An Al‐containing MIL‐53 metal‐organic framework with very high surface area (SBET=1130 m2.g−1, N2 sorption) was used as sacrificial template to prepare a nickel‐alumina‐based catalyst (Ni0AlMIL) highly active and stable in the reaction of dry reforming of methane (DRM). The procedure consisted in impregnating the activated (solvent free) MIL‐53 sample with a nickel precursor solution, then calcining the material to remove the organic linkers and subsequently reducing it to form the reduced nickel active phase. At the step of calcination, this procedure results in the formation of a porous uniform spinel phase with Ni nanospecies embedded in the alumina‐based matrix, as deduced from XRD, TPR and TEM analyses. This leads after reduction to a porous lamellar γ‐Al2O3 material with small Ni0 nanoparticles homogeneously dispersed and stabilized within the support. The performances of this catalyst in DRM are better than those of two reference Ni/alumina catalysts prepared for comparison by conventional nickel impregnation of two preformed alumina supports: a first one obtained by calcination of MIL‐53 (AlMIL) and a second one consisting of a commercial γ‐Al2O3 batch (AlCOM). Under steady state conditions at a temperature of 650 °C and a pressure of 1 bar, the higher CH4 and CO2 conversions (till 3 times higher than on Ni0/AlCOM), high catalytic stability (no loss of activity after 13–100 h) and higher selectivity towards DRM (H2:CO products ratio remaining at 1) on Ni0AlMIL compared to the other catalysts is believed to come from the particularly strong interaction between the nickel and alumina phases generated by using the unique high specific surface of the parent MOF support to deposit nickel. This creates an intimate mixing favorable to a persisting interaction of the nickel nanoparticles with the alumina support in the reduced material. The lamellar shape of the γ‐Al2O3 composing the catalyst and its remaining high specific surface may also contribute to the excellent Ni resistance to sintering and in turn to the inhibition of carbon nanotubes formation during the reaction.

Two routes of preparation of mesoporous Ni-alumina materials favoring the intermediate formation of nanostructured nickel-aluminate are presented. The first one involves an aluminum containing MOF precursor used as sacrificial template to deposit nickel while the second is based on a one-pot synthesis combined to an EISA method. As shown by a set of complementary techniques, the nickel-aluminate nanospecies formed after calcination are homogeneously distributed within the developed mesoporous alumina matrices whose porous characteristics vary depending on the preparation method. A special attention is paid to electron-microscopy observations using especially STEM imaging with high chemical sensitivity and EDS elemental mapping modes that help visualizing the extremely high nickel dispersion and highlight the strong metal anchoring to the support that persists after reduction. This leads to active nickel nanoparticles particularly stable in the reaction of dry reforming of methane.