Abstract
Aluminium-containing spherical mesoporous silica nanoparticle (AlSMSN) materials were synthesized for the first time using cetyltrimethylammonium bromide (CTMABr) as a structure-directing agent under nonhydrothermal conditions at room temperature. The effect of the nature of the Al source on the synthesis of the AlSMSN materials was investigated using a variety of Al sources. The effect of higher Al ion incorporation on the structural and textural properties of the AlSMSN materials was evaluated by varying the n(Si)/n(Al) ratios, and an efficient chemical treatment method was developed for the removal of superficial octahedral Al ions from the surface of the AlSMSN materials. The synthesized AlSMSN materials were characterized using ICP-AES, XRD, N-2 adsorption, Al-27 & Si-29 MAS NMR, FTIR, TEM, and FE-SEM techniques. ICP-AES results revealed incorporation of a high Al ion content (n(Si)/n(Al) = 24) into the spherical mesoporous silica nanoparticle materials. For all of the calcined AlSMSN materials, the XRD reflection peaks shifted to lower angle with increasing Al ion content, resulting in an increase of the unit cell parameter. The textural parameters of the AlSMSN materials, except for the surface area, found from nitrogen adsorption measurements, increase with an increase in the amount of aluminium isopropoxide in the synthesis gel. The location and coordination of Al ions on the walls of the AlSMSN materials and the amount of Al ions incorporation were determined from the Al-27 MAS NMR measurements. TEM and FE-SEM images demonstrated that the AlSMSN materials comprise spherical particles with hexagonally packed uniform mesoporous channels. Furthermore, the AlSMSN(20) with a higher Al content exhibits better hydrothermal stability than the AlSMSN(100) congener with a lower Al content. Catalyst recyclability studies showed that the washed catalyst (W-AlSMSN(20)) exhibited exceptional catalytic activity during t-butylation of phenol with 95.4% 4-t-butylphenol (4-TBP) selectivity due to removal of superficial octahedrally coordinated Al ions on the surface of active sites.