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Title: A Comparison of Photocatalytic Activities of Gold Nanoparticles Following Plasmonic and Interband Excitation and a Strategy for Harnessing Interband Hot Carriers for Solution Phase Photocatalysis

Light driven excitation of gold nanoparticles (GNPs) has emerged as a potential strategy to generate hot carriers for photocatalysis through excitation of localized surface plasmon resonance (LSPR). In contrast, carrier generation through excitation of interband transitions remains a less explored and underestimated pathway for photocatalytic activity. Photoinduced oxidative etching of GNPs with FeCl3 was investigated as a model reaction in order to elucidate the effects of both types of transitions. Our quantitative results show that interband transitions more efficiently generate hot carriers and that those carriers exhibit higher reactivity as compared to those generated solely by LSPR. Furthermore, by leveraging the strong π-acidic character of the resulting photogenerated Au+ hole, an interband transition induced cyclization reaction of alkynylphenols was developed. One thing of note is that the, alkyne coordination to the Au+ hole intercepts the classic oxidation event and leads to the formation of the catalytically active gold clusters on subnanometer scale.
Authors:
 [1] ; ORCiD logo [2] ;  [3] ;  [1] ; ORCiD logo [4] ; ORCiD logo [5] ;  [6] ; ORCiD logo [7]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Hamburg Centre for Ultrafast Imaging (Germany)
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Kavli Energy NanoScience Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  4. Hamburg Centre for Ultrafast Imaging (Germany); Univ. of Hamburg (Germany). Inst. of Physical Chemistry
  5. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Kavli Energy NanoScience Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division and Materials Science Division
  6. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kavli Energy NanoScience Inst. and Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
  7. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Grant/Contract Number:
AC02-05CH11231; DEAC02-05CH11231
Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1356866
Alternate Identifier(s):
OSTI ID: 1361541; OSTI ID: 1379860