Defect-engineered nonstoichiometric perovskite hosting high-activity PdO sites for enhanced hydrocarbon oxidation.

Yu, Jihang; Wang, Zhi-Qiang; Jiang, Yongjun; Yan, Jiaorong; Guo, Yanglong; Guo, Yun; Wang, Li; Wang, Aiyong et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

Supported noble metal catalysts are central to industrial, environmental, and energy applications, yet precisely constructing active sites with optimized geometry remains a formidable challenge beyond conventional particle size control. Here, we introduce a perovskite-based surface defect engineering strategy that enables atomic-level regulation of noble metal active sites. By tailoring La stoichiometry in LaAlO<sub>3</sub>, we engineer three distinct surface morphologies (planar, stepped, and crater-like) that serve as templates for anchoring and replicating supported PdO nanoparticles. Among these, the step-rich PdO configuration on La<sub>0.9</sub>AlO<sub>3-δ</sub> exhibits the highest methane oxidation activity, with a linear correlation between Pd step-site density and catalytic performance. The enhancement arises from low-coordination Pd atoms at step sites, which form stable Pd-C(CH<sub>3</sub>) covalent bonds and facilitate C-H bond activation, the rate-determining step in methane oxidation. This work establishes a generalizable approach to precisely tailor noble metal active sites through perovskite surface engineering, providing a robust framework for the rational design of efficient and durable oxidation catalysts.