Synthesis and Structural Analysis of High-Silica ERI Zeolite with Spatially-Biased Al Distribution as a Promising NH3-SCR Catalyst.

Erionite (ERI) zeolite has recently attracted considerable attention for its application prospect in the selective catalytic reduction of NOx with NH3 (NH3-SCR), provided that the high-silica (Si/Al > 5.5) analog with improved hydrothermal stability can be facilely synthesized. In this work, ERI zeolites with different Si/Al ratios (4.6, 6.4, and 9.1) are synthesized through an ultrafast route, and in particular, a high-silica ERI zeolite with a Si/Al ratio of 9.1 is obtained by using faujasite (FAU) as a starting material. The solid-state 29Si MAS NMR spectroscopic study in combination with a computational simulation allows for figuring out the atomic configurations of the Al species in the three ERI zeolites. It is revealed that the ERI zeolite with the highest Si/Al ratio (ERI-9.1, where the number indicates the Si/Al ratio) exhibits a biased Al occupancy at T1 site, which is possibly due to the presence of a higher fraction of the residual potassium cations in the can cages. In contrast, the Al siting in ERI-4.6 and ERI-6.4 proves to be relatively random.

Synthesis of titanosilicate nanoparticles with high titanium content from a silsesquioxane-based precursor for a model epoxidation reaction.

In conventional hydrothermal synthesis of porous titanosilicate materials, undesired aggregation of TiO2 species during the synthesis limits the content of active four-coordinated Ti to an Si/Ti ratio of about 40. Aiming to increase the content of active four-coordinated Ti species, we report a bottom-up synthesis of titanosilicate nanoparticles using a Ti-incorporated cubic silsesquioxane cage as a precursor, which allowed incorporating a larger number of four-coordinated Ti species in the silica matrix to reach an Si/Ti ratio of 19. Even at this relatively high Ti concentration, the catalytic activity in the epoxidation of cyclohexene over the titanosilicate nanoparticles was comparable to that of a conventional reference Ti catalyst, Ti-MCM-41, with an Si/Ti ratio of 60. The activity per Ti site was not affected by the Ti content in the nanoparticles, suggesting that well dispersed and stabilized Ti species were the active sites.

Synthesis of Carbon Nanoparticles with Cobalt-Rich Shell via Pyrolysis of Zn-ZIF@Co/Zn-ZIF: Relevance of Co(III) Precursors.

To the best of our knowledge, this is the first report on the rapid one-pot synthesis of a unique core-shell-structured zeolitic imidazolate framework (ZIF) using Co(III) and Zn(II) precursors. The key to obtaining this unique structure is the use of a Co(III) precursor as the starting material. Transmission electron microscopy (TEM) reveals that Co was present within a 30-nm-thick shell layer of the ZIF material. Thermal decomposition of the ZIF material affords core-shell-structured carbon nanoparticles that have Co on the external surface of the carbon grain. We have previously demonstrated that this carbonaceous material obtained by thermal decomposition exhibited high performance as an adsorbent for nitric oxide, even in the presence of excess oxygen and water vapor, and therefore, it was a suitable material for NOx elimination at low temperatures. The growth mechanism of the synthesized ZIF particles and the differences between synthesized ZIF and conventional Co(II)-ZIF-67 are discussed. The reactivity of the Co(III) precursor is much lower than that of the Co(II) species, leading to slower precipitation of Co(III) than that of Zn(II), thus forming the core-shell structure.

High NH3-SCR reaction rate with low dependence on O2 partial pressure over Al-rich Cu-*BEA zeolite.

Dependence of NH3-SCR reaction rate on O2 partial pressure was investigated at 473 K over Cu ion-exchanged MOR, MFI, CHA and *BEA zeolites with varying "Cu density in micropores". Among the zeolites, Cu-*BEA zeolite demonstrated promising potential as an effective catalyst for NH3-SCR over a wide range of O2 partial pressure.

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation.

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.

Development of Imidazo[1,2- a]pyridine Derivatives with an Intramolecular Hydrogen-Bonded Seven-Membered Ring Exhibiting Bright ESIPT Luminescence in the Solid State.

Imidazo[1,2- a]pyridine derivatives with different hydroxyaryl units (1-3), which could potentially form an intramolecular hydrogen-bonded seven-membered ring in either a planar or a twisted conformation, were newly developed, and the effect of conformation and steric repulsion on the excited-state intramolecular proton transfer (ESIPT) luminescence was evaluated. Among them, 1 and 2 formed an intramolecular hydrogen-bonded seven-membered ring in the crystalline state and exhibited efficient ESIPT luminescence in the solid state (quantum yield up to 0.45).

Identification of the Basic Sites on Nitrogen-Substituted Microporous and Mesoporous Silicate Frameworks Using CO2 as a Probe Molecule.

Carbon dioxide was shown to identify surface basic properties of nitrogen-substituted microporous and mesoporous silicas, in addition to conventional basic oxides, by a detailed study using isotherm and heat of adsorption measurements as well as by infrared spectroscopy. A hydrogen-bonded weak interaction was primarily observed between CO2 and silanol (Si-OH) and silamine (Si-NH-Si) groups. The heat of adsorption of CO2 demonstrated that the latter adspecies were formed preferentially over the former, although a much higher amount of linear CO2 adspecies were found on SBA-15 mesoporous silica because of the presence of a large quantity of silanol groups on its surface. Carbamate-type chemisorbed adspecies were not detected on silamino sites, whereas carbonate-type adspecies were formed on alkali ion-exchanged zeolites and also residual sodium ions on the surface of silicalite-1. CO2 was shown to be a successful probe molecule for identifying weakly interactive hydrogen-bonding sites, and it has potential as a surface probe for strongly interactive nucleophilic sites derived from alkaline ions or a methylated silamino group, Si-N(CH3)-Si.

Direct observation of catalytic oxidation of particulate matter using in situ TEM.

The ability to observe chemical reactions at the molecular level convincingly demonstrates the physical and chemical phenomena occurring throughout a reaction mechanism. Videos obtained through in situ transmission electron microscopy (TEM) revealed the oxidation of catalytic soot under practical reaction conditions. Carbon oxidation reactions using Ag/SiO2 or Cs2CO3/nepheline catalysts were performed at 330 °C under an O2 flow of 0.5 Pa in the TEM measurement chamber. Ag/SiO2 catalyzed the reaction at the interface of the mobile Ag species and carbon, while the Cs species was fixed on the nepheline surface during the reaction. In the latter case, carbon particles moved, remained attached to the Cs2CO3/nepheline surface, and were consumed at the interface by the oxidation reaction. Using this technique, we were able to visualize such mobile and immobile catalysis according to different mechanisms.

Heat storage properties of organic phase-change materials confined in the nanospace of mesoporous SBA-15 and CMK-3.

A novel type of material encapsulating phase-change materials (PCMs) is reported concerning their implication for use as thermal energy storage devices. The composites of siliceous SBA-15 or carbonaceous CMK-3 mesoporous assemblies and organic PCMs could be used to make leak-free devices that retain their capabilities over many thermal cycles for heat storage/release. A confinement effect was observed that alters the thermal properties of the encapsulated PCM, especially in CMK-3 without any similar effects in other carbon materials.

A unique heterogeneous nucleophilic catalyst comprising methylated nitrogen-substituted porous silica provides high product selectivity for the Morita-Baylis-Hillman reaction.

Methylated nitrogen-substituted microporous and mesoporous silica exhibited almost the same catalytic performance as that of a conventional homogeneous base catalyst. They also demonstrated unexpectedly high product selectivity for the Morita-Baylis-Hillman reaction of formaldehyde with methyl acrylate at high temperatures.

A simple modification creates a great difference: new solid-base catalyst using methylated N-substituted SBA-15.

A simple modification, methylation of the nitrogen-substituted mesoporous silica SBA-15, enhances the basicity of a solid-base catalyst. The methyl group donates an electron to the nitrogen atom in the silica framework. This catalyst accelerates Knoevenagel condensation using benzaldehyde and diethyl malonate, which conventional solid-base catalysts reported to date cannot do. This report demonstrates a possible new type of base catalyst using nitrogen-substituted mesoporous silica materials.

Pt/CeO(2)-ZrO(2) present in the mesopores of SBA-15--a better catalyst for CO oxidation.

Platinum loaded CeO(2)-ZrO(2)/SBA-15 composite material catalyzes CO oxidation at lower temperatures (<100 degrees C) than conventionally prepared Pt/CeO(2)-ZrO(2) (>150 degrees C). A sequence of reduction and reoxidation of CeO(2)- and ZrO(2)-loaded samples promotes the formation of CeO(2)-ZrO(2) solid solution on the siliceous surface as indicated by wide-angle X-ray diffraction (XRD) patterns. Furthermore, initial coating of ZrO(2) on the silica walls is quite important before CeO(2)-ZrO(2) loading in order to obtain the CeO(2)-ZrO(2) solid solution. The presence of CeO(2)-ZrO(2) particles inside the mesopores is confirmed by N(2) adsorption, low-angle X-ray diffraction, and scanning transmission electron microscopy (STEM) images. The solid solution of CeO(2)-ZrO(2) in the confined mesoporous space forms more Ce(3+) centers associated with oxygen vacancies on the surface due to the smaller size of the dispersed particles and these Ce(3+) centers are believed to be responsible for the higher catalytic activity.

Nepheline from K2CO3/nanosized sodalite as a prospective candidate for diesel soot combustion.

Nepheline group materials obtained by a thermal treatment of K2CO3-supported nanosized sodalite are identified as cost-effective materials which show promising activity and durability toward diesel soot combustion.

In situ observation of homogeneous nucleation of nanosized zeolite A.

The formation of zeolite A (LTA) in the presence of tetramethylammonium cations is studied using in situ small angle and wide angle X-ray scattering (SAXS/WAXS) techniques. The SAXS measurements show the formation of homogeneous precursors 10 nm in size prior to the crystallization of LTA which were consumed during the crystallization. The crystal size is estimated by fitting the SAXS patterns with an equation for a cubic particle, and it is revealed that the final crystal size of the LTA depends on the synthesis temperature. However, although such temperature dependence is noted for the final crystal size, the initial precursor particles size appears to be closely similar (ca. 10 nm) irrespective of the synthesis temperature.

A new approach to the determination of atomic-architecture of amorphous zeolite precursors by high-energy X-ray diffraction technique.

The structure of amorphous precursor species formed under hydrothermal conditions, prior to the onset of crystallization of microporous aluminosilicate zeolites, is determined employing high-energy X-ray diffraction (HEXRD). The investigation, combined with the use of reverse Monte Carlo modelling suggests that even numbered rings, especially 4R (R: ring) and 6R, which are the dominant aluminosilicate rings in zeolite A, have already been produced in the precursor. The model implies that the formation of double 4Rs occurs at the final step of the crystallization of zeolite A.

Synthesis of mesoporous aluminosilicate with zeolitic characteristics using vapor phase transport.

A mesoporous material with zeolitic characteristics is synthesized by use of a vapor phase transport method for the first time, along with stabilization of the mesostructure during crystallization of the amorphous walls by carbon filling.

Characterization of ESR active species on lithium chloride-modified mesoporous silica.

The surface of mesoporous silica with regular nanometer-sized pores and high surface area has been modified by metal ions or functional groups to introduce specific interactions. We found that ESR active species were formed on lithium chloride (LiCl)-modified mesoporous silica after heat treatment. The structure and the surface properties of LiCl-modified mesoporous silica were characterized by XRD, ESR, nitrogen adsorption, UV-vis-NIR, and TPD. The results suggest that the ESR active species were generated on the surface in response to heat treatment above 673 K. Moreover, it was found for the first time that LiCl-modified mesoporous silica after the heat treatment has reversible adsorption properties for hydrogen under room temperature and atmospheric pressure.

Investigation on the drying induced phase transformation of mesoporous silica; a comprehensive understanding toward mesophase determination.

Phase transformation of mesoporous silica during the drying process is investigated. As-synthesized hexagonal p6mm obtained under the conditions used in this study is transformed to cubic Ia3d as drying proceeds, even at room temperature. Prolonged synthesis results in the formation of a well-ordered hexagonal mesophase, with almost no phase transformation. Drying at a higher temperature promotes the phase transformation of not only hexagonal to cubic, but also cubic to lamellar mesophases. Release of water is detected during drying, which is followed by the phase transformation of the mesophases. The phase transformations observed here proceed against the direction estimated on the basis of the state-of-the-art understanding. Here, considering the degree of silicate condensation and the amount of residual water in the as-synthesized mesoporous silica, a comprehensive explanation of mesophase determination is proposed including thermodynamic and kinetic aspects to account for the results observed here and those in the literature.