This article combines a systematic literature review on the fabrication of macroporous α-Al₂O₃ with increased specific surface area with recent results from our group. Publications claiming the fabrication of α-Al₂O₃ with high specific surface areas (HSSA) are comprehensively assessed and critically reviewed. An account of all major routes towards HSSA α-Al₂O₃ is given, including hydrothermal methods, pore protection approaches, dopants, anodically oxidized alumina membranes, and sol-gel syntheses. Furthermore, limitations of these routes are disclosed, as thermodynamic calculations suggest that γ-Al₂O₃ may be the more stable alumina modification for A_BET > 175 m²/g. In fact, the highest specific surface area unobjectionably reported to date for α-Al₂O₃ amounts to 16–24 m²/g and was attained via a sol-gel process. In a second part, we report on some of our own results, including a novel sol-gel synthesis, designated as mutual cross-hydrolysis. Besides, the Mn-assisted α-transition appears to be a promising approach for some alumina materials, whereas pore protection by carbon filling kinetically inhibits the formation of α-Al₂O₃ seeds. These experimental results are substantiated by attempts to theoretically calculate and predict the specific surface areas of both porous materials and nanopowders.

One of the major routes to synthesize macroporous α-Al₂O₃ is the sol-gel process in presence of templates. Templates include polymers as well as carboxylic acids, such as citric acid. By careful choice of the template, pore diameters can be adjusted between 110 nm and several µm. We report the successful establishment of plain short-chain dicarboxylic acids (DCA) as porogenes in the sol-gel synthesis of macroporous α-Al₂O₃. By this extension of the recently developed synthesis route, a very precise control of pore diameters is achieved, in addition to enhanced macropore volumes in α-Al₂O₃. The formation mechanism thereof is closely related to the one postulated for citric acid, as thermal analyses show. However, since branching in the DCA-linked alumina nuclei is not possible, close monomodal pore width distributions are attained, which are accompanied by enhanced pore volumes. This is a significant improvement in terms of controlled enhanced porosity in the synthesis of macroporous α-Al₂O₃.

Ceramic alumina foams are suitable catalyst supports with high temperature stability used, for example, in catalytic cracking processes or combined heat and power units. Herein, such replica foams are generated from macroporous α‐Al₂O₃ powder synthesized by a sol–gel process. The foam windows, constituting intrinsic (macroscopic) foam porosity, are supplemented by an additional porosity within the struts of the foams. These pores, originating from the sol–gel process, are preserved during sintering at 1350 °C. This results in less dense foams compared with foams from conventional alumina powders. Foams sintered at 1350 °C exhibit an increased strut porosity of ≈62%, of which ≈84% are open, with pore diameters in the range of 200–500 nm and a compressive strength of 0.2 MPa. Foams sintered at 1600 °C or higher possess an almost tenfold compressive strength but no additional strut porosity. Due to the use of carboxylic acids as porogenes in the sol–gel process, all samples generated from sol–gel‐derived alumina powder exhibit significantly higher porosity values than the respective reference foams made from commercial alumina powder. Although specific surface areas of ≈3 m² g⁻¹ are still small, this value is significantly improved by additional strut porosity.

Glass foams (GF) are materials with a porous framework characterized by pore sizes spanning different orders of magnitude. In this study, we report for the first time the synthesis and characterization of GF with cavities ranging from macro- to mesopore size obtained via the combination of a foaming process with phase separation and followed by selective leaching. A combination of techniques, namely N₂ sorption, Hg intrusion, scanning electron microscopy, and high-resolution X-ray computed tomography, enabled us to characterize the pores within different size ranges, showing that the GF produced have a complex multimodal pore structure. Computed tomography provided a visual and detailed quantitative description of the pores of hundreds of nanometers to several hundred micrometers and confirmed the presence of residues of the foaming agents still present in the GF walls. We present a comparison of the techniques used for characterizing the produced foams with a discussion of their advantages and limitations. Our results reveal that our multi-technique approach to characterize pores is valuable for developing novel porous materials with features in the nanometric range since it enables building a complete overview of the porous architecture in different size ranges, as no single technique alone would provide.

When impregnated with manganiferous precursors, γ-Al₂O₃ may be converted into α-Al₂O₃ under relatively mild and energy-saving conditions. In this work, a manganese assisted conversion to corundum at temperatures as low as 800 °C is investigated. To observe the alumina phase transition, XRD and solid-state ²⁷Al-MAS-NMR are applied. By post-synthetical treatment in concentrated HCl, residual manganese is removed up to 3 wt.-%. Thereby, α-Al₂O₃ with a high specific surface area of 56 m² g⁻¹ is obtained after complete conversion. Just as for transition alumina, thermal stability is an important issue for corundum. Long-term stability tests were performed at 750 °C for 7 days. Although highly porous corundum was synthesized, the porosity decreased with time at common process temperatures.