Published August 25, 2019 | Version v1
Journal article Open

Cascade Reactions in Nanozymes: Spatially Separated Active Sites inside Ag-Core−Porous-Cu-Shell Nanoparticles for Multistep Carbon Dioxide Reduction to Higher Organic Molecules

Creators

  • 1. School of Chemistry and Australian Centre for NanoMedicine, University of New South Wales, Sydney 2052, Australia
  • 2. Analytical Chemistry - Center for Electrochemical Sciences (CES), Faculty of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, D-44780 Bochum, Germany
  • 3. Chemical Technology III, Faculty of Chemistry and CENIDE, Center for Nanointegration University Duisburg Essen, Carl-Benz-Straße 199, D-47057 Duisburg, Germany
  • 4. Electron Microscope Unit, Mark Wainwright Analytical Centre, University of New South Wales, Sydney 2052, Australia

Description

Enzymes can perform complex multistep cascade reactions by linking multiple distinct catalytic sites via substrate channeling. We mimic this feature in a generalized approach with an electrocatalytic nanoparticle for the carbon dioxide reduction reaction comprising a Ag core surrounded by a porous Cu shell, providing different active sites in nanoconfined volumes. The architecture of the nanozyme provides the basis for a cascade reaction, which promotes C−C coupling reactions. The first step occurs on the Ag core, and the subsequent steps on the porous copper shell, where a sufficiently high CO concentration due to the nanoconfinement facilitates C−C bond formation. The architecture yields the formation of n-propanol and propionaldehyde at potentials as low as −0.6 V vs RHE.

Notes

W.S. is grateful for financial support by the Deutsche Forschungsgemeinschaft (EXC-2033-390677874) and the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (grant agreement no. 833408). This work was supported by the DAAD in the framework of the PPP project 57446293 as well as the Ruhr University Research school PLUS through a research stay of P.W. at UNSW, funded by Germany's Excellence Initiative (DFG GSC 98/3). This research was financially supported by the Australian Research Council of Centre of Excellence in Convergent Bio-Nano Science and Technology (CE140100036), the ARC Australian Laureate Fellowship (FL150100060), the Discovery Project (DP190102659), and the Mark Wainwright Analytical Centre (MWAC) at UNSW. This work used the facilities supported by Microscopy Australia at the Electron Microscope Unit at UNSW. The authors are grateful to Dr. Douglas Lawes for discussion and assistance with 1H NMR experiments. P.B.O'M. acknowledges the Australian Government Research Training Program Scholarship for financial support. P.W. is grateful to the Association of the Chemical Industry e.V. (VCI) for funding of the Ph.D. fellowship.

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DOI10.1021jacs.9b07310.pdf

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Additional details

Funding

CASCAT – Catalytic cascade reactions. From fundamentals of nanozymes to applications based on gas-diffusion electrodes 833408
European Commission