further pyrolyzed. The N* mesoporous carbon films, which were finally obtained after removing the silica from the carbon­silica composite exhibited a high specific surface area and can be employed as an efficient electrode material for supercapacitors. Liu synthesized chiral CNTs from self-assembled chiral PPy nanotubes prepared by using surfactants derived from L- and D-glutamic acids.386 The final leftand right-handed chiral CNTs had distinct optical activity and were obtained from the carbonization of the left- and righthanded chiral PPy nanotubes, respectively. 5. Summary As time goes, nanoporous materials seem to offer limitless possibilities in a wide range of applications, such as catalysis, absorbents, sensors, optical and photovoltaic devices, fuel cells as well as biochemical technology like drug delivery or molecular sensing, and still, they have not reveal their entire potential yet. As previously mentioned, the procedures based on templated syntheses are simple enough to be carried out

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Figure 27. (a) Schematic representation of the preparation of a helical graphite film with concentrically curled morphology, and (b, c) SEM images of helical carbon films. Reproduced from ref 382.

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Award recipient Prof. Yusuke Yamauchi received his bachelor’s degree in 2003, master’s degree in 2004, and Ph.D. in 2007 from Waseda University in Japan. After receiving his Ph.D., he joined NIMS as permanent staff. Since 2008, he started his own research group: the “Inorganic Materials Laboratory”. He has published more than 350 papers in international refereed journals with more than 8500 citations. He concurrently serves as a visiting professor in several universities (Tianjin Univ. in China, Wollongong Univ. in Australia, King Saud Univ. in Saudi Arabia, and Waseda Univ. in Japan), an associate editor of APL Materials published by the American Institute of Physics (AIP), and an editorial board member of Scientific Reports published by the Nature Publishing Group (NPG). He has received many outstanding awards, such as the CSJ Award for Young Chemists, the Chemical Society of Japan (CSJ) in 2014, the Young Scientists’ Prize of the Commendation for Science and Technology by MEXT in 2013, the PCCP Prize by the Royal Society of Chemistry in 2013, the Tsukuba Encouragement Prize in 2012, the Ceramic Society of Japan (CerSJ) Award in 2010, and the Inoue Research Award for Young Scientists in 2010. His major research interest is tailored design of novel nanoporous materials with various shapes and compositions toward practical applications.

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© 2015 The Chemical Society of Japan

Prof. Katsuhiko Ariga is the Director of the Supermolecules Group and Principal Investigator of the World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA) at the National Institute for Materials Science (NIMS). He was born in 1962, and received his B.Eng., M.Eng., and Ph.D. degrees from the Tokyo Institute of Technology (TIT). He was an Assistant Professor at TIT, worked as a postdoctoral fellow at the University of Texas at Austin, USA, and then served as a group leader in the Supermolecules Project at Japan Science and Technology Agency (JST). Thereafter, he worked as an Associate Professor at the Nara Institute of Science and Technology and then got involved with the ERATO Nanospace Project at JST. In January 2004, he moved to NIMS. He has been also appointed as a Principal Investigator of WPI MANA. His major interests are the fabrication of novel functional nanostructures based on molecular recognition and self-assembly including Langmuir­Blodgett films, layer-by-layer films, and mesoporous materials.

Dr. Victor Malgras received his bachelor degree in physics engineering at the Polytechnic School of Montreal (Canada), his master degree in nanoscience at the University Toulouse III (France), and his Ph.D. in photovoltaic nanomaterial engineering at the University of Wollongong (Australia). He specialized himself in various fields such as carbon nanotubes, hybrid surface characterization, surfactant-assisted synthesis of porous titania and chemical synthesis and analysis of semiconducting nanostructures for photovoltaic applications. He is now undergoing a postdoctoral fellowship in Prof. Yamauchi’s group at the National Institute for Materials Science (Japan) on the synthesis of mesostructured photoactive metal­organic perovskite.

Dr. Qingmin Ji earned her Ph.D. (2005) in chemistry from the University of Tsukuba and worked as a postdoctoral researcher in the National Institute of Advanced Industrial Science and Technology (AIST) under the supervision of Prof. Toshimi Shimizu. She joined in the Supermolecules Group at the National Institute for Materials Science (NIMS) in 2006. Her research currently focuses on the formation of layer-by-layer films and the application of mesoporous structures.

Mr. Yuichiro Kamachi received his bachelor’s degree in 2010 and master’s degree in 2012 from Department of Life, Environment and Materials Science, Fukuoka Institute of Technology (FIT). He specialized himself in surfactant-assisted synthesis of porous materials. He is now technical assistant in Prof. Yamauchi’s group at the National Institute for Materials Science (Japan).

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Dr. Taizo Mori graduated from the Department of Polymer Chemistry at Kyoto University and obtained his Ph.D. in 2009. He joined the Supermolecules Group at the National Institute for Materials Science (NIMS) in 2009 and is now a postdoctoral research associate in the Liquid Crystal Institute, at Kent State University since 2015. His research interests include supramolecular science, synthesis of conjugated polymer in liquid crystal and chirality control of molecules. Prof. Fa-Kuen Shieh received his bachelor’s degree majoring in Chemistry in 1994 and master’s degree studying in Biochemistry in 1996 from National Chiao-Tung University, Taiwan. After 2years mandatory military service and 3-years high school teaching, he joined Prof. Norbert O. Reich as Ph.D. student in the Department of Chemistry & Biochemistry at UC Santa Barbara, USA in 2002 and meanwhile he was awarded the scholarship of government sponsorship for overseas from Ministry of Education, Taiwan. After graduating with a Ph.D. degree in Protein Crystallography in 2007, he moved to UC Los Angeles, joining the laboratory of Prof. Robert T. Clubb for one year post-doctoral training in the Molecular Biology Institute. In August 2008, he went back to Taiwan and was appointed an Assistant Professor in the Department of Chemistry at the National Central University. Currently, he is an Associate Professor and his major interests are concentrating on obtaining nanostructured MOFs by use of green synthetic system and their applications in the fields of enzymatic catalysis, drug delivery, etc.

Prof. Kevin C.-W. Wu received his Ph.D. from the University of Tokyo, Japan in 2005. From April 2005 to September 2006, he worked on the orientational control of 2D hexagonal mesoporous thin films (Waseda University, Japan) as a postdoctoral fellow. From October 2006 to July 2008, he underwent a postdoctoral fellowship in Prof. Victor S.-Y. Lin’s group (Iowa State University, U.S.A.). He was appointed an Assistant Professor at the Department of Chemical Engineering, National Taiwan University, Taiwan in August 2008 and was promoted as Associate Professor in 2012. His current interest is the synthesis of nanoporous materials with desired morphologies and functionalities for biomedical and energy-related applications.

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© 2015 The Chemical Society of Japan