Explaining the Size Dependence in Platinum‐Nanoparticle‐Catalyzed Hydrogenation Reactions

Abstract

Hydrogenation reactions are industrially important reactions that typically require unfavorably high H pressure and temperature for many functional groups. Herein we reveal surprisingly strong size-dependent activity of Pt nanoparticles (PtNPs) in catalyzing this reaction. Based on unambiguous spectral analyses, the size effect has been rationalized by the size-dependent d-band electron structure of the PtNPs. This understanding enables production of a catalyst with size of 1.2 nm, which shows a sixfold increase in turnover frequency and 28-fold increase in mass activity in the regioselective hydrogenation of quinoline, compared with PtNPs of 5.3 nm, allowing the reaction to proceed under ambient conditions with unprecedentedly high reaction rates. The size effect and the synthesis strategy developed herein may provide a general methodology in the design of metal-nanoparticle-based catalysts for a broad range of organic syntheses.

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“…The results corroborate the strong Pt-BP interaction. [34,36,39] These results reveal the formation of a PtP x O y complex on the surface of Pt/BP. [34,36,39] These results reveal the formation of a PtP x O y complex on the surface of Pt/BP.…”

“…As shown by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM, Figure 1c), the PtNPs with a diameter of about 1.1 nm are uniformly distributed www.advmat.de www.advancedsciencenews.com on the entire surface of the BP nanosheets. [34][35][36] The chemical composition of the Pt/BP heterostructure is determined by energy-dispersive X-ray spectroscopy (EDS) which confirms the uniform distribution of PtNPs on the BP nanosheets (Figure 1f,g). [34] The crystal structure of the Pt/BP heterostructure is characterized by high-resolution STEM, TEM (Figure 1d,e), as well as X-ray diffraction (XRD, Figure S2b, Supporting Information).…”

“…[34] The morphologies of the BP nanosheets ( Figure S1, Supporting Information) and Pt/BP heterostructures (Figure 1a,b) examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM) reveal an average size and thickness of about 500 and 23 nm, respectively. [34] The crystal structure of the Pt/BP heterostructure is characterized by high-resolution STEM, TEM (Figure 1d,e), as well as X-ray diffraction (XRD, Figure S2b, Supporting Information). The PtNPs with such a small size give rise to good catalytic activity according to a recent study.…”

“…Dissociation of molecular H 2 occurs easily on the Pt surface [34] and the primary isotope effect is observed with the ratio of the reaction rates (K H /K D ) being as large as 3.2 (Figure 4c), suggesting that H ad atoms insertion into styrene is the rate-limiting step in hydrogenation. Dissociation of molecular H 2 occurs easily on the Pt surface [34] and the primary isotope effect is observed with the ratio of the reaction rates (K H /K D ) being as large as 3.2 (Figure 4c), suggesting that H ad atoms insertion into styrene is the rate-limiting step in hydrogenation.…”

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“…The possible reason for the aggregation of Au NPs may be that the abundant phenolic groups of the gradually formed RF resin layer provide strong multidentate coordination interactions with the ultrasmall Au NPs formed by chemical reduction. 33,34 And the dynamic formation and growth process of the RF resin layer on the heterogeneous interface of DPSSs-NH 2 @Au NPs may drive adjacent ultrasmall Au NPs to grow into somewhat larger Au NPs. However, the exact reason is still very unclear.…”