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Fine‐Tunable Electronic Energy Levels of Mixed‐Metal Prussian‐Blue Alloy Nanoparticles
Author(s) -
Ishizaki Manabu,
Ono Kenta,
Suzuki Kento,
Naito Wataru,
Kanaizuka Katsuhiko,
Kawamoto Tohru,
Tanaka Hisashi,
Kurihara Masato
Publication year - 2017
Publication title -
chemnanomat
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.947
H-Index - 32
ISSN - 2199-692X
DOI - 10.1002/cnma.201700084
Subject(s) - prussian blue , alloy , materials science , nanoparticle , metal , indium tin oxide , tin , phase (matter) , metal ions in aqueous solution , chemical engineering , inorganic chemistry , nanotechnology , metallurgy , electrochemistry , chemistry , thin film , electrode , organic chemistry , engineering
A specific electronic interaction among metal ions emerges in solution‐processed films of coordination polymer (CP) nanoparticles (NPs). The most classic CP, Prussian blue (PB), is alloyed with Ni to form Fe x Ni 3− x [Fe(CN) 6 ] 2 showing an identical X‐ray crystallographic phase in all composition ratios of 0≤ x ≤3. By surface modification using [Fe(CN) 6 ] 4− , the PB alloy NPs are dispersed into water, and spin‐coated films of the NPs adhere to indium‐tin‐oxide substrates via a low‐temperature heating process at 100 °C. It is revealed that systematic fine tuning of the electronic energy levels is optically and electrochemically possible in the films by controlling the composition ratios. This is possible due to the d ( t 2g )– π *(C≡N − ) electronic conjugation among three redox‐active iron species, Fe II −C≡N, Fe III −C≡N, and Fe III −N≡C, which coexist by alloying with Ni. The heating process conducts the restoration of discontinued d–π* bonding networks among the NPs.