TY - JOUR
T1 - Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology
AU - Lin, Jian
AU - Qie, Meiying
AU - Zhang, Linjuan
AU - Wang, Xiaomei
AU - Lin, Yuejian
AU - Liu, Wei
AU - Bao, Hongliang
AU - Wang, Jianqiang
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/11/20
Y1 - 2017/11/20
N2 - Systematic control of the molar ratio between thorium hydroxides and selenic acid and their reaction temperature under hydrothermal conditions results in four novel thorium-based selenate complexes, namely, [Th8O4(OH)8(SeO4)6(H2O)16]·(SeO4)2·13H2O (Th-1), [Th8O4(OH)8(SeO4)8(H2O)13]·7H2O (Th-2), Th(OH)2(SeO4)H2O (Th-3), and Th3(SeO4)6(H2O)6·2.5H2O (Th-4), as well as the thorium mixed selenite selenate compound Th(SeO3)(SeO4) (Th-5). Smaller [H2SeO4]/[Th(IV)] ratio or lower temperature give rise to the formation of octameric [Th8(μ3-O)4(μ2-OH)8]16+ cores in Th-1/Th-2 and infinite [Th(μ2-OH)2H2O]2+ chains in Th-3, respectively. Increasing the [H2SeO4]/[Th(IV)] ratio or elevating the temperature generates a microporous (11.3 Å voids) open-framework Th-4, a monomeric thorium species without oxo/hydroxyl ligands, and a three-dimensional thorium structure Th-5. Formation of these compounds suggests that variables including acidity and temperature play a critical role in the hydrolysis and oligomerization of ThIV ions. Increasing acidity limits the deprotonation of water molecules and formation of nucleophilic hydroxo/oxo-aquo Th species, and high temperature appears to suppress the olation/oxolation hydrolysis reactions, which in both ways limit the formation of the thorium oligomers.
AB - Systematic control of the molar ratio between thorium hydroxides and selenic acid and their reaction temperature under hydrothermal conditions results in four novel thorium-based selenate complexes, namely, [Th8O4(OH)8(SeO4)6(H2O)16]·(SeO4)2·13H2O (Th-1), [Th8O4(OH)8(SeO4)8(H2O)13]·7H2O (Th-2), Th(OH)2(SeO4)H2O (Th-3), and Th3(SeO4)6(H2O)6·2.5H2O (Th-4), as well as the thorium mixed selenite selenate compound Th(SeO3)(SeO4) (Th-5). Smaller [H2SeO4]/[Th(IV)] ratio or lower temperature give rise to the formation of octameric [Th8(μ3-O)4(μ2-OH)8]16+ cores in Th-1/Th-2 and infinite [Th(μ2-OH)2H2O]2+ chains in Th-3, respectively. Increasing the [H2SeO4]/[Th(IV)] ratio or elevating the temperature generates a microporous (11.3 Å voids) open-framework Th-4, a monomeric thorium species without oxo/hydroxyl ligands, and a three-dimensional thorium structure Th-5. Formation of these compounds suggests that variables including acidity and temperature play a critical role in the hydrolysis and oligomerization of ThIV ions. Increasing acidity limits the deprotonation of water molecules and formation of nucleophilic hydroxo/oxo-aquo Th species, and high temperature appears to suppress the olation/oxolation hydrolysis reactions, which in both ways limit the formation of the thorium oligomers.
UR - https://www.scopus.com/pages/publications/85034649626
U2 - 10.1021/acs.inorgchem.7b02335
DO - 10.1021/acs.inorgchem.7b02335
M3 - 文章
C2 - 29116766
AN - SCOPUS:85034649626
SN - 0020-1669
VL - 56
SP - 14198
EP - 14205
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -