新規層状ケイ酸塩HUSs : 機能材料としての応用展望

広島大学(Hiroshima University)博士(工学)Doctor of Engineeringdoctora

Conversion of ethanol to propylene over HZSM-5(Ga) co-modified with lanthanum and phosphorous

Conversion of ethanol to propylene was carried out over HZSM-5(Ga) co-modified with lanthanum and phosphorous (La/P/HZSM-5(Ga)). The propylene yield was strongly dependent on both the La/Ga and P/Ga ratios, and the highest value of ca.29 C-% was obtained at a P/Ga ratio of 1 and a La/Ga ratio of 0.4. FT-IR, P-31 MAS NMR, and Ga-71 MAS NMR measurements demonstrate that the introduced lanthanum reacts with the pre-introduced phosphorous to regenerate some of Bronsted acid sites (Si(OH)Ga), and accordingly, the Bronsted acid sites are homogeneously distributed within the zeolite framework. In addition, the catalytic stability as well as the catalytic activity of HZSM-5(Ga) was effectively enhanced by co-modification with lanthanum and phosphorous because of the suppression of carbonaceous deposition and elimination of gallium from the zeolite framework

Preparation of Preyssler-type Phosphotungstate with One Central Potassium Cation and Potassium Cation Migration into the Preyssler Molecule to form Di-Potassium-Encapsulated Derivative

A mono-potassium cation-encapsulated Preyssler-type phosphotungstate, [P5W30O110K]14− (1), was prepared as a potassium salt, K14[P5W30O110K] (1a), by heating mono-bismuth- or mono-calcium-encapsulat ed Prey ssler-type p hosphot ungstates (K12[P5W30O110Bi(H2O)] or K13[P5W30O110Ca(H2O)]) in acetate buffer. Characterization of the potassium salt 1a by single-crystal X-ray structure analysis, 31P and 183W nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectroscopy, and elemental analysis revealed that one potassium cation is encapsulated in the central cavity of the Preyssler-type phosphotungstate molecule with a formal D5h symmetry. Density functional theory calculations have confirmed that the potassium cation prefers the central position of the cavity over a side position, in which no water molecules are coordinated to the encapsulated potassium cation. 31P NMR and cyclic voltammetry analyses revealed the rapid protonation−deprotonation of the oxygens in the cavity compared to that of other Preyssler-type compounds. Heating of 1a in the solid state afforded a di-K+-encapsulated compound, K13[P5W30O110K2](2a), indicating that a potassium counter-cation is introduced in one of the side cavities, concomitantly displacing the internal potassium ion from the center to a second side cavity, thus providing a new method to encapsulate an additional cation in Preyssler compounds.M.S. is grateful for the A-STEP program of the Japanese Science and Technology Agency (JST), and Furukawa Foundation for the Promotion of Technology. X.L. thanks the Spanish Ministry of Science and Innovation (MICINN) (project CTQ2011-29054-C02-01/BQU), the DGR of the Generalitat de Catalunya (grant no. 2014SGR199), and the XRQTC. This work was also supported by the Center for Functional Nano Oxide at Hiroshima University. M.N.K.W. thanks the Indonesian Endowment Fund for Education (LPDP), Ministry of Finance, Republik Indonesia, for a Ph.D. scholarship

Layered zeolitic materials: an approach to designing versatile functional solids

Relevant layered zeolites have been considered in this perspective article from the point of view of the synthesis methodologies, materials characterization and catalytic implications, considering the unique physico-chemical characteristics of lamellar materials. The potential of layered zeolitic precursors to generate novel lamellar accessible zeolites through swelling, intercalation, pillarization, delamination and/ or exfoliation treatments is studied, showing the chemical, functional and structural versatility exhibited by layered zeolites. Recent approaches based on the assembly of zeolitic nanosheets which act as inorganic structural units through the use of dual structural directing agents, the selective modification of germanosilicates and the direct generation of lamellar hybrid organic inorganic aluminosilicates are also considered to obtain layered solids with well-defined functionalities. The catalytic applications of the layered zeolites are also highlighted, pointing out the high accessibility and reactivity of active sites present in the lamellar framework.The authors thank financial support to Spanish Government by Consolider-Ingenio MULTICAT CSD2009-00050, MAT2011-29020-C02-01 and Severo Ochoa Excellence Program SEV-2012-0267.Díaz Morales, UM.; Corma Canós, A. (2014). Layered zeolitic materials: an approach to designing versatile functional solids. Dalton Transactions. 43(27):10292-10316. https://doi.org/10.1039/c3dt53181cS10292103164327Mallouk, T. E., & Gavin, J. A. (1998). Molecular Recognition in Lamellar Solids and Thin Films. Accounts of Chemical Research, 31(5), 209-217. doi:10.1021/ar970038pSuslick, K. S., & Price, G. J. (1999). APPLICATIONS OF ULTRASOUND TO MATERIALS CHEMISTRY. Annual Review of Materials Science, 29(1), 295-326. doi:10.1146/annurev.matsci.29.1.295Du, X., Zhang, D., Gao, R., Huang, L., Shi, L., & Zhang, J. (2013). 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Multifunctional Hybrid Organic−Inorganic Catalytic Materials with a Hierarchical System

Efficient cycloaddition of carbon dioxide with epoxide to produce five-membered cyclic carbonates by amine-functionalized silicoaluminophosphates molecular sieves

The synthesis of functionalized microporous materials as very effective catalysts is a significant and rapidly increasing research topic with the goal for providing more efficient energy alternatives and contributing to the reduction of atmospheric CO2 levels. Carbon dioxide is a greenhouse gas that traps heat in the atmosphere, contributing to global warming and climate change. SAPO-5 and SAPO-34 molecular sieves were post-synthetically –NH2 functionalized, and the existence of –NH2 functionalities in the SAPO structure wall was demonstrated by FT-IR, CHN analysis. Powder XRD confirmed the crystalline structures of the modified SAPO-34 materials with amine functionalities. FE-SEM examined the morphology of the materials. The functionalized silicoaluminophosphate materials were investigated in the cyclo-addition of CO2 to epoxide (cyclohexene oxide and styrene oxide), where the catalytic performance of post-synthetically functionalized materials as catalyst were found to be superior. The amine group of the silicoaluminophosphates materials were essential for the activation of CO2. For treated SAPO-34, reactant conversion in cyclohexene oxide and styrene oxide was reported to be 94% and 93%, respectively. Because of the high recyclability of these materials, the catalysts are found to be both cost-effective and environmentally benign

Microporous materials formed via intercalation of ultrathin coordination polymers in a layered silicate

Development of microporous materials, like zeolites and metal-organic frameworks (MOFs), with unique and better properties, is crucially important, while yet challenging, for many energy applications. Herein, we report on a new family of microporous hybrids having well-defined permanent porosity, which is formed by pillaring a layered silicate with packed coordination polymers. This inorganic-organic hybrid material, having well-defined/two-faced micropores surrounded by the polymers and silicate walls, exhibits superior adsorption toward methanol due to co-operative interactions compared with conventional microporous materials. The material could be used as an adsorbent to selectively and effectively recover methanol from a methanol/water vapour mixture