In this work, the macro-mesoporous alumina monolith has been achieved for the first time via co-polymerization of styrene emulsion and aluminum precursor. After elimination of organic components by calcination at 800 °C, the well-crystallized η-Al2O3 phase was obtained, with SBET of 247.7 m2/g. The spherical macropores in the micrometer range originated from a condensation reaction during drying, and the wormhole-like mesopores (ca. 3.6 nm) distributed on the macroporous walls were the result of the assembly of nanoparticles. The method can be extended to prepare other porous metal oxide monoliths.Highlights► Co-polymerization method is carried out to prepare monoliths. ► Aluminum nitrate is used as precursor of alumina. ► The monolith exhibits continuous macropores.

Bimodal mesoporous γ-Al2O3 (BMA) synthesized by a simple hydrothermal route was applied as support for CoMo-based catalyst. The materials were characterized and evaluated for hydrodesulfurization of 4,6-Dimethyldibenzothiophene (4,6-DMDBT) in a fixed-bed reactor. BMA displayed simultaneously high surface area, large porosity and particular hierarchically mesoporous structure after calcination at 550 °C. By taking advantage of these properties, CoMo-BMA catalyst bearing high active species dispersion, good reducibility and enhanced diffusibility was used in this work to compare with commercial γ-Al2O3 supported catalyst. The obtained results showed that BMA had a good potential as support for hydrodesulfurization catalysts.