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Title: Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO2

Abstract

The study of the electrochemical behavior (in the presence of N2 or CO2) of size-controlled naked Cu5 and Cu20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO2 on them. Cu20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu5 nanoclusters coordinate effectively CO2 (hydrogen carbonate) in solution, different from Cu20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu5 nanoclusters to reduce CO2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO2.

Authors:
 [1];  [1];  [1];  [2];  [2];  [2];  [2];  [3]
  1. Univ. of Messina (Italy). Dept. of Chemical, Biological, Pharmaceutical and Environmental Science; Univ. of Messina (Italy). Dept. of Mathematical and Computer Sciences, Physical Sciences and Earth Sciences
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division, X-ray Science Division, Nanoscience and Technology Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division, X-ray Science Division, Nanoscience and Technology Division; Yale Univ., New Haven, CT (United States). Dept. of Chemical and Environmental Engineering; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering (IME)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1352618
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 18; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Passalacqua, Rosalba, Parathoner, Siglinda, Centi, Gabriele, Halder, Avik, Tyo, Eric C., Yang, Bing, Seifert, Sönke, and Vajda, Stefan. Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO2. United States: N. p., 2016. Web. doi:10.1039/c6cy00942e.
Passalacqua, Rosalba, Parathoner, Siglinda, Centi, Gabriele, Halder, Avik, Tyo, Eric C., Yang, Bing, Seifert, Sönke, & Vajda, Stefan. Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO2. United States. https://doi.org/10.1039/c6cy00942e
Passalacqua, Rosalba, Parathoner, Siglinda, Centi, Gabriele, Halder, Avik, Tyo, Eric C., Yang, Bing, Seifert, Sönke, and Vajda, Stefan. Thu . "Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO2". United States. https://doi.org/10.1039/c6cy00942e. https://www.osti.gov/servlets/purl/1352618.
@article{osti_1352618,
title = {Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO2},
author = {Passalacqua, Rosalba and Parathoner, Siglinda and Centi, Gabriele and Halder, Avik and Tyo, Eric C. and Yang, Bing and Seifert, Sönke and Vajda, Stefan},
abstractNote = {The study of the electrochemical behavior (in the presence of N2 or CO2) of size-controlled naked Cu5 and Cu20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO2 on them. Cu20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu5 nanoclusters coordinate effectively CO2 (hydrogen carbonate) in solution, different from Cu20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu5 nanoclusters to reduce CO2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO2.},
doi = {10.1039/c6cy00942e},
journal = {Catalysis Science and Technology},
number = 18,
volume = 6,
place = {United States},
year = {Thu Aug 04 00:00:00 EDT 2016},
month = {Thu Aug 04 00:00:00 EDT 2016}
}

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