Two-Dimensional Submonolayer Pt Clusters with Optimal Pt 0 –Pt δ+ Sites for Efficient Methylcyclohexane Dehydrogenation

作者：Zheng Jian Li, Mingzhi Wang, Huayue Yang, Yanyan Jia, Shumin Liu, Shuangli Yang, Mingshu Chen, Pei Wang, Sheng Dai, Linan Zhou, Yun Zhao, Guangxu Chen · 发表于：ACS Nano · 年份：2025 · DOI：10.1021/acsnano.5c12158 · 被引用次数：7 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Electrocatalysts for Energy Conversion、Catalytic Processes in Materials Science

Methylcyclohexane dehydrogenation (MCHDH) is vital in hydrogen storage and carriage technologies. However, Pt/Al 2 O 3, as a classic practical catalyst for MCHDH, remains ambiguous regarding the catalytic structure of active Pt sites for C–H activation at the atomic scale due to a shortage of subnanometer characterization. Here, based on comprehensive structural characterizations and density functional theory (DFT) calculations, we demonstrate optimal active Pt sites: two-dimensional (2D) submonolayer clusters (SLCs) interfaced with γ-Al 2 O 3 with an appropriate ratio of Pt δ+ to Pt 0 to form optimal Pt 0 –Pt δ+ interfacial sites that have superior activity for the MCHDH reaction. This SLC’s catalyst achieves a reaction rate of up to 29,353 mmol g Pt –1 min –1 at 320 °C, with a 99.98% selectivity for toluene over MCHDH, which is significantly better than that of the corresponding Pt single atoms and conventional Pt nanoparticles (NPs) catalysts. The excellent MCHDH performance of Pt 2D SLCs is attributed to their sufficient 5d-electron domination and the optimal Pt 0 –Pt δ+ sites, which facilitate the sequential activation of multiple C–H bonds and toluene desorption. In comparison, the presence of too many continuous Pt 0 –Pt 0 sites in Pt 2D SLCs can hinder these processes. Our study highlights that constructing atomic-scale 2D submonolayer metal clusters is a promising strategy for optimizing efficient catalysts with abundant M 0 –M δ+ (M = metal) sites, enhancing the cat...