Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology

Jian Lin; Meiying Qie; Linjuan Zhang; Xiaomei Wang; Yuejian Lin; Wei Liu; Hongliang Bao; Jianqiang Wang

doi:10.1021/acs.inorgchem.7b02335

Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology

Jian Lin
, Meiying Qie
, Linjuan Zhang
, Xiaomei Wang
, Yuejian Lin
, Wei Liu
, Hongliang Bao
, Jianqiang Wang

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

Abstract

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 Th^IV 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.

Original language	English
Pages (from-to)	14198-14205
Number of pages	8
Journal	Inorganic Chemistry
Volume	56
Issue number	22
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02335
State	Published - 20 Nov 2017
Externally published	Yes

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10.1021/acs.inorgchem.7b02335

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@article{0981dc16ab16445e927e58ecded1c860,

title = "Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology",

abstract = "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 {\AA} 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.",

author = "Jian Lin and Meiying Qie and Linjuan Zhang and Xiaomei Wang and Yuejian Lin and Wei Liu and Hongliang Bao and Jianqiang Wang",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = nov,

day = "20",

doi = "10.1021/acs.inorgchem.7b02335",

language = "英语",

volume = "56",

pages = "14198--14205",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

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

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 -

Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology

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