Wenbin Yu

Facile preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance of benzene adsorption: the effects of NaOH etching pretreatment.

Hierarchically porous diatomite/MFI-type zeolite (Dt/Z) composites with excellent benzene adsorption performance were prepared. The hierarchical porosity was generated from the microporous zeolite coated at the surface of diatom frustules and from the macroporous diatomite support. A facile NaOH etching method was employed for the first time to treat the frustule support, followed by hydrothermal growth of MFI-type zeolite at the surface of frustules previously seeded with nanocrystalline silicalite-1 (Sil-1). NaOH etching enlarged the pores on diatom frustules and further increased the coated zeolite contents (W(z)). The central macropore size of the diatom frustules increased from approximately 200-500 nm to 400-1000 nm after NaOH etching. The W(z) could reach 61.2%, while the macroporosity of the composites was largely preserved due to more voids for zeolite coating being formed by NaOH etching. The Dt/Z composites exhibited higher benzene adsorption capacity per unit mass of zeolite and less mass transfer resistance than Sil-1, evaluated via a method of breakthrough curves. These results demonstrate that etching of a diatomite support is a facile but crucial process for the preparation of Dt/Z composites, enabling the resulting composites to become promising candidates for uses in volatile organic compounds emission control.

Surface silylation of natural mesoporous/macroporous diatomite for adsorption of benzene.

Naturally occurring porous diatomite (Dt) was functionalized with phenyltriethoxysilane (PTES), and the PTES-modified diatomite (PTES-Dt) was characterized using diffuse reflectance Fourier transform infrared spectroscopy, nitrogen adsorption, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. After silylation, a functional group (-C6H5, phenyl) was successfully introduced onto the surface of Dt. PTES-Dt exhibited hydrophobic properties with a water contact angle (WCA) as high as 120°±1°, whereas Dt was superhydrophilic with a WCA of 0°. The benzene adsorption data on both Dt and PTES-Dt fit well with the Langmuir isotherm equation. The Langmuir adsorption capacity of benzene on PTES-Dt is 28.1 mg/g, more than 4-fold greater than that on Dt. Moreover, the adsorption kinetics results show that equilibrium was achieved faster for PTES-Dt than for Dt, over the relative pressure range of 0.118-0.157. The excellent benzene adsorption performance of PTES-Dt is attributed to strong π-system interactions between the phenyl groups and the benzene molecules as well as to the macroporosity of the PTES-Dt. These results show that the silylated diatomite could be a new and inexpensive adsorbent suitable for use in benzene emission control.

Preparation of porous diatomite-templated carbons with large adsorption capacity and mesoporous zeolite K-H as a byproduct.

In this study, KOH activation was performed to enhance the porosity of the diatomite-templated carbon and to increase its adsorption capacity of methylene blue (MB). In addition to serving as the activation agent, KOH was also used as the etchant to remove the diatomite templates. Zeolite K-H was synthesized as a byproduct via utilization of the resultant silicon- and potassium-containing solutions created from the KOH etching of the diatomite templates. The obtained diatomite-based carbons were composed of macroporous carbon pillars and tubes, which were derived from the replication of the diatomite templates and were well preserved after KOH activation. The abundant micropores in the walls of the carbon pillars and tubes were derived from the break and reconfiguration of carbon films during both the removal of the diatomite templates and KOH activation. Compared with the original diatomite-templated carbons and CO2-activated carbons, the KOH-activated carbons had much higher specific surface areas (988 m(2)/g) and pore volumes (0.675 cm(3)/g). Moreover, the KOH-activated carbons possessed larger MB adsorption capacity (the maximum Langmuir adsorption capacity: 645.2 mg/g) than those of the original carbons and CO2-activated carbons. These results showed that KOH activation was a high effective activation method. The zeolite K-H byproduct was obtained by utilizing the silicon- and potassium-containing solution as the silicon and potassium sources. The zeolite exhibited a stick-like morphology and possessed nanosized particles with a mesopore-predominant porous structure which was observed by TEM for the first time.

Possible mechanism of structural incorporation of Al into diatomite during the deposition process I. Via a condensation reaction of hydroxyl groups

The structural incorporation of aluminium (Al) into diatomite is investigated by preparing several Al-diatomite composites by loading an Al precursor, hydroxyl aluminum polymer (Al13), onto the surface of diatomite and heating at various temperatures. The results indicate that Al was incorporated and implanted into the structure of diatomite by the condensation reaction of the hydroxyl groups of Al13 and diatomite, and the Si-O-Al(OH) groups were formed during the condensation reaction. Al incorporation by the condensation reaction of hydroxyl groups of Al13 with single silanols of diatomite occurred more readily than that with geminal silanols. The Al incorporation increased solid acidity of diatomite after Al incorporation. The acidity improvement was various for different types of acid sites, depending on the preparation temperature of the Al-incorporated diatomite. Both Brønsted and Lewis acid sites increased greatly after heating at 250 and 350 °C, but only L acid sites significantly improved after heating at 500 °C. These results demonstrate that the structural incorporation of Al(3+) ions into diatomite can occur by the condensation reaction of the hydroxyl groups of the Al precursors and diatomite. Moreover, the rich solid acid sites of Al-incorporated diatomite show its promising application as a solid acid catalyst.