journal article·2025-10-07

Two-Dimensional Submonolayer Pt Clusters with Optimal Pt0–Ptδ+ Sites for Efficient Methylcyclohexane Dehydrogenation

Zhengjian Li, Mingzhi Wang, Huayue Yang, Yanyan Jia, Shumin Liu, Shuangli Yang, Mingshu Chen, Pei Wang, Sheng Dai, Linan Zhou, Yun Zhao, Guangxu Chen

ACS Nano· Volume 19· Issue 39
Publisher page

Abstract

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 catalytic performance for selective C–H bond activation.
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Research context

OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Electrocatalysts for Energy Conversion · Catalytic Processes in Materials Science

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, National Engineering Laboratory for VOCs Pollution Control Technology and Equipment

South China University of Technology

Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, FeringaArno Pro Nobel Prize Scientist Joint Research Centre, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering

East China University of Science & Technology

State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering

Xiamen University

College of Science

Huazhong Agricultural University

Spin-X Institute, School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices

Funding

Guangdong Provincial Introduction of Innovative Research and Development Team · National Key Research and Development Program of China · Guangdong Provincial Pearl River Talents Program · National Natural Science Foundation of China · Guangzhou Basic and Applied Basic Research Program

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