TY - JOUR
T1 - Theoretical and Experimental Evaluation of the Reduction Potential of Straight-Chain Alcohols for the Designed Synthesis of Bimetallic Nanostructures
AU - Ishijima, Masanao
AU - Matsumoto, Takatoshi
AU - Cuya Huaman, Jhon L.
AU - Shinoda, Kozo
AU - Uchikoshi, Masahito
AU - Matsuo, Kohei
AU - Suzuki, Kazumasa
AU - Miyamura, Hiroshi
AU - Balachandran, Jeyadevan
N1 - Funding Information:
One of the authors (J.L.C.H.) would like to acknowledge The Grant-in-Aid for Scientific Research (C) 16K04891 from the Ministry of Education, Culture, Sports, and Science and Technology of Japan. The in situ XAS measurements were made using the beamline (BL14B2) of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI), Proposal number, 2020A1900.
Publisher Copyright:
©
PY - 2021/7/5
Y1 - 2021/7/5
N2 - Recently, the development of bimetallic nanoparticles with functional properties has been attempted extensively but with limited control over their morphological and structural properties. The reason was the inability to control the kinetics of the reduction reaction in most liquid-phase syntheses. However, the alcohol reduction technique has demonstrated the possibility of controlling the reduction reaction and facilitating the incorporation of other phenomena such as diffusion, etching, and galvanic replacement during nanostructure synthesis. In this study, the reduction potential of straight-chain alcohols has been investigated using molecular orbital calculations and experimentally verified by reducing transition metals. The alcohols with a longer chain exhibited higher reduction potential, and 1-octanol was found to be the strongest among alcohols considered. Furthermore, the experimental evaluation carried out via the synthesis of metallic Cu, Ni, and Co particles was consistent with the theoretical predictions. The reaction mechanism of metallic particle formation was also studied in detail in the Ni-1-octanol system, and the metal ions were confirmed to be reduced via the formation of nickel alkoxide. The results of this investigation were successfully implemented to synthesize Cu-Ni bimetallic nanostructures (core-shell, wire, and tube) via the incorporation of diffusion and etching besides the reduction reaction. These results suggest that the designed synthesis of a wide range of bimetallic nanostructures with more refined control has become possible.
AB - Recently, the development of bimetallic nanoparticles with functional properties has been attempted extensively but with limited control over their morphological and structural properties. The reason was the inability to control the kinetics of the reduction reaction in most liquid-phase syntheses. However, the alcohol reduction technique has demonstrated the possibility of controlling the reduction reaction and facilitating the incorporation of other phenomena such as diffusion, etching, and galvanic replacement during nanostructure synthesis. In this study, the reduction potential of straight-chain alcohols has been investigated using molecular orbital calculations and experimentally verified by reducing transition metals. The alcohols with a longer chain exhibited higher reduction potential, and 1-octanol was found to be the strongest among alcohols considered. Furthermore, the experimental evaluation carried out via the synthesis of metallic Cu, Ni, and Co particles was consistent with the theoretical predictions. The reaction mechanism of metallic particle formation was also studied in detail in the Ni-1-octanol system, and the metal ions were confirmed to be reduced via the formation of nickel alkoxide. The results of this investigation were successfully implemented to synthesize Cu-Ni bimetallic nanostructures (core-shell, wire, and tube) via the incorporation of diffusion and etching besides the reduction reaction. These results suggest that the designed synthesis of a wide range of bimetallic nanostructures with more refined control has become possible.
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U2 - 10.1021/acs.inorgchem.1c00476
DO - 10.1021/acs.inorgchem.1c00476
M3 - Article
C2 - 33847487
AN - SCOPUS:85105115545
SN - 0020-1669
VL - 60
SP - 9432
EP - 9441
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 13
ER -