Opal and inverse opal photonic crystals: Fabrication and characterization

Three-dimensional photonic crystals made of close-packed polymethylmethacrylate (PMMA) spheres or air spheres in silica, titania and ceria matrices have been fabricated and characterized using SEM, XRD, Raman spectroscopy and UV–Vis transmittance measurements. The PMMA colloidal crystals (opals) were grown by self-assembly from aqueous suspensions of monodisperse PMMA spheres with diameters between 280 and 415 nm. SEM confirmed the PMMA spheres crystallized uniformly in a face-centred cubic (fcc) array, and UV–Vis measurements show that the colloidal crystals possess pseudo photonic band gaps in the visible and near-IR regions. Inverse opals were prepared by depositing silica (SiO₂), titania (TiO₂) or ceria (CeO₂) in the voids of the PMMA colloidal crystals using sol-gel procedures, then calcining the resulting structure at 550 °C to remove the polymer template. The resulting macroporous materials showed fcc ordering of air spheres separated by thin frameworks of amorphous silica, nanocrystalline titania or nanocrystalline ceria particles, respectively. Optical measurements confirmed the photonic nature of the inverse opal arrays. UV–Vis data collected for the opals and inverse opals obeyed a modified Bragg’s law expression that considers both diffraction and refraction of light by the photonic crystal architectures. The versatility of the colloidal crystal template approach for the fabrication of macroporous oxide structures is demonstrated.     

网状多级孔结构氧化铁的制备、合成机理及其光催化性质

以九水合硝酸铁为原料, 利用改进的聚合诱导胶体聚集(PICA)的方法制备出三维网络状多级孔结构氧化铁(HPH). 此结构的制备关键是在合成过程中尿素和甲醛聚合生成脲醛树脂(UF). 脲醛树脂一方面在铁的羟基氧化物生长过程中与之杂化形成杂化产物Fe-UF, 另一方面则进一步聚合, 形成脲醛树脂微球(UFM). 脲醛树脂微球作为模板诱导杂化产物Fe-UF在其表面的聚集. 微球与微球之间则由于表面存在的脲醛树脂间的聚合会相互交联形成网络状结构. 经过煅烧处理后, 脲醛树脂及脲醛树脂微球的分解导致不同尺寸孔结构的生成. 光催化研究结果表明, 产物对罗丹明B的降解效率是商用纳米氧化铁的4倍.     

Fabrication of synthetic opals composed of mesoporous SnO2 spheres with an anodization-assisted double template process

Synthetic opals composed of mesoporous SnO₂ spheres were successfully fabricated from anodization of Sn opals, double templated from polystyrene opals. The mesoporous SnO₂ spheres were 440 nm in diameter containing mesopores of 20–40 nm. The resultant mesoporous SnO₂ opals possessed a high specific surface area of 196 m²/g and a grain size of 12 nm as estimated from XRD patterns. Such a hierarchical structure of SnO₂ is a promising candidate for applications in gas sensors, catalysts, and electrode materials since the regularity of the sub-micron opal structure eases transfers of relevant chemical species within the structure while the mesoporosity of the constituent SnO₂ spheres offers sufficient functioning surfaces for targeted applications.     

The size dependent shift of the surface plasmon absorption band of small spherical metal particles

It has been previously established that the surface plasmon of small spherical silver particles, which are embedded in a noble gas matrix, shifts to higher energies (blue shift) as the mean diameterD of the particles decreases (100 Å>D>20 Å). This blue shift has also been found for supported silver particles, and quite recently we observed it by elastic light scattering in the gas phase. This latter experiment proves unambiguously that the blue shift in small silver particles is not induced by interactions with the environment, the presence of which is clearly recognized in less inert matrices such as O₂ or CO. From self-consistent calculations of the surface response of planar jellium surfaces one would expect a red shift, which is also directly confirmed by a few calculations for selected jellium spheres. The contradiction between the observed blue shift for small particles and the predicted red shift for jellium spheres disappears, if one accounts for thed-electrons of silver in a very simple approximation.     

Adsorption properties of ultradispersed powders of aluminum alloys with rare-earth metals,before and after water treatment

Adsorption of nitrogen on Al-3% La, Al-1.5% Sc, and Al-3% Ce powders before and after processing with water in the relative pressure range p/p _s = 10^～3 to 0.999 is experimentally studied at a temperature of 78 K. It is shown that the interaction between ultradispersed powder and water depends on the properties of the original powder, including the original content and composition of the oxide-hydroxide phases in the surface layers of metal particles, and the length and conditions of storage. Results confirming that processing powders containing rare-earth metals with water at room temperature leads to the formation of new phases and affects their morphology are presented. It is shown that the nanopores formed between crystallites on the surface of the particles during oxidation with water and subsequent thermal dehydration play an important role in the properties of powders processed with water. The specific surface and the porosity of powders are calculated.     

Percolation of randomly centered rods and spheres

The percolation properties of randomly centered rods and spheres are studied. The approach is based on the detailed study of frequencies of cluster occurrences. For random rods, the analytic expressions are derived for all cluster frequencies. It is then shown that one-dimensional systems of random rods exhibit critical behaviour with? _c = ∞,γ = 1. For randomly centered spheres, we designed a numerical method for calculating the cluster frequencies. The approach is based on the principles of the Monte Carlo method. It can cope with clusters containing up to seven particles, which should suffice for the evaluation of accurate values of critical density and critical exponents.     

Combination of microspheres and sol-gel electrophoresis for the formation of large-area ordered macroporous SiO2

A simple and effective fabrication scheme involving sequential electrophoretic depositions of polystyrene (PS) microspheres (500 nm and 1 μm in diameter) and SiO₂ sols (~ 5 nm in diameter) to produce large-area ordered macroporous SiO₂ inverse opals (2 × 2 cm²) on ITO substrates is demonstrated. The zeta potentials for PS microsphere suspension and SiO₂ sols are measured to determine an optimized processing window in which both samples carry negative surface charges and sol-gel transformation can be properly implemented. Our approach entails the electrophoresis of PS microspheres to render a colloidal crystal with negligible defects. Afterward, SiO₂ sols are infiltrated to the interstitial voids among the closely-packed PS microspheres via another electrophoresis process, followed by an oxidation treatment to remove the PS colloidal template and complete the densification of SiO₂ gels. The resulting SiO₂ inverse opals reveal impressive surface uniformity and structural integrity. Fourier transform infrared spectroscopy confirms the complete removal of PS microspheres, leaving an intact SiO₂ skeleton, whereas X-ray diffraction pattern indicates its amorphous nature.     

Dynamics of water vapor sorption in a CaCl2/Silica Gel/Binder bed: The effect of the bed pore structure

The dynamics of water vapor sorption in a compact, binder-containing bed of a CaCl₂-in-silica-gelpores sorbent has been investigated by NMR microscopy. The procedure suggested for the preparation of this bed allows the porous structure of the bed to be modified in a wide range. The bed pore structure and water transfer in the bed have been studied in relation to the particle size of the initial silica gel, the size of mesopores in the sorbent particles, and the binder content. By varying these parameters, it is possible to optimize the ratio of the diffusion resistance of the interparticle macropores to that of the internal mesopores of the particles. If sorption is controlled by water diffusion in the macropores, a sorption front forms in the sample to move inside the bed. The distance traveled by the front is proportional to the sorption time to the power 1/2. The effective diffusion coefficient of water in the macropores is estimated from the front motion dynamics to be between 0.8 × 10^?9 and 3.0 × 10^?9 m²/s, depending on the porous structure of the bed.     

具有微孔/大孔双孔道体系沸石材料的合成

近年来 ,随着精细化工反应中大分子及液相反应的增多 ,沸石催化材料由于其孔道狭窄 ,存在较大扩散阻力 ,越来越不能满足反应的需要 .而多级孔道体系材料由于能同时提供不同大小的孔道 ,因此对解决传质问题将会有很大帮助[14].但目前绝大部分研究集中在中孔 /大孔体系[4 6 ],对于微孔 /大孔体系的研究则较少 .最近 ,Ｈｏｌｌａｎｄ等[7]利用硬球模板技术首次制得微孔 /大孔沸石 ,这类材料中由于存在丰富的大孔 ,对解决扩散阻力较大反应中的传质问题可能会有显著功效 ;同时 ,大孔孔壁是由晶化的微孔沸石构成 ,因此将期望具有较好的水热稳定性…     

Preparation and characterization of Pb<Subscript>0.56</Subscript>Sr<Subscript>0.44</Subscript>Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>O<Subscript>3</Subscript> inverse opal

Pb_0.56Sr_0.44Zr_0.52Ti_0.48O₃ (PSZT) inverse opal photonic crystals (PCs) have been synthesized by a process of self-assembly in combination with a sol–gel procedure. PSZT inverse opals show pure perovskite structure with good orders in three dimensions. The evident photonic band gaps have been observed in the transmittance spectra with a blue-shift phenomenon due to the decrease of opal template periods. PSZT inverse opals also exhibit the reflection peaks in basic agreement with the calculated results. This three-dimensional (3D) ordered PSZT inverse opals have shown interesting optical characteristics and potential applications in optoelectronic and photonic devices.     

The structure of the compound Cd3P2

Structure of Cd₃P₂ (P4₂/nmc, a = b = 8.7390 Å, c = 12.2523 Å) has been solved and refined up to R = 3.78% using precision X-ray diffraction experimental data (λ-MoK _α, graphite monochromator on a primary beam, 11529 reflections). Interatomic distances and valence angles are determined. Phosphorus forms a face-centered cubic lattice in which 3/4 tetrahedral voids are occupied by cadmium atoms in the crystal structure. The structure can be described by two equivalent models in which the positions of cadmium atoms, which occupy tetrahedral voids following the “diamond principle,” are preserved, while the remaining free and occupied voids change their places.     

Controlled Synthesis of Hollow PbS‐TiO2 Hybrid Structures through an Ion Adsorption–Heating Process and their Photocatalytic Activity

Hollow hybrid nanostructures have received significant attention because of their unique structural features. This study reports a facile ion adsorption–heating method to fabricate hollow PbS‐TiO₂ hybrid particles. In this method, the TiO₂ spheres used as a substrate material to grow PbS are aggregates of many small amorphous TiO₂ particles, and each small particle is covered with thioglycolic acid ligands through Ti⁴⁺–carboxyl coordination. When Pb²⁺ ions are added to a colloidal solution of these TiO₂ spheres, these ions are adsorbed by sulfhydryl (‐SH) groups to form metal thiolates, and the C−S bond is dissociated by heating to release S²⁻. The S²⁻ ions react with Pb²⁺ ions to form PbS without additive sulfur sources. Additionally, the amorphous TiO₂ spheres are transformed into the anatase phase during the heating process. As a result, the crystallization of TiO₂ spheres along with the formation of PbS is simultaneously carried out by heating. During the heating process, owing to the Kirkendall effect of S²⁻ diffusion and the Ostwald ripening effect of the crystallization of amorphous TiO₂ spheres, PbS‐TiO₂ hollow hybrid structures can be obtained. The XRD and XPS characterizations proved the formation of anatase TiO₂ and PbS. The TEM characterization confirmed the formation of hollow structures in the PbS‐TiO₂ hybrid sample. The photocatalytic activity of the hollow PbS‐TiO₂ hybrid spheres have been investigated for the degradation of Cr⁶⁺ under visible light. The results show that hollow PbS‐TiO₂ hybrid spheres exhibited the highest photocatalytic activity, in which almost all the Cr⁶⁺ was degraded after 140 min.     

Diffusing probe measurements in Newtonian and elastic solutions

The diffusion coefficients of polystyrene latex spheres and hematite particles in both Newtonian and elastic liquids have been measured using dynamic light scattering. The diffusion coefficients of the latex particles measured in glycerol/water (Newtonian) solutions obey Stokes–Einstein behaviour over a range of solvent viscosities and temperatures. Two apparent diffusion coefficients for the particles are measured in visco-elastic polyacrylamide and polyacrylate solutions and are designated D_fast and D_slow. The apparent fast diffusion coefficients measured in the elastic solutions show an increase to a maximum, above that measured in the solvent water, with increasing polyelectrolyte concentration. At higher polyelectrolyte concentrations the observed D_fast values decrease below the value obtained in the solvent water. D_fast increases with the scattering vector squared (q²) while D_slow, is independent of q².     

Preparation of a large Mesoporous CeO2 with crystalline walls using PMMA colloidal crystal templates

Inverse opals of crystalline CeO₂ were synthesized by using close-packed poly(methyl methacrylate) (PMMA) latex spheres of various sizes as templates, resulting in pore sizes, which could be scaled down even to the mesopore region (30–40 nm). The latex spheres were synthesized by emulsion polymerization, and the PMMA particle size could be substantially decreased by addition of sodium dodecyl sulfate (SDS) as surfactant. Owing to the larger pore wall thickness, the CeO₂ with large mesopores preserves an intact porosity to higher temperatures than previously reported mesoporous CeO₂ obtained from surfactant templates. The porosity and crystallinity were studied by microscopic techniques, wide angle X-ray diffraction (XRD), N₂ sorption, and Hg porosimetry. The evolution of crystallinity (crystallite size and lattice parameters) was determined for different annealing temperatures by means of Rietveld refinements of the XRD data. Thereby, our study allowed getting general insights into the crystallization behavior of sol–gel derived porous CeO₂ frameworks.     

Synthesis of Hierarchical Macro‐/Mesoporous Solid‐Solution Photocatalysts by a Polymerization–Carbonization–Oxidation Route: The Case of Ce0.49Zr0.37Bi0.14O1.93

A hierarchical macro‐/mesoporous Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution network has been synthesized on a large scale by means of a simple and general polymerization–carbonization–oxidation synthetic route. The as‐prepared product has been characterized by SEM, XRD, TEM, BET surface area measurement, UV/Vis diffuse‐reflectance spectroscopy, energy‐dispersive X‐ray spectroscopy (EDS), and photoelectrochemistry measurements. The photocatalytic activity of the product has been demonstrated through the photocatalytic degradation of methyl orange. Structural characterization has indicated that the hierarchical macro‐/mesoporous solid‐solution network not only contains numerous macropores, but also possesses an interior mesoporous structure. The mesopore size and BET surface area of the network have been measured as 2–25 nm and 140.5 m² g^?1, respectively. The hierarchical macro‐/mesoporous solid‐solution network with open and accessible pores was found to be well‐preserved after calcination at 800 °C, indicating especially high thermal stability. Due to its high specific surface area, the synergistic effect of the coupling of macropores and mesopores, and its high crystallinity, the Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution material shows a strong structure‐induced enhancement of visible‐light harvest and exhibits significantly improved visible‐light photocatalytic activity in the photodegradation of methyl orange compared with those of its other forms, such as mesoporous hollow spheres and bulk particles.     

Enhanced thermoelectric performance and novel nanopores in AgSbTe2 prepared by melt spinning

We report a melt-spinning spark-plasma-sintering synthesis process of the polycrystalline p-type material composed of AgSbTe₂ coarse grains and evenly formed 5-10 nm pores that occur primarily on the surface of matrix grains. The formation mechanism of nanopores and their influences on the thermoelectric properties have been studied and correlated. Microstructure analysis shows that the as-prepared sample can be regarded as a nanocomposite of matrix and in situ generated nanopores evenly coated on matrix grains. For the single-phase component and the possible energy-filter effect caused by the nanopores, the electrical transport properties are improved. Moreover, the thermal conductivity is significantly reduced by strong phonon scattering effect resulted from the nanopores. The thermoelectric performance of the as prepared sample enhances greatly and a ZT of 1.65 at 570 K is achieved, increasing∼200% compared with the sample prepared by traditional melt and slow-cooling method.     

Colloidal Templating Fabrication of Aluminum‐Organophosphonate Films Using High Molecular Weight PS‐b‐PEO

High molecular weight polystyrene‐block‐poly(ethylene oxide) diblock copolymer (PS‐b‐PEO) is utilized as colloidal spheres in the presence of water. Adequately thick films with multilayers of spherical macropores are fabricated in one‐pot under highly concentrated conditions of PS‐b‐PEO. The frameworks are constructed using aluminum organophosphonate as a complicated hybrid component. The macropores (30–200 nm) are homogeneously distributed over the entire films and pore windows between the macropores are tunable (up to nearly 10 nm) by changing the relative amount of PS‐b‐PEO in the precursor solutions.     

Ionic Liquid Assisted Synthesis of Au–Pd Bimetallic Particles with Enhanced Electrocatalytic Activity

Morphology‐ and composition‐controlled synthesis of Au–Pd bimetallic particles was realized by a facile ionic liquid assisted route at room temperature. The morphologies of the synthesized particles, such as nanoflake‐constructed spheres with a core–shell structure, nanoparticle‐constructed spheres, and nanoparticle‐constructed dendrites, could be well controlled by the present route. The ionic liquid was found to play a key role in the formation of these interesting particles. Moreover, the composition (Au:Pd) of the particles could be modulated by means of the molar ratio of the metal precursors in the feeding solutions. The Au–Pd bimetallic particles exhibit high electrocatalytic activity toward oxidation of ethanol and formic acid. Furthermore, cyclic voltammetric studies on the as‐prepared Au–Pd bimetallic particles revealed good electroactivity for H₂O₂, which results in an effective amperometric H₂O₂ sensor.     

Drying dissipative structures of lightly cross-linked poly(2-vinyl pyridine) cationic gel spheres stabilized with poly(ethylene glycol) in the deionized aqueous suspension

Drying dissipative patterns of deionized and colloidal crystal-state suspensions of the cationic gel spheres of lightly cross-linked poly(2-vinyl pyridine) stabilized with poly(ethylene glycol) were observed on a cover glass, a watch glass, and a Petri glass dish. Convectional patterns were recognized with the naked eyes. The broad rings were observed in the drying pattern and their size and width decreased as gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed. This work clarified the formation of the drying microscopic structures of (a) ordered rings, (b) flickering ordered spoke-lines, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles. The ordering of the agglomerated particles of the cationic gel spheres is similar to that of the anionic thermo-sensitive gel spheres of poly(N-isopropyl acrylamide). The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrates during dryness are important for the ordering. The microscopic drying patterns of gel spheres were different from those of linear-type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation at the edges were similar to each other. The addition of sodium chloride shifted the microscopic patterns from lattice to net structures.     

Synthesis of hierarchical macro/mesoporous dicalcium phosphate monolith via epoxide-mediated sol–gel reaction from ionic precursors

Starting from calcium chloride dihydrate (CaCl₂·2H₂O), phosphoric acid (H₃PO₄), and poly(acrylic acid) (PAA) dissolved in a mixture of water and methanol (MeOH), dicalcium phosphate anhydrous (DCPA, CaHPO₄) monoliths with co-continuous macropores and mesopores have been synthesized by the addition of propylene oxide. Macropores are formed as a result of phase separation, while mesopores as interstices between primary particles with the size of ca. 30 nm. Propylene oxide acts as a proton scavenger and leads to moderate pH increase in a reaction solution, which brings about gelation in several minutes. On the other hand, PAA acts as a crystal growth inhibitor as well as a phase separation inducer. The extensive crystal growth of DCPA is hindered by the addition of PAA which allows morphological control of the structure in micrometer range. Fourier transform infrared spectroscopy indicates that PAA and DCPA form composite via interaction between the carboxyl groups and the surface of crystals, and together form gel phase. The solvent phase, which is converted to macropores after evaporative drying, is mainly comprised of solvent. The degree of supersaturation in a reaction solution considerably influence on the crystallization process, and thereby, influences on the porous structure in nano- and micrometer ranges.