Defect-driven nanostructuring of low-nuclearity Pt-Mo ensembles for continuous gas-phase formic acid dehydrogenation

• Published in: Nature communications Vol. 14; no. 1; p. 7518
• Main Authors: Guo, Luyao, Zhuge, Kaixuan, Yan, Siyang, Wang, Shiyi, Zhao, Jia, Wang, Saisai, Qiao, Panzhe, Liu, Jiaxu, Mou, Xiaoling, Zhu, Hejun, Zhao, Ziang, Yan, Li, Lin, Ronghe, Ding, Yunjie
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 18-11-2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 639/638/77/887; 639/925/357; Acids; Bimetals; Carbon; Catalysis; Catalysts; Chemistry; Clean technology; Decomposition; Defects; Dehydrogenation; Density functional theory; Energy; Engineering; Formic acid; Humanities and Social Sciences; Infrared spectroscopy; Laboratories; Metal clusters; Metals; Molybdenum; multidisciplinary; Nanoclusters; Nitrogen; Phase decomposition; Platinum; Porous materials; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-42759-5

Supported metal clusters comprising of well-tailored low-nuclearity heteroatoms have great potentials in catalysis owing to the maximized exposure of active sites and metal synergy. However, atomically precise design of these architectures is still challenging for the lack of practical approaches. Here, we report a defect-driven nanostructuring strategy through combining defect engineering of nitrogen-doped carbons and sequential metal depositions to prepare a series of Pt and Mo ensembles ranging from single atoms to sub-nanoclusters. When applied in continuous gas-phase decomposition of formic acid, the low-nuclearity ensembles with unique Pt
3
Mo
1
N
3
configuration deliver high-purity hydrogen at full conversion with unexpected high activity of 0.62 mol
HCOOH
mol
Pt
−1
s
−1
and remarkable stability, significantly outperforming the previously reported catalysts. The remarkable performance is rationalized by a joint operando dual-beam Fourier transformed infrared spectroscopy and density functional theory modeling study, pointing to the Pt-Mo synergy in creating a new reaction path for consecutive HCOOH dissociations.
Precise design of bimetallic low-nuclearity catalysts is challenging. Here, the authors report a defect-driven nanostructuring strategy combining defect engineering of nitrogen-doped carbons and sequential metal depositions, yielding a series of platinum and molybdenum ensembles in the sub-nano regime.