Surface-modified mesoporous silicas as recyclable adsorbents of an endocrine disrupter, bisphenol A

Surface-modified mesoporous silicas (MSs) were investigated for recyclable adsorption of an endocrine disrupter, bisphenol A (BPA). Surface-modified MSs were prepared by (i) post-synthesis surface modification of MSs using surface hydroxyl groups and organosilanes (m-MS) and by (ii) co-condensation of tetraethoxysilane and the corresponding organosilanes (d-MS). Infrared measurements indicated that organic groups mainly existed on the surface of m-MS, which resulted in a surface characterized by high hydrophobicity. Both organic groups and isolated hydroxyl groups existed on the surface of d-MS, resulting in both hydrophobicity and hydrophilicity on the surface. The amount of BPA adsorbed on surface-modified MSs per organic group was similar for m-MS and d-MS, however, the d-MS established equilibrium for BPA adsorption faster than m-MS, as measured by UV-vis spectra. A larger amount of BPA per surface area could be adsorbed on carbon materials than on the surface-modified MSs, however, the regeneration of carbon materials by washing could not be done easily. The surface-modified MSs retain adsorption capacity for BPA after several regeneration cycles, demonstrating that the surface-modified MSs are effective recyclable adsorbents of the endocrine disrupter, bisphenol A.     

EXAFS Study on Structural Change of Charcoal-supported Ruthenium Catalysts during Lignin Gasification in Supercritical Water

Lignin gasification in supercritical water over charcoal supported ruthenium trivalent salts was studied using a batch reactor at 673 K. Ruthenium (III) nitrosyl nitrate on charcoal (Ru(NO)(NO₃)₃/C) was more active than ruthenium (III) chloride on charcoal (RuCl₃/C) for the gasification reaction. EXAFS analysis revealed that ruthenium metal particles were formed in both RuCl₃/C and Ru(NO)(NO₃)₃/C catalysts during the lignin gasification and that the size of ruthenium metal in Ru(NO)(NO₃)₃/C was smaller than that in RuCl₃/C. It was concluded that well-dispersed ruthenium metal particles were active for the lignin gasification in supercritical water.     

Time-resolved DXAFS study on the reduction processes of Cu cations in ZSM-5

The time-resolved reduction process of copper cations in/on ZSM-5 during temperature-programmed reduction (300–700 K) was studied by energy-dispersive X-ray absorption fine structure (DXAFS) as well as transmission electron microscopy (TEM). Two Cu-ZSM-5 samples with different Cu loadings were prepared by an ion-exchange method. The Cu K-edge DXAFS spectra for isolated Cu₂₊ species in the channels of ZSM-5 and CuO particles on the outer surfaces of ZSM-5 were recorded at an interval of 1 s during the reduction. The curve fitting analysis of the EXAFS data and the XANES analysis revealed that the isolated Cu₂₊ species in the channels were reduced stepwise. They were reduced to isolated Cu₊ species at 400–450 K and the Cu₊ species to Cu₀ metallic clusters at 550–650 K. Small clusters like Cu₄ were initially formed, followed by particle growth. A small part of them went out to the outer surfaces of ZSM-5 during the reduction. In contrast, CuO particles on the outer surfaces were reduced directly to Cu₀ metallic particles around 450 K.     

Dispersive XAFS Study on Cu and Mo Species in Zeolites During the Catalyst Preparation

A time-resolved energy dispersive XAFS (DXAFS) technique is applied to elucidate the local structure of catalyst precursors and active species during the preparation of catalysts. The structure of ion-exchanged copper species in ZSM-5 zeolite during temperature-programmed reduction and the structure of molybdenum carbonyl species in NaY zeolite during temperature-programmed decarbonylation were investigated by the DXAFS technique. The way of the analysis of XAFS data during the dynamic processes is also discussed. The XANES spectra were analyzed to determine the ratio of different species involved in the system as a function of temperature as well as the curve-fitting analysis of the time-resolved EXAFS. The detailed analysis of the XANES and EXAFS shed light on the structural changes during the dynamic processes. In Cu-ZSM-5, a stepwise reduction process of Cu species and the subsequent growth of Cu particles during the reduction were elucidated. In Mo–NaY, the formation of Mo subcarbonyl monomer species as an intermediate of molybdenum oxycarbide dimer species was observed. This paper demonstrates that the DXAFS technique is useful to study the chemistry of catalyst preparation and can provide vital information that cannot be obtained by other techniques.     

Gasification of Organosolv-lignin Over Charcoal Supported Noble Metal Salt Catalysts in Supercritical Water

Charcoal supported metal salt catalysts showed activities for the lignin gasification at 673 K, especially the catalysts without chloride anion showed the complete gasification. The order of activity for the gasification among the metal species was following: ruthenium > rhodium > platinum > palladium ~ nickel. X-ray absorption fine structure analysis revealed that small metal particles were formed on the charcoal support after the gasification for the supported ruthenium, rhodium, and platinum salt catalysts without chloride anion; on the other hand, larger metal particles were formed in the presence of chloride anion. Lower activities and deactivation for supported metal salt catalysts having the chloride anion were caused by poisoning by chloride anions and the smaller number of metal sites.     

Energy-dispersive XAFS study on the decarbonylation process of Mo(CO)6 in NaY zeolite

The temperature-programmed decarbonylation process of Mo(CO)₆ in NaY zeolite was studied by means of a time-resolved energy-dispersive XAFS method. The XANES analysis demonstrated that the decarbonylation proceeded by two successive steps via a stable intermediate which existed between 440 and 490 K. The curve fitting analysis of the EXAFS data revealed that the intermediate was a molybdenum monomer subcarbonyl species Mo(CO)₃(O_L)₃ coordinated by three CO ligands and three oxygen atoms of zeolite framework (O_L). Molybdenum dimer subcarbonyl species were not observed. This study demonstrated that the DXAFS technique is a powerful method to study the dynamic behavior of the Mo carbonyl species during decarbonylation process.     

Efficient Conversion of Glycerol into High Value-Added Chemicals by Partial Oxidation

Glycerol can be effectively converted to glyceric acid, a high value-added pharmaceutical raw material, through its partial oxidation over an Au/Al₂O₃ catalyst under strongly basic conditions. The factors important for the highly selective production of glyceric acid were investigated experimentally. It was clarified that NaOH was involved in the glycerol activation step to a glycerol alkoxide intermediate (2, 3-dihydroxypropoxide) in the liquid phase, then glyceric acid was formed by OOH species derived from O₂ on an Au catalyst in the partial oxidation step. We have newly discovered the concerted effect of NaOH and O₂ in different reaction steps.     

Dehydration of Triol Compounds in High-Temperature Liquid Water Under High-Pressure Carbon Dioxide

High-temperature liquid water treatment of triol compounds [1,2,3-propanetriol (glycerol), 1,2,4-butanetriol (1,2,4-BTO), and 1,2,5-pentanetriol (1,2,5-PTO)] was carried out using a batch reactor. Intramolecular dehydration to hydroxyacetone from glycerol, 3-hydroxytetrahydrofuran from 1,2,4-BTO, and both tetrahydrofurfuryl alcohol and 3-hydroxytetrahydropyran from 1,2,5-PTO proceeded in water at 573 K. The dehydration rates were enhanced by the addition of high-pressure carbon dioxide.