Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation
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Date
2018-07-06
Publication Type
Journal Article
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yes
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Abstract
Ensemble control has been intensively pursued for decades to identify sustainable alternatives to the Lindlar catalyst (PdPb/CaCO3) applied for the partial hydrogenation of alkynes in industrial organic synthesis. Although the geometric and electronic requirements are known, a literature survey illustrates the difficulty of transferring this knowledge into an efficient and robust catalyst. Here, we report a simple treatment of palladium nanoparticles supported on graphitic carbon nitride with aqueous sodium sulfide, which directs the formation of a nanostructured Pd3S phase with controlled crystallographic orientation, exhibiting unparalleled performance in the semi-hydrogenation of alkynes in the liquid phase. The exceptional behavior is linked to the multifunctional role of sulfur. Apart from defining a structure integrating spatially-isolated palladium trimers, the active ensembles, the modifier imparts a bifunctional mechanism and weak binding of the organic intermediates. Similar metal trimers are also identified in Pd4S, evidencing the pervasiveness of these selective ensembles in supported palladium sulfides.
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published
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Volume
9 (1)
Pages / Article No.
2634
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Nature
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Subject
Catalytic mechanisms; Density functional theory; Heterogeneous catalysis
Organisational unit
03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier
Notes
Funding
169679 - Doing more with less: efficient single-atom catalysts based on carbon nitride for sustainable chemical transformations (SNF)