Reactions of rare earth hydrated nitrates and oxides with formamide: Relevant to recycling rare earth metals

Pradeep Samarasekere, Xiqu Wang, Kaveevivitchai Watchareeya, Allan J. Jacobson

研究成果: Article

4 引文 (Scopus)

摘要

Reactions of hydrated rare earth nitrates with formamide under mild solvothermal reaction conditions give three different rare earth formate structure types Ln(HCOO)3, Ln(HCOO)3·(HCONH2)2, and [CH(NH2)2][Ln(HCOO)4]. The conditions for the formation of a specific structure type were determined as a function of the size of the rare earth cation, the reaction time, and the reaction temperature. Thirteen previously unreported rare earth formates were obtained; nine were isostructural compounds with the composition Ln(HCOO)3·(HCONH2)2 (denoted by LnFA, Ln = Y (1Y), Sm (2Sm), Eu (3Eu), Gd (4Gd), Tb (5Tb), Ho (6Ho), Tm (7Tm), Yb (8Yb), and Lu (9Lu)), and four were isostructural compounds with the composition [CH(NH2)2][Ln(HCOO)4] (denoted by LnFMD, Ln = Sm (10Sm), Ho (11Ho), Tm (12Tm), and Lu (13Lu)). All compounds contain metal ions that are eight coordinated by oxygen atoms and are connected by anti-anti bridging formato ligands to form frameworks. The coordination geometry is bisdisphenoid in LnFA and square antiprismatic in LnFMD. In contrast, the larger rare earth ions that adopt the Ln(HCOO)3 structure are nine coordinated by oxygen atoms in tricapped trigonal prismatic coordination geometry. The luminescence properties of 2Sm, 3Eu, 5Tb, and 10Sm were investigated by solid state photoluminescence spectroscopy in the range of 300-800 nm. Rare earth oxides were also found to react directly with formamide in the presence of a small amount of water to give the same compositions suggesting that the reaction chemistry can provide a basis for a process to recover rare earth metals from end-of-life products containing oxides such as the phosphors used in fluorescent light bulbs. This possibility was demonstrated by crystallizing rare earth formates starting with a commercially available trichromatic phosphor.

原文English
頁(從 - 到)1119-1128
頁數10
期刊Crystal Growth and Design
15
發行號3
DOIs
出版狀態Published - 2015 三月 4

指紋

Rare Earth Metals
recycling
Nitrates
Oxides
Rare earths
nitrates
Recycling
rare earth elements
oxides
Metals
metals
Formates
formates
formic acid
Phosphors
phosphors
Chemical analysis
oxygen atoms
Oxygen
Atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

引用此文

@article{0785ac2227a448c4ba8a268dcbd1d25d,
title = "Reactions of rare earth hydrated nitrates and oxides with formamide: Relevant to recycling rare earth metals",
abstract = "Reactions of hydrated rare earth nitrates with formamide under mild solvothermal reaction conditions give three different rare earth formate structure types Ln(HCOO)3, Ln(HCOO)3·(HCONH2)2, and [CH(NH2)2][Ln(HCOO)4]. The conditions for the formation of a specific structure type were determined as a function of the size of the rare earth cation, the reaction time, and the reaction temperature. Thirteen previously unreported rare earth formates were obtained; nine were isostructural compounds with the composition Ln(HCOO)3·(HCONH2)2 (denoted by LnFA, Ln = Y (1Y), Sm (2Sm), Eu (3Eu), Gd (4Gd), Tb (5Tb), Ho (6Ho), Tm (7Tm), Yb (8Yb), and Lu (9Lu)), and four were isostructural compounds with the composition [CH(NH2)2][Ln(HCOO)4] (denoted by LnFMD, Ln = Sm (10Sm), Ho (11Ho), Tm (12Tm), and Lu (13Lu)). All compounds contain metal ions that are eight coordinated by oxygen atoms and are connected by anti-anti bridging formato ligands to form frameworks. The coordination geometry is bisdisphenoid in LnFA and square antiprismatic in LnFMD. In contrast, the larger rare earth ions that adopt the Ln(HCOO)3 structure are nine coordinated by oxygen atoms in tricapped trigonal prismatic coordination geometry. The luminescence properties of 2Sm, 3Eu, 5Tb, and 10Sm were investigated by solid state photoluminescence spectroscopy in the range of 300-800 nm. Rare earth oxides were also found to react directly with formamide in the presence of a small amount of water to give the same compositions suggesting that the reaction chemistry can provide a basis for a process to recover rare earth metals from end-of-life products containing oxides such as the phosphors used in fluorescent light bulbs. This possibility was demonstrated by crystallizing rare earth formates starting with a commercially available trichromatic phosphor.",
author = "Pradeep Samarasekere and Xiqu Wang and Kaveevivitchai Watchareeya and Jacobson, {Allan J.}",
year = "2015",
month = "3",
day = "4",
doi = "10.1021/cg501421u",
language = "English",
volume = "15",
pages = "1119--1128",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "3",

}

Reactions of rare earth hydrated nitrates and oxides with formamide : Relevant to recycling rare earth metals. / Samarasekere, Pradeep; Wang, Xiqu; Watchareeya, Kaveevivitchai; Jacobson, Allan J.

於: Crystal Growth and Design, 卷 15, 編號 3, 04.03.2015, p. 1119-1128.

研究成果: Article

TY - JOUR

T1 - Reactions of rare earth hydrated nitrates and oxides with formamide

T2 - Relevant to recycling rare earth metals

AU - Samarasekere, Pradeep

AU - Wang, Xiqu

AU - Watchareeya, Kaveevivitchai

AU - Jacobson, Allan J.

PY - 2015/3/4

Y1 - 2015/3/4

N2 - Reactions of hydrated rare earth nitrates with formamide under mild solvothermal reaction conditions give three different rare earth formate structure types Ln(HCOO)3, Ln(HCOO)3·(HCONH2)2, and [CH(NH2)2][Ln(HCOO)4]. The conditions for the formation of a specific structure type were determined as a function of the size of the rare earth cation, the reaction time, and the reaction temperature. Thirteen previously unreported rare earth formates were obtained; nine were isostructural compounds with the composition Ln(HCOO)3·(HCONH2)2 (denoted by LnFA, Ln = Y (1Y), Sm (2Sm), Eu (3Eu), Gd (4Gd), Tb (5Tb), Ho (6Ho), Tm (7Tm), Yb (8Yb), and Lu (9Lu)), and four were isostructural compounds with the composition [CH(NH2)2][Ln(HCOO)4] (denoted by LnFMD, Ln = Sm (10Sm), Ho (11Ho), Tm (12Tm), and Lu (13Lu)). All compounds contain metal ions that are eight coordinated by oxygen atoms and are connected by anti-anti bridging formato ligands to form frameworks. The coordination geometry is bisdisphenoid in LnFA and square antiprismatic in LnFMD. In contrast, the larger rare earth ions that adopt the Ln(HCOO)3 structure are nine coordinated by oxygen atoms in tricapped trigonal prismatic coordination geometry. The luminescence properties of 2Sm, 3Eu, 5Tb, and 10Sm were investigated by solid state photoluminescence spectroscopy in the range of 300-800 nm. Rare earth oxides were also found to react directly with formamide in the presence of a small amount of water to give the same compositions suggesting that the reaction chemistry can provide a basis for a process to recover rare earth metals from end-of-life products containing oxides such as the phosphors used in fluorescent light bulbs. This possibility was demonstrated by crystallizing rare earth formates starting with a commercially available trichromatic phosphor.

AB - Reactions of hydrated rare earth nitrates with formamide under mild solvothermal reaction conditions give three different rare earth formate structure types Ln(HCOO)3, Ln(HCOO)3·(HCONH2)2, and [CH(NH2)2][Ln(HCOO)4]. The conditions for the formation of a specific structure type were determined as a function of the size of the rare earth cation, the reaction time, and the reaction temperature. Thirteen previously unreported rare earth formates were obtained; nine were isostructural compounds with the composition Ln(HCOO)3·(HCONH2)2 (denoted by LnFA, Ln = Y (1Y), Sm (2Sm), Eu (3Eu), Gd (4Gd), Tb (5Tb), Ho (6Ho), Tm (7Tm), Yb (8Yb), and Lu (9Lu)), and four were isostructural compounds with the composition [CH(NH2)2][Ln(HCOO)4] (denoted by LnFMD, Ln = Sm (10Sm), Ho (11Ho), Tm (12Tm), and Lu (13Lu)). All compounds contain metal ions that are eight coordinated by oxygen atoms and are connected by anti-anti bridging formato ligands to form frameworks. The coordination geometry is bisdisphenoid in LnFA and square antiprismatic in LnFMD. In contrast, the larger rare earth ions that adopt the Ln(HCOO)3 structure are nine coordinated by oxygen atoms in tricapped trigonal prismatic coordination geometry. The luminescence properties of 2Sm, 3Eu, 5Tb, and 10Sm were investigated by solid state photoluminescence spectroscopy in the range of 300-800 nm. Rare earth oxides were also found to react directly with formamide in the presence of a small amount of water to give the same compositions suggesting that the reaction chemistry can provide a basis for a process to recover rare earth metals from end-of-life products containing oxides such as the phosphors used in fluorescent light bulbs. This possibility was demonstrated by crystallizing rare earth formates starting with a commercially available trichromatic phosphor.

UR - http://www.scopus.com/inward/record.url?scp=84929157453&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84929157453&partnerID=8YFLogxK

U2 - 10.1021/cg501421u

DO - 10.1021/cg501421u

M3 - Article

AN - SCOPUS:84929157453

VL - 15

SP - 1119

EP - 1128

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 3

ER -