TY - JOUR
T1 - Anisotropic Crystal Growth of Layered Nickel Hydroxide along the Stacking Direction Using Amine Ligands
AU - Muramatsu, Keisuke
AU - Jimba, Mina
AU - Yamada, Yumiko
AU - Wada, Hiroaki
AU - Shimojima, Atsushi
AU - Kuroda, Kazuyuki
N1 - Funding Information:
The authors thank Shinpei Enomoto, Haruo Otsuji, Yuya Kamiusuki, Dr. Masakazu Koike, and Dr. Takamichi Matsuno (Waseda University) for their assistance in the TEM and SEM observations and fruitful discussions. This work was partly supported by a Grant-in-Aid for Challenging Research (Exploratory) (no. 20K20450), a Grant-in-Aid for JSPS Fellows (no. 21J00679), and the cooperation of organization between Waseda University and JXTG Nippon Oil & Energy Corporation. K.M. is grateful to the JSPS Research Fellowship for Young Scientist from MEXT, Japan.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/6/6
Y1 - 2022/6/6
N2 - Edge surfaces of two-dimensional crystals play crucial roles in their properties, such as intercalation behavior and catalytic activities; however, reports on the preparation of crystals with a high aspect ratio of thickness to lateral size, typically a prism-like crystal morphology composed of stacked layers, are scarce. We report the anisotropic crystal growth of β-Ni(OH)2along the stacking direction using bidentate amine ligands, which act as both the base and the reservoir of Ni2+through the formation of Ni-diamine complexes. Various characterization results of the crystal structure, composition, and crystal orientation indicate the formation of hexagonal prisms of β-Ni(OH)2with an unusually high aspect ratio of the thickness to the lateral size higher than 1. A systematic investigation focusing on the molar ratio of amine ligands to Ni2+, the concentration of Ni-diamine complexes, and stability constants of the complexes revealed that anisotropic growth was promoted when the supersaturation was relatively high and was maintained constant for a long time. We clarified the role of amine ligands in controlling supersaturation through the controlled release of metal ions from stable complexes. β-Co(OH)2with a hexagonal prism shape was prepared using this protocol. This study provides valuable indications for developing synthetic chemistry for various layered compounds to achieve a controlled aspect ratio.
AB - Edge surfaces of two-dimensional crystals play crucial roles in their properties, such as intercalation behavior and catalytic activities; however, reports on the preparation of crystals with a high aspect ratio of thickness to lateral size, typically a prism-like crystal morphology composed of stacked layers, are scarce. We report the anisotropic crystal growth of β-Ni(OH)2along the stacking direction using bidentate amine ligands, which act as both the base and the reservoir of Ni2+through the formation of Ni-diamine complexes. Various characterization results of the crystal structure, composition, and crystal orientation indicate the formation of hexagonal prisms of β-Ni(OH)2with an unusually high aspect ratio of the thickness to the lateral size higher than 1. A systematic investigation focusing on the molar ratio of amine ligands to Ni2+, the concentration of Ni-diamine complexes, and stability constants of the complexes revealed that anisotropic growth was promoted when the supersaturation was relatively high and was maintained constant for a long time. We clarified the role of amine ligands in controlling supersaturation through the controlled release of metal ions from stable complexes. β-Co(OH)2with a hexagonal prism shape was prepared using this protocol. This study provides valuable indications for developing synthetic chemistry for various layered compounds to achieve a controlled aspect ratio.
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U2 - 10.1021/acs.inorgchem.2c00421
DO - 10.1021/acs.inorgchem.2c00421
M3 - Article
C2 - 35612816
AN - SCOPUS:85131701048
SN - 0020-1669
VL - 61
SP - 8490
EP - 8497
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -