Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic zr chlorides and sulfates

Yung Jin Hu, Karah E. Knope, S. Skanthakumar, Mercouri G Kanatzidis, John F. Mitchell, L. Soderholm

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H 2O)16]8+, generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO 4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH) 26O20(H2O)23.2(SO4) 12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm-1 that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of

Original languageEnglish
Pages (from-to)14240-14248
Number of pages9
JournalJournal of the American Chemical Society
Volume135
Issue number38
DOIs
Publication statusPublished - Sep 25 2013

Fingerprint

Sulfates
Chlorides
Crystallization
X ray scattering
Oligomers
Dimers
Self assembly
Distribution functions
Raman scattering
Precipitates
Evaporation
X-Rays
Crystals

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic zr chlorides and sulfates. / Hu, Yung Jin; Knope, Karah E.; Skanthakumar, S.; Kanatzidis, Mercouri G; Mitchell, John F.; Soderholm, L.

In: Journal of the American Chemical Society, Vol. 135, No. 38, 25.09.2013, p. 14240-14248.

Research output: Contribution to journalArticle

@article{6999309dfb9b45439d82aaccf3bad58a,
title = "Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic zr chlorides and sulfates",
abstract = "The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H 2O)16]8+, generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO 4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH) 26O20(H2O)23.2(SO4) 12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm-1 that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of",
author = "Hu, {Yung Jin} and Knope, {Karah E.} and S. Skanthakumar and Kanatzidis, {Mercouri G} and Mitchell, {John F.} and L. Soderholm",
year = "2013",
month = "9",
day = "25",
doi = "10.1021/ja405555h",
language = "English",
volume = "135",
pages = "14240--14248",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "38",

}

TY - JOUR

T1 - Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic zr chlorides and sulfates

AU - Hu, Yung Jin

AU - Knope, Karah E.

AU - Skanthakumar, S.

AU - Kanatzidis, Mercouri G

AU - Mitchell, John F.

AU - Soderholm, L.

PY - 2013/9/25

Y1 - 2013/9/25

N2 - The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H 2O)16]8+, generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO 4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH) 26O20(H2O)23.2(SO4) 12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm-1 that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of

AB - The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H 2O)16]8+, generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO 4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH) 26O20(H2O)23.2(SO4) 12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm-1 that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of

UR - http://www.scopus.com/inward/record.url?scp=84884873369&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84884873369&partnerID=8YFLogxK

U2 - 10.1021/ja405555h

DO - 10.1021/ja405555h

M3 - Article

VL - 135

SP - 14240

EP - 14248

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 38

ER -