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Cooperative communication within and between single nanocatalysts

Nature Chemistryvolume 10pages607614 (2018) | Download Citation

Abstract

Enzymes often show catalytic allostery in which reactions occurring at different sites communicate cooperatively over distances of up to a few nanometres. Whether such effects can occur with non-biological nanocatalysts remains unclear, even though these nanocatalysts can undergo restructuring and molecules can diffuse over catalyst surfaces. Here we report that phenomenologically similar, but mechanistically distinct, cooperative effects indeed exist for nanocatalysts. Using spatiotemporally resolved single-molecule catalysis imaging, we find that catalytic reactions on a single Pd or Au nanocatalyst can communicate with each other, probably via hopping of positively charged holes on the catalyst surface, over ~102 nanometres and with a temporal memory of ~101 to 102 seconds, giving rise to positive cooperativity among its surface active sites. Similar communication is also observed between individual nanocatalysts, however it operates via a molecular diffusion mechanism involving negatively charged product molecules, and its communication distance is many micrometres. Generalization of these long-range intra- and interparticle catalytic communication mechanisms may introduce a novel conceptual framework for understanding nanoscale catalysis.

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Acknowledgements

This research is supported mainly by the Army Research Office grants W911NF-17–1–0590 and W911NF-14–1–0377; and in part by the Army Research Office grant W911NF-14–1–0620; the Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program (grant DE-SC0004911); and National Science Foundation (grant CBET-1263736). Part of the work was carried out at the Cornell Center for Materials Research (grant DMR-1719875) and the Cornell NanoScale Facility (grant ECS-1542081). We thank J. B. Sambur and R. F. Loring for discussions.

Author information

Author notes

    • Xiaochun Zhou

    Present address: Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu, PR China

    • Nesha May Andoy

    Present address: BioMed X Innovation Center, Heidelberg, Germany

    • Guokun Liu

    Present address: College of the Environment and Ecology, Xiamen University, Xiamen, PR China

  1. These authors contributed equally: Ningmu Zou, Xiaochun Zhou and Guanqun Chen.

Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    • Ningmu Zou
    • , Xiaochun Zhou
    • , Guanqun Chen
    • , Nesha May Andoy
    • , Won Jung
    • , Guokun Liu
    •  & Peng Chen

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Contributions

N.Z. performed the experiments on Au nanorods catalysing the deacetylation and deoxygenation reactions, analysed the intra-particle and inter-particle catalytic communication behaviours, and performed simulations. X.Z. performed the early experiments, analyses, and simulations on the catalytic communications of Au nanorods catalysing the deacetylation reaction. G.C. performed experiments and analysis of Pd nanorods catalysing the disproportionation reaction. N.M.A. performed experiments and analysis of Au nanoplates catalysing the deoxygenation reaction. W.J. derived the diffusive model for analysing the intraparticle catalytic communication as a function of both distance and time separations. G.L. performed part of the electron microscopy measurements. P.C. conceived and directed the research. N.Z., X.Z., G.C. and P.C. discussed results and wrote the paper.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Peng Chen.

Supplementary information

  1. Supplementary Information

    Supplementary Methods, Supplementary Data, Supplementary Analysis, Supplementary Discussion, Supplementary Figs. 1–29, and Supplementary Tables 1,2

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DOI

https://doi.org/10.1038/s41557-018-0022-y