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Rational Low‐Temperature Synthesis of Ultrasmall Nanocrystalline Manganese Binary Oxide Catalysts under Controlled Metal Cation Hydration in Organic Media
Author(s) -
Miyamoto Yumi,
Kuroda Yoshiyuki,
Uematsu Tsubasa,
Oshikawa Hiroyuki,
Shibata Naoya,
Ikuhara Yuichi,
Suzuki Kosuke,
Hibino Mitsuhiro,
Yamaguchi Kazuya,
Mizuno Noritaka
Publication year - 2016
Publication title -
chemnanomat
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.947
H-Index - 32
ISSN - 2199-692X
DOI - 10.1002/cnma.201600034
Subject(s) - ammoxidation , spinel , catalysis , inorganic chemistry , nanocrystalline material , manganese , oxide , chemistry , metal , materials science , organic chemistry , acrylonitrile , nanotechnology , copolymer , metallurgy , polymer
Ultrasmall nanocrystalline manganese binary oxides with various compositions and crystal structures were synthesized by a convenient, rational low‐temperature method. These oxides were obtained in 2‐propanol‐based solutions using the organic‐solvent‐soluble MnO 4 − as a manganese source under controlled metal cation template hydration. Three‐dimensional spinel oxides were generated selectively by suppressing the hydration of metal cation templates. One‐dimensional tunnels and two‐dimensional layered structures predominated under adequate and high hydration, respectively. These oxides acted as efficient reusable heterogeneous catalysts for primary alcohol ammoxidation and amidation using aqueous NH 3 as a nitrogen source and O 2 (air) as a terminal oxidant. In particular, ultrasmall Co−Mn spinel oxide effectively catalyzed the ammoxidation of primary alcohols into their corresponding nitriles. The Li−Mn spinel oxide promoted the hydration of ammoxidation‐derived nitriles, facilitating the one‐pot conversion of primary alcohols into primary amides.