Abstract
The sintering of Supported Transition Metal Catalysts (STMCs) is a core issue during high temperature catalysis. Perovskite oxides as host matrix for STMCs are proven to be sintering-resistance, leading to a family of self-regenerative materials. However, none other design principles for self-regenerative catalysts were put forward since 2002, which cannot satisfy diverse catalytic processes. Herein, inspired by the principle of high entropy-stabilized structure, a concept whether entropy driving force could promote the self-regeneration process is proposed. To verify it, a high entropy cubic Zr0.5(NiFeCuMnCo)0.5Ox is constructed as a host model, and interestingly in situ reversible exsolution-dissolution of supported metallic species are observed in multi redox cycles. Notably, in situ exsolved transition metals from high entropy Zr0.5(NiFeCuMnCo)0.5Ox support, whose entropic contribution (TΔSconfig = T⋆12.7 J mol−1 K−1) is predominant in ∆G, affording ultrahigh thermal stability in long-term CO2 hydrogenation (400 °C, >500 h). Current theory may inspire more STWCs with excellent sintering-resistance performance.
Highlights
The sintering of Supported Transition Metal Catalysts (STMCs) is a core issue during high temperature catalysis
Inspired by the principle of the high entropy-stabilized structure, the synthesis of high entropy ZrO2 catalyst was carefully investigated by a mechanochemical process (Fig. 2)
The contribution of high entropy for the sintering-resistance ability of supported transition metals was figured out, while severe particle growth occurred on Zr0.5Cu0.5Ox and Zr0.5(CuCoNi)0.5Ox treated in H2
Summary
The sintering of Supported Transition Metal Catalysts (STMCs) is a core issue during high temperature catalysis. Based on the configurational entropy[34] (it refers to the number of conformations of a molecule and the number of ways that atoms or molecules pack together in the oxide) formula (Fig. 1.bi), more disorder of system and higher randomness of structure with a lower Gibbs free energy can contribute to the stability of host structure, especially during high temperature catalysis (ΔG = H-TΔS)[31,36] (Fig. 1bii) From another perspective, the reintegration process can be promoted due to an entropy-added motivation by the oxidative transformation of isolated metals back into parent metal oxides. The self-regenerative talent of high entropy material may open an alternative for the design of sintering-resistance catalysts
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