Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 25, Pages 7463-7467Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201801115
Keywords
bipolar electrochemistry; electron tunneling; hydrogen evolution reaction; nanoparticles; scanning electrochemical microscopy
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Funding
- U.S. Department of Energy, Basic Energy Sciences [DE-SC0017603]
- National Science Foundation [CHE-1763337]
- U.S. Department of Energy (DOE) [DE-SC0017603] Funding Source: U.S. Department of Energy (DOE)
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Electrochemical experiments at individual nanoparticles (NPs) can provide new insights into their structure-activity relationships. By using small nanoelectrodes as tips in a scanning electrochemical microscope (SECM), we recently imaged individual surface-bound 10-50nm metal NPs. Herein, we introduce a new mode of SECM operation based on tunneling between the tip and a nanoparticle immobilized on the insulating surface. The obtained current vs. distance curves show the transition from the conventional feedback response to electron tunneling between the tip and the NP at separation distances of less than about 3nm. In addition to high-resolution imaging of the NP topography, the tunneling mode enables measurement of the heterogeneous kinetics at a single NP without making an ohmic contact with it. The developed method should be useful for studying the effects of nanoparticle size and geometry on electrocatalytic activity in real-world applications.
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