Postalkoxysilylation with diethoxydimethylsilane has been carried out on the zeolitic lamellar precursors of various topologies such as MWW, FER, CDO and MCM-47 aiming to construct new crystalline structures with expanded pore apertures between the layers. The silylation process and the crystalline and pore structures of the resulting materials have been investigated with the techniques of XRD, IR, (13)C and (29)Si MAS NMR, ICP, SEM, HRTEM, elemental analyses, and N 2 adsorption. In contrast to forming known three-dimensional zeolite structures after direct calcination of the lamellar precursors, the silylation led to new crystalline structures with opener pores, as evidenced by the shift of layer-related diffractions to the lower-angle region in XRD patterns and the enlarged interlayer pores found by HRTEM images. After optimizing the treatment conditions, particularly the amount of silane agent, a maximum and homogeneous silylation was realized, which guaranteed the phase purity in interlayer expanded zeolites. The expanded structures were well preserved after calcination at 823 K or reflux in water for 1 to 2 weeks, indicating a high thermal stability and also a hydrothermal stability. The interlayer expanded zeolites prepared from the metallosilicate precursors of MWW topology exhibited higher catalytic activities in the redox and solid acid-catalyzed reactions of bulky molecules than that of their counterparts with conventional MWW topology.
p-Arsanilic acid (p-ASA), is a widely used animal feed additive in many developing countries, and is often introduced to agricultural soils with animal wastes. A common soil metal oxide, birnessite (δ-MnO2), was found to mediate its degradation with fast rates under acidic conditions. Experimental results indicate that adsorption and degradation of p-ASA on the surface of δ-MnO2 were highly pH dependent, and the overall kinetics for p-ASA degradation and formation of precursor complex could be described by a retarded first-order rate model. For the reaction occurring between pH 4.0 and 6.2, the initial rate equation was determined to be rinit=2.36×10(-5)[ASA]0.8[MnO2]0.9[H+]0.7. p-ASA first forms a surface precursor complex on δ-MnO2 during degradation, followed by formation of p-ASA radicals through single-electron transfer to δ-MnO2. The p-ASA radicals subsequently undergo cleavage of arsenite group (which is further oxidized to arsenate) or radical-radical self-coupling. Instead of full mineralization (with respect to arsenic only), about one-fifth of the p-ASA "couples" to form an arsenic-bearing azo compound that binds strongly on δ-MnO2. The fast transformation of p-ASA to arsenite and arsenate mediated by δ-MnO2 significantly increases the risk of soil arsenic pollution and deserves significant attention in the animal farming zones still using this feed additive.
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