Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500 degrees C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35 degrees to 80 degrees C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140 degrees C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.

A family of highly ordered mesoporous (20−300 Å) silica structures have been synthesized by the use of commercially available nonionic alkyl poly(ethylene oxide) (PEO) oligomeric surfactants and poly(alkylene oxide) block copolymers in acid media. Periodic arrangements of mescoscopically ordered pores with cubic Im3̄m, cubic Pm3̄m (or others), 3-d hexagonal (P63/mmc), 2-d hexagonal (p6mm), and lamellar (Lα) symmetries have been prepared. Under acidic conditions at room temperature, the nonionic oligomeric surfactants frequently form cubic or 3-d hexagonal mesoporous silica structures, while the nonionic triblock copolymers tend to form hexagonal (p6mm) mesoporous silica structures. A cubic mesoporous silica structure (SBA-11) with Pm3̄m diffraction symmetry has been synthesized in the presence of C16H33(OCH2CH2)10OH (C16EO10) surfactant species, while a 3-d hexagonal (P63/mmc) mesoporous silica structure (SBA-12) results when C18EO10 is used. Surfactants with short EO segments tend to form lamellar mesostructured silica at room temperature. Hexagonal mesoporous silica structures with d(100) spacings of 64−77 Å can be synthesized at 100 °C by using oligomeric nonionic surfactants. Highly ordered hexagonal mesoporous silica structures (SBA-15) with unusually large d(100) spacings of 104−320 Å have been synthesized in the presence of triblock poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) (PEO−PPO−PEO) copolymers. SBA-15 mesoporous structures have been prepared with BET surface areas of 690−1040 m2/g, pore sizes of 46−300 Å, silica wall thicknesses of 31−64 Å, and pore volumes as large as 2.5 cm3/g. A novel cubic (Im3̄m) cage-structured mesoporous silica structure (SBA-16) with a large cell parameter (a = 176 Å) has been synthesized using triblock copolymers with large PEO segments. The EO/PO ratio of the copolymers can be used to control the formation of the silica mesophase:  lowering this ratio of the triblock copolymer moieties promotes the formation of lamellar mesostructured silica, while higher ratios favor cubic mesostructured silica. Cubic mesoporous structures are also obtained when star diblock copolymers are used as structure-directing agents. The calcined ordered mesoporous silicas reported in this paper are thermally stable in boiling water for at least 48 h. The assembly of the inorganic and organic periodic composite materials appears to take place by a hydrogen bonding (S0 H+)(X-I+) pathway. The assembly rate r increases with increasing concentration of [H+] and [Cl-], according to the kinetic expression r = k[H+]0.31[Cl-]0.31.

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THE recent synthesis of silica-based mesoporous materials by the cooperative assembly of periodic inorganic and surfactant-based structures has attracted great interest because it extends the range of molecular-sieve materials into the very-large-pore regime. If the synthetic approach can be generalized to transition-metal oxide mesostructures, the resulting nanocomposite materials might find applications in electrochromic or solid-electrolyte devices, as high-surface-area redox catalysts and as substrates for biochemical separations. We have proposed recently6 that the matching of charge density at the surfactant/inorganic interfaces governs the assembly process; such co-organization of organic and inorganic phases is thought to be a key aspect of biomineralization. Here we report a generalized approach to the synthesis of periodic mesophases of metal oxides and cationic or anionic surfactants under a range of pH conditions. We suggest that the assembly process is controlled by electrostatic complementarity between the inorganic ions in solution, the charged surfactant head groups and—when these charges both have the same sign—inorganic counterions. We identify a number of different general strategies for obtaining a variety of ordered composite materials

The low-temperature formation of liquid-crystal-like arrays made up of molecular complexes formed between molecular inorganic species and amphiphilic organic molecules is a convenient approach for the synthesis of mesostructure materials. This paper examines how the molecular shapes of covalent organosilanes, quaternary ammonium surfactants, and mixed surfactants in various reaction conditions can be used to synthesize silica-based mesophase configurations, MCM-41 (2d hexagonal, p6m), MCM-48 (cubic Ia3d), MCM-50 (lamellar), SBA-1 (cubic Pm3n), SBA-2 (3d hexagonal P6 3 /mmc), and SBA-3 (hexagonal p6m from acidic synthesis media). The structural function of surfactants in mesophase formation can to a first approximation be related to that of classical surfactants in water or other solvents with parallel roles for organic additives. The effective surfactant ion pair packing parameter, g ) V/a 0 l, remains a useful molecular structure-directing index to characterize the geometry of the mesophase products, and phase transitions may be viewed as a variation of g in the liquid-crystal-like solid phase. Solvent and cosolvent structure direction can be effectively used by varying polarity, hydrophobic/hydrophilic properties and functionalizing the surfactant molecule, for example with hydroxy group or variable charge. Surfactants and synthesis conditions can be chosen and controlled to obtain predicted silica-based mesophase products. A room-temperature synthesis of the bicontinuous cubic phase, MCM-48, is presented. A low-temperature (100 °C) and low-pH (7-10) treatment approach that can be used to give MCM-41 with high-quality, large pores (up to 60 Å), and pore volumes as large as 1.6 cm 3 /g is described.

The organization of cationic or anionic organic and inorganic molecular species to produce three-dimensional periodic biphase arrays is described. The approach uses cooperative nucleation of molecular inorganic solution species with surfactant molecules and their assembly at low temperatures into liquid-crystal-like arrays. The organic/inorganic interface chemistry makes use of four synthesis routes with (S+I-), (S-I+), (S+X-I+), and (S-M+I-) direct and mediated combinations of surfactant (cationic S+, anionic S-) and soluble inorganic (cationic I+, anionic I-) molecular species. The concepts can be widely applied to generate inorganic oxide, phosphate or sulfide framework compositions. Distinct lamellar, cubic silica mesophases were synthesized in a concentrated acidic medium (S+X-I+), with the hexagonal and the cubic phases showing good thermal stability. For the hexagonal mesostructured silica materials high BET surface areas (>1000 m₂/g) are found. Hexagonal tungsten(V1) oxide materials were prepared in the presence of quaternary ammonium surfactants in the pH range 4-8. Cubic (Ia3d) and hexagonal antimony(V) oxides were obtained by acidifying (pH = 6-7) homogeneous solutions of soluble Sb(V) anions and quaternary ammonium surfactants at room temperature (S+I-). Using anionic surfactants, hexagonal and lamellar lead oxide mesostructures were found (S-I+). Crystalline zinc phosphate lamellar phases were obtained at low synthesis temperatures (4°C) and lamellar sulfide phases could be also readily generated at room temperature. The synthesis procedure presented is relevant to the coorganization of organic and inorganic phases in biomineralization processes, and some of the biomimetic implications are discussed

I1I. SUPPLENIEN TARY NO &ES

Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.