Synthesis of Ordered Mesoporous Carbon Materials by Dry Etching

A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT‐6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro‐ and mesopore volumes (0.6 and 1.6 cm³ g^?1, respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m² g^?1 was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.     

Nanocast mesoporous mixed metal oxides for catalytic applications

Since the initial discovery of ordered mesoporous silica in early 1990s, considerable innovations were achieved regarding their synthesis, characterization and applications. One of the best outcomes of these intense research efforts is the development of a solid templating method called “nanocasting”, which is based on using mesoporous silica (or carbon) as a rigid template. This solid-to-solid replication method opened the pathway for synthesizing high surface area non-silica mesostructured materials that are challenging to obtain through conventional self-assembly processes which are based on amphiphilic soft structure-directing agents. In particular, the replicated metal oxide mesostructures obtained by this method were found to be highly versatile for a wide range of applications, especially in catalysis, owing to their large specific surface area. Furthermore, the nanocasting method is particularly suited for the synthesis of mixed metal compositions, favored by the possible confinement of mixed precursors in the nanopores of the template. In this account, we discuss some of the recent developments regarding the synthesis of nanocast mixed metal oxides and their perspectives of catalytic applications. It is here the choice of the authors to place emphasis on a few representative examples of compositions (e.g., non-noble metal-based catalysts, perovskites) and catalytic reactions (e.g., hydrogen production, gas-phase oxidation).     

A strategy for the synthesis of mesostructured metal oxides with lower oxidation states

A detailed study on the pseudomorphic conversion of ordered mesoporous Co(3)O(4) and ferrihydrite into CoO and Fe(3)O(4), respectively, by using alcohol/water vapor as a gentle reducing agent is described. The reduction conditions for the transformation were optimized. In addition, the first one-pot synthesis of mesostructured CoO by using nanocasting with cubic ordered silica as a hard template is demonstrated.     

双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

Ordered mesoporous non-oxide materials

Ordered mesoporous inorganic non-oxide materials attract increasing interest due to their plenty of unique properties and functionalities and potential applications. Lots of achievements have been made on their synthesis and structural characterization, especially in the last five years. In this critical review, the ordered mesoporous non-oxide materials are categorized by compositions, including non-oxide ceramics, metal chalcogenides, metal nitrides, carbides and fluorides, and systematically summarized on the basis of their synthesis approaches and mechanisms, as well as properties. Two synthesis routes such as hard-templating (nanocasting) and soft-templating (surfactant assembly) routes are demonstrated. The principal issues in the nanocasting synthesis including the template composition and mesostructure, pore surface chemistry, precursor selection, processing and template removal are emphatically described. A great number of successful cases from the soft-templating method are focused on the surfactant liquid-crystal mesophases to synthesize mesostructured metal chalcogenide composites and the inorganic-block-organic copolymer self-assembly to obtain non-oxide ceramics (296 references).     

Synthesis of highly ordered mesoporous crystalline WS(2) and MoS(2) via a high-temperature reductive sulfuration route

A high-temperature reductive sulfuration method is demonstrated to synthesize highly ordered mesoporous metal sulfide crystallites by using mesoporous silica as hard templates. H2S gas is utilized as a sulfuration agent to in situ convert phosphotungstic acid H3PW12O40.6H2O to hexagonal WS2 crystallites in the silica nanochannels at 600 degrees C. Upon etching silica, mesoporous, layered WS2 nanocrystal arrays are produced with a yield as high as 96 wt %. XRD, nitrogen sorption, SEM, and TEM results reveal that the WS2 products replicated from the mesoporous silica SBA-15 hard template possess highly ordered hexagonal mesostructure (space group, p6mm) and rodlike morphology, analogous to the mother template. The S-W-S trilayers of the WS2 nanocrystals are partially oriented, parallel to the mesochannels of the SBA-15 template. This orientation is related with the reduction of the high-energy layer edges in layered metal dichalcogenides and the confinement in anisotropic nanochannels. The mesostructure can be 3-D cubic bicontinuous if KIT-6 (Iad) is used as a hard template. Mesoporous WS2 replicas have large surface areas (105-120 m2/g), pore volumes ( approximately 0.20 cm3/g), and narrow pore size distributions ( approximately 4.8 nm). By one-step nanocasting with the H3PMo12O40.6H2O (PMA) precursor into the mesochannels of SBA-15 or KIT-6 hard template, highly ordered mesoporous MoS2 layered crystallites with the 2-D hexagonal (p6mm) and 3-D bicontinuous cubic (Iad) structures can also be prepared via this high-temperature reductive sulfuration route. When the loading amount of PMA precursor is low, multiwalled MoS2 nanotubes with 5-7 nm in diameter can be obtained. The high-temperature reductive sulfuration method is a general strategy and can be extended to synthesize mesoporous CdS crystals and other metal sulfides.     

Synthesis and characterization of nanocast silica NCS-1 with CMK-3 as a template

Nanocast silica (NCS-1) was synthesized by a casting process by employing the mesoporous carbon CMK-3 (the replica of SBA-15) as a template, tetraethoxysilane (TEOS) as the silica source, and hydrochloric acid (HCl) as the catalyst. The ordered carbon template was removed by employing different methods, such as calcination, thermal treatment followed by calcination, and controlled combustion. According to XRD and TEM characterization, NCS-1 exhibits an ordered structure with hexagonal symmetry and retains the morphology of the original SBA-15 used for the synthesis of CMK-3 over two replication steps on the nanometer scale. This demonstrates the well-connected porosity in CMK-3 type carbon, which can be used as a mold to synthesize mesostructured materials. The nitrogen adsorption isotherms generally show type IV shape, indicating mesoporous characteristics. The structure of NCS-1 is strongly influenced by variables of the nanocasting process, such as the loading amount of silica, hydrolysis temperature, and carbon removal methods. The surface area, pore size, and pore volume of NCS-1 can be tuned to a certain range by varying these parameters.     

Ordered mesoporous carbon nitrides with graphitic frameworks as metal-free, highly durable, methanol-tolerant oxygen reduction catalysts in an acidic medium

Developments of high-performance cost-effective electrocatalyts that can replace Pt catalysts have been a central theme in polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). In this direction, nitrogen-doped carbon nanostructures free of metallic components have attracted particular attention. Here we show that directing graphitic carbon nitride frameworks into mesoporous architecture can generate a highly promising metal-free electrocatalyst for an oxygen reduction reaction (ORR) in an acidic medium. The ordered mesoporous carbon nitride (OMCN) was synthesized with a nanocasting strategy using ordered mesoporous silica as a template. A variety of characterizations revealed that the OMCN is constructed with graphitic carbon nitride frameworks and ordered arrays of uniform mesopores. The OMCN showed significantly enhanced electrocatalytic activity for ORR compared to bulk carbon nitride and ordered mesoporous carbon in terms of the current density and onset potential. A high surface area and an increased density of catalytically active nitrogen groups in the OMCN appear to contribute concomitantly to the enhanced performance of the OMCN. Furthermore, the OMCN exhibited superior durability and methanol tolerance to a Pt/C catalyst, suggesting its widespread utilization as an electrocatalyst for PEMFCs and DMFCs.     

Block copolymer-templated mesoporous oxides

Block copolymers (BC) are indeed suitable and versatile templates for the creation of mesostructured and mesoporous materials. Great advances have been achieved in the last 3 years. Nowadays, it is possible to obtain highly controlled large-pore and highly stable mesostructured and mesoporous materials (silica, non-silica oxides, carbons,…) shaped as powders, films, monoliths or aerosols. This paper reviews mainly the synthesis of BC-templated mesostructured oxides, stressing in the physical, chemical and processing parameters, which have to be thoroughly controlled to reproducibly obtain mesoporous materials.     

Facile synthesis and characterization of novel mesoporous and mesorelief oxides with gyroidal structures.

In this paper, we bring forward an effective strategy, solvothermal postsynthesis, to prepare ordered mesoporous silica materials with highly branched channels. Structural characterizations indicate that the titled mesoporous materials basically have the cubic double gyroidal (space group Ia-3d) structure with small fraction of distortions. The mesopore sizes and surface areas can be up to 8.8 nm and 540 m2/g, respectively, when microwave digestion is employed to remove the organic templates. A phase transition model is proposed, and possible explanations for the successful phase transition are elucidated. The results show that the flexible inorganic framework, high content of organic matrix, and nonpenetration of poly(ethylene oxide) segments may facilitate the structural evolution. This new synthetic strategy can also be extended to the preparation of other double gyroidal silica-based mesoporous materials, such as metal and nonmetal ions doped silica and organo-functionalized silica materials. The prepared 3D mesoporous silica can be further utilized to fabricate various ordered crystalline gyroidal metal oxide "negatives". The mesorelief "negatives" (Co3O4 and In2O3 are detailed here) prepared by impregnation and thermolysis procedures exhibit undisplaced, displaced, and uncoupled enantiomeric gyroidal subframeworks. It has been found that the amount of metal oxide precursors (hydrated metal nitrates) greatly influence the (sub)framework structure and single crystallinity of the mesorelief metal oxide particles. The single crystalline gyroidal metal oxides are ordered both at mesoscale and atomic scale. However, these orders are not commensurate with each other.     

Functional-template directed self-assembly (FTDSA) of mesostructured organic-inorganic hybrid materials

Since the discovery of a surfactant directed self-assembly approach for the fabrication of mesoporous silica in 1992, increasing attention has been focused on the design and synthesis of mesostructured functional materials. Organic functionalization is becoming a major topic in this research field, since highly ordered mesostructured organic-inorganic hybrids offer novel functionalities and enhanced performance over their individual components. We begin with a brief overview of the three fundamental methods (post-synthetic grafting technique, co-condensation method, and preparation of periodic mesoporous organosilicas) for the preparation of organically functionalized mesostructured silica, and focus on one of the most promising approaches, which herein was named as functional-template directed self-assembly (FTDSA) approach, and in the eyes of the authors it has a special position in the preparation of this class of hybrid materials. A comprehensive overview of the state of research in the area of FTDSA and its potential applications will be given.     

Random‐Graft Polymer‐Directed Synthesis of Inorganic Mesostructures with Ultrathin Frameworks

A widely employed route for synthesizing mesostructured materials is the use of surfactant micelles or amphiphilic block copolymers as structure‐directing agents. A versatile synthesis method is described for mesostructured materials composed of ultrathin inorganic frameworks using amorphous linear‐chain polymers functionalized with a random distribution of side groups that can participate in inorganic crystallization. Tight binding of the side groups with inorganic species enforces strain in the polymer backbones, limiting the crystallization to the ultrathin micellar scale. This method is demonstrated for a variety of materials, such as hierarchically nanoporous zeolites, their aluminophosphate analogue, TiO₂ nanosheets of sub‐nanometer thickness, and mesoporous TiO₂, SnO₂, and ZrO₂. This polymer‐directed synthesis is expected to widen our accessibility to unexplored mesostructured materials in a simple and mass‐producible manner.     

有序介孔二氧化硅/聚苯胺复合物

本文综述了有序介孔二氧化硅/聚苯胺复合物从出现至今的10余年里的研究进展,介绍了复合物的合成方法,包括气相法、液相法和一步合成法,以及模板剂单体原位合成法等。引入苯胺单体后在孔道内聚合生成聚苯胺,即聚苯胺与有序介孔二氧化硅形成了复合物。该复合物的结构和形貌,以及孔道中聚苯胺的结构形态和电学性质,与本体聚苯胺相比具有显著的变化。这种以有序介孔二氧化硅为模板制备的聚苯胺的单分子导线,有潜力应用在新型的电子或光电子器件上。此外,该复合物因为其独特性质很可能在燃料电池的聚合物电解质膜、湿度传感器、电流变材料以及电化学电容器等方面得到应用。     

Synthesis of ordered mesoporous materials using surfactant liquid crystals or micellar solutions

Formation of ordered mesoporous materials using surfactant templating proceeds via mechanisms relying on optimising interactions between the inorganic and organic components of the synthesis. For oxides, the rates of hydrolysis and condensation of the inorganic species relative the rate of assembly of the mesostructure is crucial. Synthetic strategies to control these factors have been reviewed and it appears that mesostructured silica can be prepared in most phases found in binary surfactant–water systems by optimising the volume fraction of the surfactant and the hydrolysed inorganic precursor.     

Nanoporous silica films containing aluminum and titanium

By utilizing surfactant aggregates as supramolecular templates, mesoporous and mesostructured silicas with highly ordered structures became available. The resulting mesoporous silicas are promising candidates to host various photo- and electro-active species along with catalytically active species, due to their large and controllable pore sizes, highly ordered pore arrangements with low dimensional geometries, and reactive surfaces. We have developed the rapid solvent evaporation method, which is a modified sol-gel process, for synthesizing the mesostructured silica-surfactant films as well as the mesoporous silica films. Supported thin films, self-standing films and bubbles of mesoporous silicas have been synthesized by the rapid solvent evaporation method. The microstructures of the films have also been successfully controlled by changing the synthetic conditions. Taking advantage of the ease of synthetic operation and the transparency and homogeneity of the resulting materials, we have been interested in the introduction of functional units into the mesostructured materials. This paper reports the synthesis of transparent films of titanium- and aluminum-containing nanoporous silicas to modify the surface properties (such as adsorptive and catalytic) of nanoporous silicas. The incorporation of Al led to the formation of cation exchange or acidic sites on the mesopore surface, as revealed by the cationic dye adsorption experiments. The photocatalytic reactions of the Ti-containing nanoporous silica films were also examined.     

Mesoporous silica hybrid membranes for precise size-exclusive separation of silver nanoparticles

One-dimensional (1D) nanomaterials have unique applications due to their inherent physical properties. In this study, hexagonally ordered mesoporous silica hybrid anodic alumina membranes (AAM) were synthesized using template-guided synthesis with a number of nonionic n-alkyl-oligo(ethylene oxide), Brij-type (C(x)EO(y)), which are surfactants that have different molecular sizes and characteristics. The hexagonal mesoporous silicas are vertically aligned in the AAM channels with a predominantly columnar orientation. The hollow mesostructured silicas had tunable pore diameters varying from 3.7 to 5.1 nm. In this synthesis protocol, the surfactant molecular natures (corona/core features) are important for the controlled generation of ordered structures throughout AAM channels. The development of ultrafiltration membranes composed of silica mesostructures could be used effectively in separating silver nanoparticles (Ag NPs) in both aqueous and organic solution phases. This would be relevant to the production of well-defined Ag NPs with unique properties. To create a size-exclusive separation system of Ag NPs, we grafted hydrophobic trimethylsilyl (TMS) groups onto the inner pores of the mesoporous silica hybrid AAM. The immobilization of the TMS groups allowed the columnar mesoporous silica inside AAM to retain this inner pore order without distortion during the separation of solution-phase Ag NPs in organic solvents that may cause tortuous-pore membranes. Mesoporous TMS-silicas inside 1D AAM channels were applicable as a size-exclusive separation system to isolate organic solution-phase Ag NPs of uniform morphology and size.     

Fabrication and characterization of hexagonal mesoporous silica monolith via post-synthesized hydrothermal process

Large-sized, optical transparent mesostructured Brij 56/silica monolith has been fabricated using a lyotropic liquid crystal of Brij 56 (C₁₆EO₁₀) as a template and TMOS as a silica source, combined with a optimizing sol-gel process and a hydrothermal aging process. By programmed temperature drying and calcinations, translucent mesoporous silica monolith with two-dimensional hexagonal structure (P6mm) has bee obtained. The ordered mesoporous silica monoliths have been characterized by small-angle X-ray diffraction, transmission electron microscopy (TEM), and nitrogen adsorption, which shows that the materials have a highly ordered two-dimensional hexagonal mesostructure with the high specific surface area of 837 m² · g⁻¹ and narrow pore distribution with a mean BJH pore diameter of 2.73 nm. Based on calculations and differential scanning calorimetry and thermogravimetric analyses, the action mechanism of the hydrothermal aging process has been proposed: the 100°C hydrothermal conditions and autogenous 2.3 atm pressure promote the condensation and dehydration of silanol groups, with the result that cross-linking degree, the flaws and moisture content in gels are reduced notably. Those processes guarantee the integrity of gels in the following drying process.     

A "teardown" method to create large mesotunnels on the pore walls of ordered mesoporous silica

A "teardown" method to create large mesotunnels (approximately 9 nm) on the pore walls of ordered mesoporous silicas is demonstrated by digesting the organic constituents from polymer-silicate nanocomposites. The ordered mesostructured polymer-silicate composites were first obtained via the evaporation-induced triconstituent co-assembly method by using a low-molecular-weight phenolic resin (resols) as an organic precursor; prehydrolyzed TEOS as an inorganic precursor, and triblock copolymer F127 as a template. All of organic components including F127 and phenolic resins are removed by the microwave digestion (MWD) method from mesostructured polymer-silica composites. While the removal of triblock copolymer F127 generates main pore channels, the phenolic resins can also be torn down from the pore walls, yielding mesotunnels between the channels. The resulting silica products exhibit ordered 2-D hexagonal mesostructure, large pore volume (up to 1.92 cm(3)/g), and very large pore size (up to 22.9 nm), which is even larger than their mesostructural cell parameter (14.2 nm). TEM images confirm the existence of mesotunnels on the silica pore walls. FT-IR and (29)Si solid-state NMR results reveal that these silica products have a large number of silanol groups.     

功能模板导向的自组装合成介孔结构有机／无机复合材料

回顾了近年来硅基介孔材料有机功能化的基本方法和研究进展．基于作者的相关研究工作,着重介绍一种新型的介孔氧化硅有机功能化的方法——功能模板导向的自组装法,阐述了该方法在自组装合成新型有机／无机复合材料方面的应用．     

Hydrophobic mesoporous silica applied in GC separation of hexene isomers

A novel CH₃-functionalized mesoporous silica material (PTM) with nearly spherical morphology was synthesized by a one-step synthesis route using polymethylhydrosiloxane and tetraethoxylsilane in the presence of triblock copolymer P123 as structure-directing agent. Thus-obtained material possessed highly-ordered mesopore arrays and texture with highly CH₃-functionalized surface. As compared with pure siliceous SBA-15, PTM showed the high performance for gas chromatographic separation of hexene isomers.