Thermally Induced Growth of ZnO Nanocrystals on Mixed Metal Oxide Surfaces

An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG‐MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH₄NO₃). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X‐ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate.     

Amine‐Assisted Syntheses of Carbonate‐Free and Highly Crystalline Nitrate‐Containing Zn‐Al Layered Double Hydroxides

Zn‐Al layered double hydroxides (LDHs), with nitrate as the charge balancing anion in the interlayer space, were synthesized by precipitation from homogeneous solution containing different amines [e.g., hexamethylenetetraamine (HMTA), diethylenediamine (DEDA), trimethylamine (TMA) and dimethylamine (DMA)]. The applied method does not require nitrogen atmosphere. The solution pH and concentration of different amines were varied in order to identify the controlling parameters and whether nitrate or carbonate are the interlayer anion. Particularly, the addition of amines turns out to be an effective tool for the synthesis of nitrate containing Zn‐Al LDHs independent from the nitrogen atmosphere. The structure, textural, composition, and morphological properties were investigated using the powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA), FT‐IR spectroscopy, and scanning electron microscopy (SEM). The analyses showed that the samples had high crystallinity and purity. The NO₃‐ZnAl LDHs samples show that LDH sheets are predominantly smooth textured and the thickness of LDH sheets are found to be around 23 nm. The results also indicate that this method successfully produces a NO₃^– form Zn‐Al LDH that is almost identical to the one synthesized by conventional methods.     

Reactivity of Extra‐framework Species of USY Zeolites in Alkaline Medium

Zeolites of type USY (ultra‐stable Y) were obtained by steaming of NH₄NaY modification. Samples were modified by subsequent alkaline treatment in KOH solution. USY and USY‐KOH were characterised by chemical element analysis, XRD, IR, ²⁹Al and ²⁹Si MAS NMR spectroscopic measurements. Correct silicon to aluminium ratios (Si/Al) were determined by XRD and IR (double ring vibration w_DR) data whereas values calculated according to data of ²⁹Si MAS NMR and IR spectroscopy (asymmetrical TOT valence vibration w_TOT) appeared to be too high., In the latter case, the signals of the zeolite framework were strongly superimposed by that of extra‐framework silica gel (EFSi) formed during steaming. It was found that alkaline leaching induces desilication of silicon‐rich area of the zeolite framework and partial dissolution of EFSi. Silicate ions of both react with likewise dissolved extra‐framework aluminium (EFAl) to form X‐ray amorphous aluminosilicate. Consequently, the superposition of the ²⁹Si MAS NMR signals of the zeolite framework by silica gel was reduced for Q⁴(0Al) but increased for Q⁴ (2Al) and Q⁴(3Al) structure units. A reinsertion of EFAl into the zeolite framework has not been observed.     

NMR Crystallography Reveals Carbonate Induced Al-Ordering in ZnAl Layered Double Hydroxide

Layered double hydroxides (LDHs) serve a score of applications in catalysis, drug delivery, and environmental remediation. Smarter crystallography, combining X-ray diffraction and NMR spectroscopy revealed how interplay between carbonate and pH determines the LDH structure and Al ordering in ZnAl LDH. Carbonate intercalated ZnAl LDHs were synthesized at different pH (pH 8.5, pH 10.0, pH 12.5) with a Zn/Al ratio of 2, without subsequent hydrothermal treatment to avoid extensive recrystallisation. In ideal configuration, all Al cations should be part of the LDH and be coordinated with 6 Zn atoms, but NMR revealed two different Al local environments were present in all samples in a ratio dependent on synthesis pH. NMR-crystallography, integrating NMR spectroscopy and X-ray diffraction, succeeded to identify them as Al residing in the highly ordered crystalline phase, next to Al in disordered material. With increasing synthesis pH, crystallinity increased, and the side phase fraction decreased. Using ¹H−¹³C, ¹³C−²⁷Al HETCOR NMR in combination with ²⁷Al MQMAS, ²⁷Al-DQ-SQ measurements and Rietveld refinement on high-resolution PXRD data, the extreme anion exchange selectivity of these LDHs for CO₃²⁻ over HCO₃⁻ was linked to strict Al and CO₃²⁻ordering in the crystalline LDH. Even upon equilibration of the LDH in pure NaHCO₃ solutions, only CO₃²⁻ was adsorbed by the LDH. This reveals the structure directing role of bivalent cations such as CO₃²⁻ during crystallization of [M²⁺₄M³⁺₂(OH)₂]²⁺[A²⁻]₁⋅yH₂O LDH phases.     

Cu–Al Spinel Oxide as an Efficient Catalyst for Methanol Steam Reforming

Cu–Al spinel oxide, which contains a small portion of the CuO phase, has been successfully used in methanol steam reforming (MSR) without prereduction. The omission of prereduction not only avoids the copper sintering prior to the catalytic reaction, but also slows down the copper‐sintering rate in MSR. During this process, the CuO phase can initiate MSR at a lower temperature, and CuAl₂O₄ releases active copper gradually. The catalyst CA2.5‐900, calcined at 900 °C with n(Al)/n(Cu)=2.5, has a higher CuAl₂O₄ content, higher BET surface area, and smaller CuAl₂O₄ crystal size. Its activity first increases and then decreases during MSR. Furthermore, both fresh and regenerated CA2.5‐900 showed better catalytic performance than the commercial Cu–Zn–Al catalyst.     

Thermal and photocatalytic behavior of Ti/LDH nanocomposites

The development of nanocomposite photocatalyst based on layered double hydroxides (LDHs) associated with TiO₂ was the subject of this research. The thermally activated Zn–Al LDHs were selected as catalyst support precursor because of their proven photocatalytic activity and therefore their possible contribution to overall activity of novel Ti–Zn–Al nanocomposite. The catalyst precursor (Zn–Al LDH) was synthesized by low supersaturation coprecipitation method, and its association with active TiO₂ component targeting the formation of novel Ti–Zn–Al nanocomposite was achieved by wet impregnation. Simultaneous thermal analysis (TG–DTA) was used to investigate the thermal behavior of Zn–Al LDH and Ti–Zn–Al LDHs. Complementary, morphology, texture, and structure characterization was carried out. The photocatalytic test reaction was performed under UV light using the methylene blue degradation. The results confirmed a successful impregnation of TiO₂ on catalyst support precursor Zn–Al–LDH followed by considerable change in morphology and structure of Zn–Al LDH precursor. It was concluded that the synergic effect between TiO₂ and Zn–Al LDH precursor contributes to the overall photocatalytic activity.     

Synthesis and Characterization of [Zn‐Al] Layered Double Hydroxides: Effect of the Operating Parameters

In this study, [Zn‐Al] layered double hydroxides (LDHs ) were prepared using the coprecipitation method at constant pH . The synthesis parameters (including the aging time, synthesis pH , nature of the alkali, concentration of metallic salts, and the cationic molar ratio R = Zn/Al) were varied in order to elucidate their effect on the properties of the obtained materials. Different characterization techniques, namely X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis‐differential thermogravimetry, transmission electron microscopy, energy‐dispersive X‐ray, inductively coupled plasma, and photoluminescence, were used in this study. It was found that obtaining well‐crystallized LDHs requires (i) an aging time of 24 h and (ii) a synthesis pH value in the range 8–12. Our results also show that the concentration of the cationic metallic salts has no influence on the structural properties of the LDHs . The use of NH₄OH as alkali for adjusting the pH value during the synthesis favors the formation of nitrated LDH phases while NaOH gives rise to carbonated ones. Moreover, it was found that irrespective of the molar cationic ratio used (between 1 and 5), [Zn‐Al] LDHs could be obtained. The sample synthesized at R = 2 exhibited the best crystallinity.     

Biodegradable Gelatin as Template for the Preparation of Mesoporous Alumina

In this study, we propose a time‐ and energy‐saving method using biodegradable gelatin as a green template and a low‐toxicity inorganic aluminum salt (Al(NO₃)₃·9H₂O) as a low‐cost aluminum source for the preparation of mesoporous alumina (γ‐Al₂O₃). The effects of pH (pH 8.0–10.0), gelatin to aluminum source ratio (0–1.9), and the hydrothermal treatment time (0–72 h) are thoroughly explored. The gelatin can assemble with the aluminum species γ‐AlOOH via hydrogen bonding to prevent the self‐condensation of the γ‐AlOOH during the hydrothermal treatment. Distinctly, the mesoporous γ‐Al₂O₃ was obtained from the calcination of the resulting gelatin–γ‐AlOOH composites. Without gelatin, high‐crystallinity γ‐AlOOH formed after the hydrothermal treatment, which transformed into the nonporous γ‐Al₂O₃ with a small surface area (20 m²/g). Finally, it was found that with a gelatin/aluminum ratio of 0.81, reaction pH value of 8.0, and hydrothermal treatment time of 24 h, high‐surface‐area mesoporous γ‐Al₂O₃ (262 m²/g) with pore diameter of 6.3 nm could be synthesized.     

Highly Dispersed Pd Species Active in the Suzuki–Miyaura Reaction

Structures of Pd/zeolites immersed in solvents were measured by in situ X‐ray absorption fine structure (XAFS). Systematic studies revealed that the selection of an appropriate support (USY‐zeolite), thermal treatment temperature of USY, solvent (o‐xylene), H₂ partial pressure (6 %), and the use of a Pd amine complex affect the structure of Pd. As a result, we found that monomeric Pd can be obtained in the USY support with H₂ bubbling in o‐xylene. The structural properties of Pd correlate well with its catalytic performance in the Suzuki–Miyaura coupling reactions; a very high TON of up to 11 000 000 was obtained over the monomeric Pd.     

Synthesis of Zeolite ZSM-2 Using Zeolite NaX as Seeds

Introduction Oxygen and nitrogen have been produced tradition-ally by cryogenic distillation of air. Methods for the non-cryogenic separation based on selective adsorption have been developed and commercialized since the 1970s and have led to a cost-effective process for this important separation.1 Low-silica zeolites are important materials for producing oxygen by selective adsorption of nitrogen. In 19891990, a new generation of lith-ium-based adsorbents was developed.2,3 Highly lithium exc…     

Pervaporation Separation and Catalysis Activity of Novel Zirconium Silicalite-1 Zeolite Membrane

Novel zirconium silicalite‐1 zeolite membrane was hydrothermally prepared on the mullite porous support at 150–185°C for 40–72 h by an "in situ" method using tetraethyl orthosilicate (TEOS), zirconium butoxide (ZBOT) and tetrapropylammonium hydroxide (TPAOH) as silica source, zirconium source and organic structure directing agent, respectively. X‐ray diffraction (XRD) patterns, fourier transformed infrared (FT‐IR) spectra, and inductively coupled plasma‐atomic emission spectrometry (ICP) of the accompanying zeolite powder confirmed that the zirconium was isomorphously incorporated into the zeolite framework. The surface chemical compositions of the obtained membrane were measured with an energy‐dispersive X‐ray spectral analyzer (EDS), and the membrane morphologies were observed by a scanning electron microscope (SEM). The results showed that the zeolite crystals growing on the support were zirconium silicalite‐1 zeolites, and the dense membrane layer was composed of the well inter‐growing zeolite crystals. The zirconium silicalite‐1 zeolite membrane, which was derived from the synthesis solution having a molar ratio of 1.00SiO₂:0.01ZrO₂:0.17TPAOH:120H₂O, showed high ethanol permselectivity with a flux of 1.01 kg/(m²·h) accompanied with a separation factor of 73 for ethanol/water (5/95, w/w) system under a pervaporation condition at 60°C. Moreover, this membrane displayed pervaporation‐aided catalysis activity for iso‐propanol oxidation with hydrogen peroxide as oxidant, and the corresponding iso‐propanol conversion was 35%.     

A magnetic organic-inorganic composite: Synthesis and characterization of magnetic 5-aminosalicylic acid intercalated layered double hydroxides

A core-shell structured magnetic layered organic-inorganic material involving 5-aminosalicylic acid (5-ASA) intercalated Zn-Al layered double hydroxides (LDHs) and magnesium ferrite (MgFe₂O₄) is assembled by a coprecipitation method. The powder X-ray diffraction results show the coexistence of the clear but weak diffractions of MgFe₂O₄ and ordered relatively stronger reflections of 5-ASA intercalated LDHs. The TEM image of magnetic 5-ASA intercalated LDHs reveals that the LDHs layer covers the MgFe₂O₄ particles or their aggregates with particle size of 50-80 nm. The vibration sample magnetization (VSM) measurements exhibit the increase in saturation magnetization of magnetic 5-ASA intercalated LDHs samples with increasing amount of magnetic core. The XPS analyses account for a majority of Zn, Al and O atoms on the surface of magnetic particles. It is suggested that the magnetic core MgFe₂O₄ was coated with LDHs layer probably through Zn-O-Mg and Al-O-Mg linkages, and a core-shell structured model is tentatively proposed.     

Desilication mechanism revisited: highly mesoporous all-silica zeolites enabled through pore-directing agents

The role of pore‐directing agents (PDAs) in the introduction of hierarchical porosity in silicalite‐1 in alkaline medium was investigated. By incorporation of various PDAs in aqueous NaOH, homogenously distributed mesopores were introduced in 2.5 μm silicalite‐1 crystals. It was proven for the first time that framework aluminum is not a prerequisite for the introduction of intracrystalline mesoporosity by desilication. The pore‐directing role is not directly exerted by framework trivalent cations metals, but by species on the external surface of the zeolite. The inclusion of metal complexes (Al(OH)₄^?, Ga(OH)₄^?) and tetraalkyl ammonium cations (tetramethyl ammonium (TMA⁺), tetrapropyl ammonium (TPA⁺)) in the alkaline solution led to distinct mesopore surface areas (up to 286 m² g^?1) and pore sizes centered in the range of 5–20 nm. In the case alkaline treatment was performed in the presence of Al(OH)₄^?, all aluminum partially integrated in the zeolite giving rise to both Lewis and Brønsted acidity. Apart from the concentration and location, the affinity of the PDA to the zeolite surface plays a crucial role in the pore formation process. If the PDA is attracted too strongly (e.g., TMA⁺), the dissolution is reduced dramatically. When the pore‐directing agent is not attracted to the zeolite’s external surface, excessive dissolution occurs (standard alkaline treatment). TPA⁺ proved to be the most effective PDA as its presence led to high mesopore surface areas (>200 m² g^?1) over a broad range of PDA concentrations (0.003–0.1 M ). Importantly, our results enable to extend the suitability of desilication for controlled mesopore formation to all‐silica zeolites.     

Cu‐Based Catalyst Resulting from a Cu,Zn,Al Hydrotalcite‐Like Compound: A Microstructural,Thermoanalytical, and In Situ XAS Study

A Cu‐based methanol synthesis catalyst was obtained from a phase pure Cu,Zn,Al hydrotalcite‐like precursor, which was prepared by co‐precipitation. This sample was intrinsically more active than a conventionally prepared Cu/ZnO/Al₂O₃ catalyst. Upon thermal decomposition in air, the [(Cu_0.5Zn_0.17Al_0.33)(OH)₂(CO₃)_0.17] ? mH₂O precursor is transferred into a carbonate‐modified, amorphous mixed oxide. The calcined catalyst can be described as well‐dispersed “CuO” within ZnAl₂O₄ still containing stabilizing carbonate with a strong interaction of Cu²⁺ ions with the Zn–Al matrix. The reduction of this material was carefully analyzed by complementary temperature‐programmed reduction (TPR) and near‐edge X‐ray absorption fine structure (NEXAFS) measurements. The results fully describe the reduction mechanism with a kinetic model that can be used to predict the oxidation state of Cu at given reduction conditions. The reaction proceeds in two steps through a kinetically stabilized Cu^I intermediate. With reduction, a nanostructured catalyst evolves with metallic Cu particles dispersed in a ZnAl₂O₄ spinel‐like matrix. Due to the strong interaction of Cu and the oxide matrix, the small Cu particles (7 nm) of this catalyst are partially embedded leading to lower absolute activity in comparison with a catalyst comprised of less‐embedded particles. Interestingly, the exposed Cu surface area exhibits a superior intrinsic activity, which is related to a positive effect of the interface contact of Cu and its surroundings.     

Materials Discovery and Crystal Growth of Zeolite A Type Zeolitic–Imidazolate Frameworks Revealed by Atomic Force Microscopy

A new zeolitic–imidazolate framework (ZIF), [Zn(imidazolate)_2?x(benzimidazolate)_x], that has the zeolite A (LTA) framework topology and contains relatively inexpensive organic linkers has been revealed using in situ atomic force microscopy. The new material was grown on the structure‐directing surface of [Zn(imidazolate)_1.5(5‐chlorobenzimidazolate)_0.5] (ZIF‐76) crystals, a metal–organic framework (MOF) that also possesses the LTA framework topology. The crystal growth processes for both [Zn(imidazolate)_2?x(benzimidazolate)_x] and ZIF‐76 were observed using in situ atomic force microscopy; it is the first time the growth process of a nanoporous material with the complex zeolite A (LTA) framework topology has been monitored temporally at the nanoscale. The results reveal the crystal growth mechanisms and possible surface terminations on the {100} and {111} facets of the materials under low supersaturation conditions. Surface growth of these structurally complex materials was found to proceed through both “birth‐and‐spread” and spiral crystal‐growth mechanisms, with the former occurring through the nucleation and spreading of metastable and stable sub‐layers reliant on the presence of non‐framework species to bridge the framework during formation. These results support the notion that the latter process may be a general mechanism of surface crystal growth applicable to numerous crystalline nanoporous materials of differing complexity and demonstrate that the methodology of seeded crystal growth can be used to discover previously unobtainable ZIFs and MOFs with desirable framework compositions.     

Preparation and Charactrization of Fibrous Crystals of Boron-containing MTW-type Zeolite

Fibrous crystals of boron-containing MTW-type zeolite have been hydrothermally synthesized in B2O3-SiO2-HF-H2O gel system at 170℃ in 20 to 28d by using 1,4-diazabicyclo[2,2,2]octane (DABCO) and methylamine as the co-template, and characterized with XRD, SEM, TEM, HRTEM and SAED. The results of characterizations show that B atoms are incorporated into the zeolite framework as tetrahedron of B(OSi)4. The fibrous single crystals of 5-50μm in length and 100-500nm in width inter-grow along the c-axis of the zeolite, and the one dimension 12 oxygen ring channels are perpendicular to the fibber axis.     

Synthesis of Aluminum‐Rich Analcime Using an Ethylene Diamine Derivative as Template

The hydrothermal synthesis of analcime (ANA) with N,N′‐dibenzyl‐N,N,N′,N′‐tetramethylethylenediamine (DBTMED) as template was systematically studied. The various parameters that affect the crystallization of analcime, such as temperature, time, Al source, and Si/Al ratio were investigated. Systematic variations of these parameters revealed that ANA was obtained from the reaction mixture with the optimized ratios of SiO₂/Al₂O₃ = 5–9.5 in presence of DBTMED, whereas template‐free clear solution methods require SiO₂/Al₂O₃ ratio of greater than 25. When experiments were conducted at 130 and 150 °C for 4 days, a mixture of analcime and zeolite P was present in the samples, and a pure analcime sample could be obtained with heating in the temperature range 160–180 °C. When microwave and conventional heating were used, analcime could be obtained after 2 days. The obtained products were characterized by XRD, SEM, and IR spectroscopy.     

EU-1分子筛的合成及其在正己烷异构化反应中的催化性能

在不同硅铝比(n_SiO2/n_Al2O3)的合成凝胶(含纯硅凝胶)中引入晶种,合成了纯相的EU-1分子筛。研究了铝源、模板剂和晶种添加量对EU-1分子筛的结晶度、形貌尺寸等的影响;重点研究了不同硅铝比对样品结晶度、晶粒尺寸、酸性、比表面积和孔容等的影响。将合成结果绘制成了纯相EU-1分子筛的合成条件三元图,从三元图可看出,晶种法可显著扩大纯相EU-1分子筛的合成区域。将Pt/H-EU-1用于正己烷异构化反应,结果表明,该催化剂具有优异的正己烷异构化活性及稳定性,对异构烷烃有较高的选择性。     

Diagonally Related s‐ and p‐Block Metals Join Forces: Synthesis and Characterization of Complexes with Covalent Beryllium–Aluminum Bonds

Additions of beryllium–halide bonds in the simple beryllium dihalide adducts, [BeX₂(tmeda)] (X=Br or I, tmeda=N,N,N′,N′‐tetramethylethylenediamine), across the metal center of a neutral aluminum(I) heterocycle, [:Al(^DipNacnac)] (^DipNacnac=[(DipNCMe)₂CH]^?, Dip=2,6‐diisopropylphenyl), have yielded the first examples of compounds with beryllium–aluminum bonds, [(^DipNacnac)(X)Al‐Be(X)(tmeda)]. For sake of comparison, isostructural Mg–Al and Zn–Al analogues of these complexes, viz. [(^DipNacnac)(X)Al‐M(X)(tmeda)] (M=Mg or Zn, X=I or Br) have been prepared and structurally characterized. DFT calculations reveal all compounds to have high s‐character metal–metal bonds, the polarity of which is consistent with the electronegativities of the metals involved. Preliminary reactivity studies of [(^DipNacnac)(Br)Al‐Be(Br)(tmeda)] are reported.     

Formation and Properties of Losod,a New Sodium Zeolite

Losod, a new type of crystalline hydrated sodium aluminosilicate, Na₁₂Al₁₂Si₁₂O₄₈ · q H₂O, has been prepared from reaction mixtures containing bulky quaternary alkylammonium ions, particularly azonia-spiro[4.4]nonane, besides sodium ions. Losod crystallizes from batches with a low sodium content (Na/Al ≤ 1 and Si/Al ≈? 1). The quaternary ammonium hydroxide primarily serves as a source of hydroxide ions and is not incorporated into the zeolite crystals. These bulky bases provide a useful means for controlling the alkalinity of the system independently of the concentration of the necessary cations built into the zeolite. The crystals of Losod are hexagonal (a = 12.91 and c = 10.54 Å) and the proposed framework structure shows a polytypic relationship to sodalite and cancrinite. Losod has reversible sorption and ion exchange properties typical of a small-pore zeolite and in essential agreement with the proposed structure.