Organosilanesulfonic acid (-Si-R3S-R4SO3H, OSA)-functionalized mesoporous Zr-TMS (Zr-TMS-Si-R3S-R4SO3H, Zr-TMS-OSA) was synthesized either by post-synthetic modification of Zr-TMS (zirconia-based transition metal oxide mesoporous molecular sieves) with 3-mercaptopropyltrimethoxysilane (3-MPTS) and further with 1,4-butanesultone (1,4-BS) or by in situ one-pot synthesis procedure. A number of physico-chemical characterization techniques have been used to show that the organosilanesulfonic acid groups were anchored on to the walls of Zr-TMS. MCM-41-Si-R3S-R4SO3H-20 (MCM-41-OSA-20) was also prepared by post-synthesis procedure for comparison. Physico-chemical properties of in situ made A-Zr-OSA-20, Zr-TMS-SO3H-20 and MCM-41-OSA-20 were compared with Zr-TMS-OSA catalysts. The catalytic activity of the materials was tested in liquid phase condensation of aniline with p-formaldehyde to 4,4'-diaminodiphenylmethane (4,4'-DADPM). Results showed that Zr-TMS-OSA catalysts were more active than Zr-TMS-SO3H-20, MCM-41-OSA-20 and A-Zr-OSA-20 and more selective than Zr-TMS-SO3H-20 and A-Zr-OSA-20 catalysts. (C) 2006 Elsevier B.V. All rights reserved.

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