Structural Changes of Hierarchically Nanoporous Organosilica/Silica Hybrid Materials by Pseudomorphic Transformation

Herein, it is reported how pseudomorphic transformation of divinylbenzene (DVB)-bridged organosilica@controlled pore glasses (CPG) offers the possibility to generate hierarchically porous organosilica/silica hybrid materials. CPG is utilized to provide granular shape/size and macroporosity and the macropores of the CPG is impregnated with organosilica phase, forming hybrid system. By subsequent pseudomorphic transformation, an ordered mesopore phase is generated while maintaining the granular shape and macroporosity of the CPG. Surface areas and mesopore sizes in the hierarchical structure are tunable by the choice of the surfactant and transformation time. Two-dimensional magic angle spinning (MAS) NMR spectroscopy demonstrated that micellar-templating affects both organosilica and silica phases and pseudomorphic transformation induces phase transition. A double-layer structure of separate organosilica and silica layers is established for the impregnated material, while a single monophase consisting of randomly distributed T and Q silicon species at the molecular level is identified for the pseudomorphic transformed materials.     

Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Synthesis of Highly Luminescent Tris-Fluorenyl Chromophores as Intermediates of Potential Nonlinear Photonic Materials

In our effort to enhance the cross section of simultaneous multiphoton absorption of C₆₀-based photonic nanomaterials, a novel highly luminescent tris-fluorenyl ring-interconnected chromophore tris-DPAF-C₉ was designed and synthesized using a C ₃ symmetrical triaminobenzene core as the synthon. The structural moiety bears a close resemblance to that of 2-diphenylamino-9,9-dialkylfluorenyl attachment in the previously studied C₆₀(> DPAF-C_n)_x. The product tris-DPAF-C₉ was fully characterized by NMR, UV, IR, and MALDI-TOF MS spectroscopic methods. Based on the molecular energy calculation at MOPAC PM3 level, it suggested the presence of two possible cis/trans stereoisomers on the configuration of fluorenyl moieties. Consequently, a lower heat formation (ΔH _f) of 19.9 kcal/mol was found for the tris-cis C₉-isomer as the favorable one vs 47.9 kcal/mol for the bis-mono-trans C₉-isomer.     

有机电致磷光材料的分子设计：从主体材料到客体材料

有机电致磷光器件的设计和利用，可以突破由三线态激子跃迁自旋禁阻引起的有机电致荧光器件量子效率的限制。本文综述了有机电致磷光器件和材料的研究进展，主要介绍了主体材料和客体材料的研究现状，特别是蓝光磷光器件主客体材料的研究情况。     

Structural evolution during pyrolysis of sol-gel derived hybrid materials

Siloxane-titania materials have been prepared starting from diethoxydimethylsilane and titanium isopropoxide. The transparent starting gels can be described as nanocomposites formed with siloxane chains and TiO₂-based particles. The pyrolysis process under argon atmosphere up to 1600°C has been followed by various techniques such as infrared and solid state NMR spectroscopies, X-ray diffraction and Ti K-edge X-ray Absorption. Si-C bond cleavage begins at low temperature leading to redistribution reactions with the formation of new Si-O bonds. Crystallization of TiO₂ at low temperature is prevented and titanium carbide starts to form around 800°C. Samples pyrolyzed at 1600°C show the presence of SiO₂ and TiC crystalline phases.     

Stacking Structure of Confined 1‐Butanol in SBA‐15 Investigated by Solid‐State NMR Spectroscopy

Understanding the complex thermodynamic behavior of confined amphiphilic molecules in biological or mesoporous hosts requires detailed knowledge of the stacking structures. Here, we present detailed solid‐state NMR spectroscopic investigations on 1‐butanol molecules confined in the hydrophilic mesoporous SBA‐15 host. A range of NMR spectroscopic measurements comprising of ¹H spin–lattice (T₁), spin–spin (T₂) relaxation, ¹³C cross‐polarization (CP), and ¹H,¹H two‐dimensional nuclear Overhauser enhancement spectroscopy (¹H,¹H 2D NOESY) with the magic angle spinning (MAS) technique as well as static wide‐line ²H NMR spectra have been used to investigate the dynamics and to observe the stacking structure of confined 1‐butanol in SBA‐15. The results suggest that not only the molecular reorientation but also the exchange motions of confined molecules of 1‐butanol are extremely restricted in the confined space of the SBA‐15 pores. The dynamics of the confined molecules of 1‐butanol imply that the ¹H,¹H 2D NOESY should be an appropriate technique to observe the stacking structure of confined amphiphilc molecules. This study is the first to observe that a significant part of confined 1‐butanol molecules are orientated as tilted bilayered structures on the surface of the host SBA‐15 pores in a time‐average state by solid‐state NMR spectroscopy with the ¹H,¹H 2D NOESY technique.     

Modification of Silica by Liquid Polybutadienes Containing Alkoxysilane Groups

Summary : The present work describes a method to modify the surface of silica, reducing its polar character and making it compatible and dispersible into hydrocarbon based elastomers. A liquid low molar mass polybutadiene (PB) was grafted with mercaptopropyltrimethoxysilane (MPTS) via radical addition of the thiol group to the double bonds. The silanized PB was reacted with silica via thermal condensation with its silanol groups. ²⁹Si NMR spectra showed that the condensation reaction of the trifunctional silane involved one or two alkoxy groups, while the third alkoxy group remained unreacted, probably for steric reasons. The characterization of the functionalized silica particles was performed by contact angle measurements and TGA analysis.     

铝锂混合掺杂尖晶石相Li_(1+x)Al_yMn_(2-y)O_4材料结构性能的研究

采用一种简单的合成工艺 ,将铝和锂混合掺入到主尖晶石相锰酸锂中 ,研究不同掺杂铝量对材料的初始容量及循环稳定性能的影响 .结果表明同时掺杂铝锂的材料要比单独掺杂铝或锂的循环稳定性好 .利用扫描电镜、粉末X_射线衍射仪、红外光谱仪对材料形貌及结构进行研究 ,结果表明所合成的掺杂铝锂材料颗粒细小、分布均匀 ,具有较好的结晶性能 ,较高的初始容量和良好的循环稳定性 ,其初始容量达 119mAh/g ,循环 2 0 0次后容量仍然保持在 10 6mAh/g     

The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study

In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.     

Macroporous Activated Carbon Fibers from Rayon Precursors Impregnated with Phosphoric Acid

Novel activated carbon fibers (ACFs) from rayon precursors impregnated with phosphoric acid (H₃PO₄), containing abundant macropores (pore size>50 nm), were successfully obtained. The physical properties of these ACFs were examined. The BET surface was obtained; SEM observations showed that the concentration of H₃PO₄ impregnation strongly influenced the surface morphology and the porous texture of the resulting ACFs. The shape of the pores was nearly round and we could estimate the pore size was distributed between 20 and 150 nm. Infrared spectroscopy (IR) was applied to investigate the pyrolysis process of the rayon precursors with H₃PO_4. In addition, P‐containing substances, which should perhaps be acid phosphates or polyphosphates, can be observed on the surface of the resulting ACFs from SEM photos. Impregnation made the dehydration become more predominant during the pyrolysis process.     

Heteronuclear NMR Spectroscopy as a Surface‐Selective Technique: A Unique Look at the Hydroxyl Groups of γ‐Alumina.

The surface hydroxyl groups of γ‐alumina dehydroxylated at 500 °C were studied by a combination of one‐ and two‐dimensional homo‐ and heteronuclear ¹H and ²⁷Al NMR spectroscopy at high magnetic field. In particular, by harnessing ¹H–²⁷Al dipolar interactions, a high selectivity was achieved in unveiling the topology of the alumina surface. The terminal versus bridging character of the hydroxyl groups observed in the ¹H magic‐angle spinning (MAS) NMR spectrum was demonstrated thanks to ¹H–²⁷Al RESPDOR (resonance‐echo saturation‐pulse double‐resonance). In a further step the hydroxyl groups were assigned to their aluminium neighbours thanks to a {¹H}‐²⁷Al dipolar heteronuclear multiple quantum correlation (D‐HMQC), which was used to establish a first coordination map. Then, in combination with ¹H–¹H double quantum (DQ) MAS, these elements helped to reveal intimate structural features of the surface hydroxyls. Finally, the nature of a peculiar reactive hydroxyl group was demonstrated following this methodology in the case of CO₂ reactivity with alumina.     

Structures and Unexpected Dynamic Properties of Phosphine Oxides Adsorbed on Silica Surfaces

Solid‐state NMR spectroscopy of selected phosphine oxides adsorbed on silica surfaces establishes the surface mobilities, even of phosphine oxides with high melting points. Crystal structures of the adducts Ph₃PO ? HOSiPh₃ and Cy₃PO ? H₂O indicate that the interactions with silica involve hydrogen bonding of the P?O group to adsorbed water and surface silanol groups.     

SBA‐15‐Oxynitrides as a Solid‐Base Catalyst: Effect of Nitridation Temperature on Catalytic Activity

Solid bases, such as SBA‐15‐oxynitrides, have attracted considerable interest for potential applications as catalysts in important industrial processes. Reported herein is that by simply tuning the temperature of nitridation (ammonolysis), the catalytic activity of these solid bases can be enhanced. Solid‐state NMR spectroscopy and XPS studies provided the reasoning behind this change in activity.