From order to disorder and back again

In situ hydrothermal redox reactions of uranium phosphites and phosphates

Eric Villa, Connor J. Marr, Juan Diwu, Evgeny V. Alekseev, Wulf Depmeier, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Five new uranium phosphites, phosphates, and mixed phosphate-phosphite compounds were hydrothermally synthesized using H3PO3 as an initial reagent. These compounds are Cs4[(UO2) 8(HPO4)5(HPO3)5] ·4H2O (1), Cs[UIV(PO4)(H 1.5PO4)]2 (2), Cs4[U IV 6(PO4)8(HPO4)(HPO 3)] (3), Cs10[UIV 10(PO 4)4(HPO4)14(HPO3) 5]·H2O (4), and Cs3[UIV 4(PO4)3(HPO4)5] (5). The first contains uranium(VI) and the latter four uranium(IV). Of the U IV structures, two have extensive disordering among the cesium cation positions, one of which also contains disordering at some of the phosphate-phosphite positions. These intermediate compounds are bookended by nondisordered phases. The isolation of these transitional phases occurred at the higher of the pH conditions attempted here. Both the starting pH and the duration of the reactions have a strong influence on the products formed. Herein, we explore the second series of in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and cesium carbonate. The isolation of these disordered crystalline products helps to illuminate the complex reaction pathways that can occur in hydrothermal syntheses.

Original languageEnglish
Pages (from-to)965-973
Number of pages9
JournalInorganic Chemistry
Volume52
Issue number2
DOIs
StatePublished - Jan 18 2013
Externally publishedYes

Fingerprint

Phosphites
Uranium
Redox reactions
uranium
phosphates
Phosphates
disorders
cesium
isolation
Uranyl Nitrate
Cesium
Hydrothermal synthesis
products
reagents
Cations
nitrates
carbonates
Crystalline materials
cations
acids

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

From order to disorder and back again : In situ hydrothermal redox reactions of uranium phosphites and phosphates. / Villa, Eric; Marr, Connor J.; Diwu, Juan; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

In: Inorganic Chemistry, Vol. 52, No. 2, 18.01.2013, p. 965-973.

Research output: Contribution to journalArticle

Villa, Eric ; Marr, Connor J. ; Diwu, Juan ; Alekseev, Evgeny V. ; Depmeier, Wulf ; Albrecht-Schmitt, Thomas E. / From order to disorder and back again : In situ hydrothermal redox reactions of uranium phosphites and phosphates. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 2. pp. 965-973.
@article{82e377aa4e4646ecba0edd76ef24f84e,
title = "From order to disorder and back again: In situ hydrothermal redox reactions of uranium phosphites and phosphates",
abstract = "Five new uranium phosphites, phosphates, and mixed phosphate-phosphite compounds were hydrothermally synthesized using H3PO3 as an initial reagent. These compounds are Cs4[(UO2) 8(HPO4)5(HPO3)5] ·4H2O (1), Cs[UIV(PO4)(H 1.5PO4)]2 (2), Cs4[U IV 6(PO4)8(HPO4)(HPO 3)] (3), Cs10[UIV 10(PO 4)4(HPO4)14(HPO3) 5]·H2O (4), and Cs3[UIV 4(PO4)3(HPO4)5] (5). The first contains uranium(VI) and the latter four uranium(IV). Of the U IV structures, two have extensive disordering among the cesium cation positions, one of which also contains disordering at some of the phosphate-phosphite positions. These intermediate compounds are bookended by nondisordered phases. The isolation of these transitional phases occurred at the higher of the pH conditions attempted here. Both the starting pH and the duration of the reactions have a strong influence on the products formed. Herein, we explore the second series of in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and cesium carbonate. The isolation of these disordered crystalline products helps to illuminate the complex reaction pathways that can occur in hydrothermal syntheses.",
author = "Eric Villa and Marr, {Connor J.} and Juan Diwu and Alekseev, {Evgeny V.} and Wulf Depmeier and Albrecht-Schmitt, {Thomas E.}",
year = "2013",
month = "1",
day = "18",
doi = "10.1021/ic302198w",
language = "English",
volume = "52",
pages = "965--973",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - From order to disorder and back again

T2 - In situ hydrothermal redox reactions of uranium phosphites and phosphates

AU - Villa, Eric

AU - Marr, Connor J.

AU - Diwu, Juan

AU - Alekseev, Evgeny V.

AU - Depmeier, Wulf

AU - Albrecht-Schmitt, Thomas E.

PY - 2013/1/18

Y1 - 2013/1/18

N2 - Five new uranium phosphites, phosphates, and mixed phosphate-phosphite compounds were hydrothermally synthesized using H3PO3 as an initial reagent. These compounds are Cs4[(UO2) 8(HPO4)5(HPO3)5] ·4H2O (1), Cs[UIV(PO4)(H 1.5PO4)]2 (2), Cs4[U IV 6(PO4)8(HPO4)(HPO 3)] (3), Cs10[UIV 10(PO 4)4(HPO4)14(HPO3) 5]·H2O (4), and Cs3[UIV 4(PO4)3(HPO4)5] (5). The first contains uranium(VI) and the latter four uranium(IV). Of the U IV structures, two have extensive disordering among the cesium cation positions, one of which also contains disordering at some of the phosphate-phosphite positions. These intermediate compounds are bookended by nondisordered phases. The isolation of these transitional phases occurred at the higher of the pH conditions attempted here. Both the starting pH and the duration of the reactions have a strong influence on the products formed. Herein, we explore the second series of in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and cesium carbonate. The isolation of these disordered crystalline products helps to illuminate the complex reaction pathways that can occur in hydrothermal syntheses.

AB - Five new uranium phosphites, phosphates, and mixed phosphate-phosphite compounds were hydrothermally synthesized using H3PO3 as an initial reagent. These compounds are Cs4[(UO2) 8(HPO4)5(HPO3)5] ·4H2O (1), Cs[UIV(PO4)(H 1.5PO4)]2 (2), Cs4[U IV 6(PO4)8(HPO4)(HPO 3)] (3), Cs10[UIV 10(PO 4)4(HPO4)14(HPO3) 5]·H2O (4), and Cs3[UIV 4(PO4)3(HPO4)5] (5). The first contains uranium(VI) and the latter four uranium(IV). Of the U IV structures, two have extensive disordering among the cesium cation positions, one of which also contains disordering at some of the phosphate-phosphite positions. These intermediate compounds are bookended by nondisordered phases. The isolation of these transitional phases occurred at the higher of the pH conditions attempted here. Both the starting pH and the duration of the reactions have a strong influence on the products formed. Herein, we explore the second series of in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and cesium carbonate. The isolation of these disordered crystalline products helps to illuminate the complex reaction pathways that can occur in hydrothermal syntheses.

UR - http://www.scopus.com/inward/record.url?scp=84872547029&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84872547029&partnerID=8YFLogxK

U2 - 10.1021/ic302198w

DO - 10.1021/ic302198w

M3 - Article

VL - 52

SP - 965

EP - 973

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 2

ER -