Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic.

Liu, Shuo; Dun, Chaochao; Jiang, Qike; Xuan, Zhengxi; Yang, Feipeng; Guo, Jinghua; Urban, Jeffrey J; Swihart, Mark T · Nat Commun · 2024

basic_science · Level V

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Abstract

The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)O<sub>x</sub>, and (NiZr)O<sub>x</sub>, we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an "encapsulated exsolution" phenomenon observed upon reducing the metastable porous (Ni<sub>0.07</sub>Al<sub>0.93</sub>)O<sub>x</sub> to create ultra-stable Ni nanoparticles embedded within the walls of porous Al<sub>2</sub>O<sub>3</sub> nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO<sub>2</sub> reforming of methane, maintaining constant 96% CH<sub>4</sub> and CO<sub>2</sub> conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.