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Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics

Nature Materials volume 7, pages 992–996 (2008)Cite this article

Abstract

Nanoparticles are important catalysts for many chemical transformations. However, owing to their structural dispersions, heterogeneous distribution of surface sites and surface restructuring dynamics, nanoparticles are intrinsically heterogeneous and challenging to characterize in ensemble measurements. Using a single-nanoparticle single-turnover approach, we study the redox catalysis of individual colloidal Au nanoparticles in solution, using single-molecule detection of fluorogenic reactions. We find that for product generation, all Au nanoparticles follow a Langmuir–Hinshelwood mechanism but with heterogeneous reactivity; and for product dissociation, three nanoparticle subpopulations are present that show heterogeneous reactivity between multiple dissociation pathways with distinct kinetics. Correlation analyses of single-turnover waiting times further reveal activity fluctuations of individual Au nanoparticles, attributable to both catalysis-induced and spontaneous dynamic surface restructuring that occurs at different timescales at the surface catalytic and product docking sites. The results exemplify the power of the single-molecule approach in revealing the interplay of catalysis, heterogeneous reactivity and surface structural dynamics in nanocatalysis.

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Figure 1: Single-turnover detection of single-Au-nanoparticle catalysis.
Figure 2: Kinetic mechanism of catalysis.
Figure 3: Heterogeneous reactivity in catalysis and reaction pathways.
Figure 4: Single-nanoparticle catalytic dynamics.

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Acknowledgements

We thank Cornell University, ACS Petroleum Research Foundation (47918-G5) and Cornell Centre for Materials Research for financial support and J. Grazul for assistance in TEM.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA

    Weilin Xu, Jason S. Kong, Yun-Ting E. Yeh & Peng Chen

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  1. Weilin Xu
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  2. Jason S. Kong
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  3. Yun-Ting E. Yeh
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  4. Peng Chen
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Contributions

P.C. designed experiments; W.X., J.S.K., Y.-T.E.Y. and P.C. carried out experiments; W.X., J.S.K. and P.C. analysed data; W.X. and P.C. wrote the paper.

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Correspondence to Peng Chen.

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Xu, W., Kong, J., Yeh, YT. et al. Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics. Nature Mater 7, 992–996 (2008). https://doi.org/10.1038/nmat2319

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