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Keggin-type polyoxometalates are effective catalytic materials for acid-catalyzed reactions and oxidation reactions. In this paper, we describe the fabrication of a porous membrane of Keggin-type polyoxometalates at the gas-liquid interface and the structural characterization of the membrane via aberration-corrected scanning transmission electron microscopy. The membrane is formed by the introduction of n-octylamine vapor into aqueous solution of Keggin-type silicotungstic acid (H4SiW12O40) and cesium chloride. The membrane obtained has the cubic structure of cesium salts of silicotungstic acid (CsxH4-xSiW12O40), exposing the (110) crystal plane preferentially. The single-unit cell layer of the upper surface of the membrane is densely packed with Keggin anions, while the lower layers are rich in vacancies at both the anion and cation sites. This structure results from the fast formation of the single-unit cell layer at the surface of the solution and slow stacking of Keggin anions under the layer.
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High-dimensionally structured Mo-Fe oxide (HDS-MoFeO) was synthesized through an assembly of structural units supplied from Keplerate-type polyoxometalate, {Mo72Fe30}, under an appropriate hydrothermal condition. HDS-MoFeO showed excellent catalytic activity for the selective oxidation of methanol with slightly lower selectivity for formaldehyde than that of a conventional Mo-Fe oxide catalyst.
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High dimensionally structured niobium oxide (HDS-NbO) containing fluoride (F-) was prepared by a hydrothermal synthesis. F- could be introduced into HDS-NbO by replacing lattice oxygen up to a solid F-/Nb ratio of 0.55. The introduction of an appropriate amount of F- promoted the crystal growth of HDS-NbO, while niobium oxyfluoride having the hexagonal tungsten bronze structure (HTB-Nb(F,O)x) was concomitantly formed by excess F- addition. HAADF-STEM analysis suggested that the number of micropores (hexagonal and heptagonal channels) in HDS-NbO was increased by the introduction of an appropriate amount of F-. The catalytic activity for Brønsted acid reactions was evaluated by Friedel-Crafts alkylation. The catalytic activity was significantly increased by the introduction of F-, while excess introduction of F- significantly decreased the activity. Catalytic activity for the Lewis acid reaction in the presence of water was evaluated by the transformation of pyruvaldehyde into lactic acid. The catalytic activity was changed by the introduction of F- in a manner similar to that observed in the Friedel-Crafts alkylation. On the basis of the results obtained, we propose that the local catalyst structure around the micropores of HDS-NbO is crucial for the acid reactions.
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Synthesis of new zeolites with controlled pore architectures is important in the field of catalysis and separation related to chemical transformation, environmental protection, and energy-saving. Zeolites containing channels of different sizes in the same framework have been desirable. We report here the synthesis and structure of a novel aluminosilicate zeolite (designated as YNU-5), the first zeolite containing interconnected 12-, 12-, and 8-ring pores, as well as independent straight 8-ring channels. The synthesis procedure is quite simple and consists of conventional hydrothermal conditions as well as readily available starting materials. The framework structure is stable enough and Si/Al ratio is controllable between 9 and 350. Determination of the crystal structure is performed by utilizing X-ray diffraction-based techniques, revealing 9 independent tetrahedrally coordinated atoms. This robust structure is expected to be industrially valuable and several unusual combinations of composite building units are of considerable interest in an academic sense. The new zeolite YNU-5 is promising catalyst for the production of useful light olefins such as propylene and butylenes in the dimethyl ether-to-olefin reaction, when the Si/Al ratio is properly tuned by dealumination through simple acid treatments.
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An all-inorganic soft framework is rare but interesting for both fundamental research and practical applications. Here, an all-inorganic soft framework based on a transition metal oxide is reported. The periodic connection of a one-dimensional anionic tungstoselenate molecular wire building block with a CoII ion is used to construct the crystalline material. The crystal structure of the material was determined by high-angle annular dark-field scanning transmission electron microscopy combined with several characterization techniques. The soft framework of the material enables water adsorption/desorption with a change in its structure, leading to a high level of water adsorption. The framework of the material is flexible, and the structure of the molecular wire building block is stable during the water adsorption/desorption process.
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The structural determination of nanomaterials and their application in energy storage and transfer are of great importance. Herein, a layered zirconomolybdate with a two-dimensional structure was synthesized. Atomic resolution electron microscopy was utilized for direct visualization of the structure that was further confirmed by powder X-ray diffraction and X-ray absorption near-edge structure analyses. The structure of the molecular sheet was stable at a high temperature in an oxidative atmosphere. The electrochemical performance of the material was evaluated with a Li battery composed of the calcined material as a cathode. Li ions were reversibly inserted and extracted between the layers without collapse of the structure of the material. The electrochemical properties of the material were derived from the reversible redox activity of the Mo ions and Zr ions in the material as well as the flexibility of the molecular layer of the material.
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We describe the preparation of ε-Keggin-type cobaltomolybdate-based 3D frameworks with sodium cations, NaH9[ε-CoIIMoV8MoVI4O40CoII2], and their characterization by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure (XAFS) spectroscopy. Atomic-scale HAADF-STEM images of ε-Keggin compounds were obtained for the first time, and positions of Mo and Co were confirmed. Furthermore, clear evidence of the presence of a CoO4 tetrahedron was obtained by X-ray absorption near-edge structure (XANES) analysis. Their characterization clearly revealed that ε-Keggin-type cobaltomolybdate units, [ε-CoMo12O40]n-, constructed by a central CoIIO4 tetrahedron and 12 surrounding MoO6 octahedra, are linked with CoII to form 3D frameworks.
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Dipotassium cation (K+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110K2]13-, was prepared by heating monobismuth (Bi3+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110Bi(H2O)]12-, in acetate buffer in the presence of an excess amount of potassium cations. Characterization of the isolated potassium salt, K13[P5W30O110K2] (1a), and its acid form, H13[P5W30O110K2] (1b), by single crystal X-ray structure analysis, 31P and 183W nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV), high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and elemental analysis revealed that two potassium cations are encapsulated in the Preyssler-type phosphotungstate molecule with formal D5h symmetry, which is the first example of a Preyssler-type compound with two encapsulated cations. Incorporation of two potassium cations enhances the thermal stability of the potassium salt, and the acid form shows catalytic activity for hydration of ethyl acetate. Packing of the Preyssler-type molecules was observed by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
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The application of nanocatalysis based on metal oxides for biomass conversion is of considerable interest in fundamental research and practical applications. New acidic transition-metal oxide molecular wires were synthesized for the conversion of cellulosic biomass. The ultrafine molecular wires were constructed by repeating (NH4 )2 [XW6 O21 ] (X=Te or Se) along the length, exhibiting diameters of only 1.2â nm. The nanowires dispersed in water and were observed using high-angle annular dark-field scanning transmission electron microscopy. Acid sites were created by calcination without collapse of the molecular wire structure. The acidic molecular wire exhibited high activity and stability and promoted the hydrolysis of the glycosidic bond. Various biomasses including cellulose were able to be converted to hexoses as main products.
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A new organic-inorganic hybrid zeotype compound with amphiphilic one-dimensional nanopore and aluminosilicate composition was developed. The framework structure is composed of double aluminosilicate layers and 12-ring nanopores; a hydrophilic layer pillared by Q(2) silicon atom species and a lipophilic layer pillared by phenylene groups are alternately stacked, and 12-ring nanopores perpendicularly penetrate the layers. The framework topology looks similar to that of an AFI-type zeolite but possesses a quasi-multidimensional pore structure consisting of a 12-ring channel and intersecting small pores equivalent to 8-rings. The hybrid material with alternately laminated lipophilic and hydrophilic nanospaces can be assumed as a crystallized Langmuir-Blodgett film. It demonstrates microporous adsorption for both hydrophilic and lipophilic adsorptives, and its outer surface tightly adsorbs lysozyme whose molecular size is much larger than its micropore opening. Our results suggest the possibility of designing porous adsorbent with high amphipathicity.
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3-Acetamido-5-acetylfuran (3A5AF) is a potential platform compound for the production of nitrogen-containing pharmaceuticals and chemicals. 3A5AF can be obtained by dehydration of chitin or its monomer, N-acetylglucosamine (NAG). Here, we examined the use of solid catalysts for the dehydration of NAG to 3A5AF to achieve a more economical process that uses a recyclable catalyst. NAG was dehydrated using various solid catalysts in the presence of NaCl and N,N-dimethyl acetamide as solvent at 433â K. The yield of 3A5AF with the solid catalysts decreased in the following order: Al-exchanged montmorillonite>H-ZSM-5 (SiO2 /Al2 O3 =40)>H-montmorillonite (K-10)>Amberlyst15>H-ZSM-5 (SiO2 /Al2 O3 =300)>TiO2 >γ-Al2 O3 >ZrO2 >SiO2 â MgO>Na-montmorillonite. The highest yield of 3A5AF (14 %) was obtained with the Al-exchanged montmorillonite. The montmorillonite catalysts were characterized by using inductively coupled plasma optical emission spectroscopy, energy-dispersive X-ray spectroscopy, N2 adsorption, Fourier-transformed infrared spectroscopy, X-ray diffraction, and 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR). In addition, a combined catalyst of Al-exchanged montmorillonite and Cl- from synthetic hydrotalcite was found to be an active and recyclable solid catalyst for NAG dehydration to 3A5AF.
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Production of aromatic compounds from lignocellulosic biomass has recently been one goal of efforts to establish a sustainable society. We studied cellulose conversion into aromatic compounds over charcoal-supported metal catalysts (Pt/C, Pd/C, Rh/C, and Ru/C) in water at temperatures of 473-673 K. We found that charcoal-supported metal catalysts enhanced conversion of cellulose to aromatic compounds such as benzene, toluene, phenol, and cresol. The total yields of aromatic compounds produced from cellulose decreased in the order: Pt/C > Pd/C > Rh/C > no catalyst > Ru/C. This conversion could proceed even at 523 K. The total yield of aromatic compounds reached 5.8% with Pt/C at 673 K. The charcoal-supported metal catalysts also enhanced conversion of hemicellulose to aromatic compounds.
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Cryogenic electron microscopy is one of the fastest and most robust methods for capturing high-resolution images of proteins, but stringent sample preparation, imaging conditions, and in situ radiation damage inflicted during data acquisition directly affect the resolution and ability to capture dynamic details, thereby limiting its broader utilization and adoption for protein studies. We addressed these drawbacks by introducing synthesized giant carbon nano-test tubes (GCNTTs) as radiation-insulating materials that lessen the irradiation impact on the protein during data acquisition, physical molecular concentrators that localize the proteins within a nanoscale field of view, and vessels that create a microenvironment for solution-phase imaging. High-resolution electron microscopy images of single and aggregated hemoglobin molecules within GCNTTs in both solid and solution states were acquired. Subsequent scanning transmission electron microscopy, small-angle neutron scattering, and fluorescence studies demonstrated that the GCNTT vessel protected the hemoglobin molecules from electron irradiation-, light-, or heat-induced denaturation. To demonstrate the robustness of GCNTT as an imaging platform that could potentially augment the study of proteins, we demonstrated the robustness of the GCNTT technique to image an alternative protein, d-fructose dehydrogenase, after cyclic voltammetry experiments to review encapsulation and binding insights. Given the simplicity of the material synthesis, sample preparation, and imaging technique, GCNTT is a promising imaging companion for high-resolution, single, and dynamic protein studies under electron microscopy.
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Continuous syntheses of carbon-supported Pd@Pt core-shell nanoparticles were performed using microwave-assisted flow reaction in polyol to synthesize carbon-supported core Pd with subsequent direct coating of a Pt shell. By optimizing the amount of NaOH, almost all Pt precursors contributed to shell formation without specific chemicals.
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Polyoxometalate nanosheets were synthesized at the gas/liquid interface of an aqueous solution of Keggin-type silicotungstic acid, cesium chloride, and n-octylamine. The structure of the nanosheets was elucidated via aberration-corrected scanning transmission electron microscopy at the atomic and molecular levels.
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Here, we report the development of catalysts comprising highly dispersed Au on an alumina (Al2O3) support for the oxidation of glycerol to high-value carboxylic acids in a liquid-phase flow reactor. The catalysts were prepared by means of a deposition-precipitation method. To ensure that the catalysts could be used for long-term catalytic conversions in a liquid-phase flow reactor, we chose an alumina support with high temperature stability and a particle size (50-200 µm) large enough to prevent leakage of the catalyst from the reactor. One of the five catalysts had a high catalytic activity for the conversion of glycerol to the high-value carboxylic acids, glyceric acid and tartronic acid (conversion of glycerol >70%), and the catalyst retained its catalytic activity over long-term use (up to 1770 min). Pretreatment of the catalyst with fructose, a mild reductant, increased the activity of the catalyst. Scanning transmission electron microscopy revealed three Au species highly dispersed on the surface of the alumina support-Au nanoparticles (mode = 7.5-10 nm), Au clusters (1-2 nm), and atomic Au.
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Design of the structure and composition of crystalline microporous inorganic oxides is of great importance in catalysis. Developing new zeolites is one approach towards this design because of the tunable pore system and high thermal stability. Zeolites are limited to main group elements, which limits their applications in redox catalysis. Another promising choice is zeolitic transition metal oxides providing both porosity and redox activity, thereby further expanding the diversity of porous materials. However, the examples of zeolitic transition metal oxides are rare. Here, we report a new class of zeolitic vanadotungstates with tunable frameworks exhibiting a large porosity and redox activity. The assembly of [W4O16]8- units with VO2+ forms two isomeric porous frameworks. Owing to the complex redox properties and open porosity, the vanadotungstates efficiently catalyse the selective reduction of NO by NH3. This finding provides an opportunity for design and synthesis of inorganic multifunctional materials for future catalytic applications.
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A highly crystalline new precursor of CHA-type zeolite AlPO4-34 was obtained by using an aluminophosphate gel with a chiral diamine [(S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine; C9H18N2] as an organic structure directing agent under hydrothermal synthesis conditions. This precursor (called GAM-1) was changed into the zeolite AlPO4-34 which had a high porosity (the Brunauer-Emmett-Teller (BET) surface area is approximately 700 m3 g-1) using calcination. The GAM-1 obtained was characterized by various measurements, e.g., powder X-ray diffraction, scanning electron microscopy, and solid-state nuclear magnetic resonance spectroscopy, and so on. Structure determination from powder diffraction data revealed that the new precursor GAM-1 has triclinic symmetry [space group P1[combining macron], a = 9.16535(11) Å, b = 9.23042(11) Å, c = 9.29228(11) Å, α = 79.8243(7)°, ß = 87.4593(7)°, γ = 86.5365(7)°] and the chemical formula was estimated to be: |Al6P6O24H2F2|(C9H18N2)·2.5(H2O). It also revealed that a two edge sharing AlO4F2 octahedron with an [triple bond, length as m-dash]Al-F-Al[triple bond, length as m-dash] bridge was included in the framework. GAM-1 was transformed into AlPO4-34 with rhombohedral symmetry (R3[combining macron]) by elevating temperature to over 400 °C. At high temperatures, AlO4F2 octahedron connectivity was changed into an AlO4 tetrahedron. The crystal structure of the dehydrated AlPO4-34 changed back to a triclinic symmetry (P1) model again after rehydration in the atmosphere.
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Heteropolyanions and their arrays in microporous cesium salts of 12-tungstosilicic acid, Cs2.5H1.5[SiW12O40] and Cs4.0[SiW12O40], were observed by aberration-corrected scanning transmission electron microscopy. Microstructures that form micropores in the polyoxometalates were visualized.