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Nanoparticle‐Mediated Intervalence Charge Transfer: Core‐Size Effects
Author(s) -
Hu Peiguang,
Chen Limei,
Deming Christopher P.,
Kang Xiongwu,
Chen Shaowei
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508985
Subject(s) - nanoparticle , band gap , particle size , chemistry , delocalized electron , semiconductor , particle (ecology) , metal , surface charge , electrochemistry , platinum , conductivity , materials science , analytical chemistry (journal) , photochemistry , nanotechnology , organic chemistry , electrode , optoelectronics , catalysis , oceanography , geology
Abstract Two types of platinum nanoparticles (NPs) functionalized with ethynylferrocene were prepared. The subnanometer‐sized NPs (Pt 10 eFc) showed semiconductor‐like characteristics with a bandgap of about 1.0 eV, and the other was metal‐like with a core size of about 2 nm (Pt 314 eFc) and no significant bandgap. IR spectroscopic measurements showed a clear red‐shift of the C≡C and ferrocenyl ring =C−H vibrational energies with increasing particle core size owing to enhanced intraparticle charge delocalization between the particle‐bound ferrocenyl moieties. Electrochemical measurements showed two pairs of voltammetric peaks owing to intervalence charge transfer between the ferrocenyl groups on the nanoparticle surface, which was apparently weaker with Pt 10 eFc than with Pt 314 eFc. Significantly, the former might be markedly enhanced with UV photoirradiation owing to enhanced nanoparticle electronic conductivity, whereas no apparent effects were observed with the latter.