A Multifunctional Lanthanide Carbonate Cluster Based Metal-Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change

Qun Tang; Yan Li Yang; Ning Zhang; Zheng Liu; Shu Hua Zhang; Fu Shun Tang; Jia Yi Hu; Yan Zhen Zheng; Fu Pei Liang

doi:10.1021/acs.inorgchem.8b01023

A Multifunctional Lanthanide Carbonate Cluster Based Metal-Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change

Qun Tang
, Yan Li Yang
, Ning Zhang
, Zheng Liu
, Shu Hua Zhang
, Fu Shun Tang
, Jia Yi Hu
, Yan Zhen Zheng
, Fu Pei Liang

School of Materials Science and Engineering

Guilin University of Technology

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

54 Scopus citations

Abstract

A novel multifunctional, three-dimensional (3D) lanthanide carbonate cluster based metal-organic framework (MOF) with the general formula {[Gd₂(CO₃)(ox)₂(H₂O)₂]·3H₂O}_n (1) has been synthesized via self-assembly of gadolinium (Gd) carbonate and oxalate under hydrothermal conditions. Single-crystal X-ray diffraction reveals that the compound 1 consists of the Gd carbonate cluster with oxalic acid ligands, which form a 3D framework structure with an ordered one-dimensional (1D) pore channel along the a-axis. The coordination water molecules of Gd³⁺ ions point to the interior of the pore and form a 1D hydrogen bond pathway with oxygen atoms in adjacent oxalic acid that is stable at high temperature (up to 150 °C). The compound 1 features multiple hydrogen-bonding walls and good thermal stabilities, and shows the highest proton conductivity of 1.98 × 10^-3 S cm^-1 at T = 150 °C and in room air without additional humidity. Magnetic investigations of compound 1 demonstrate that weak antiferromagnetic couplings between adjacent Gd³⁺ ions bring about large cryogenic magnetocaloric effects. Remarkably, the maximum entropy change (-ΔS_m) of compound 1 reaches 58.5 J kg^-1 K^-1 at 2 K for a moderate field change (ΔH = 7 T). Moreover, the isomorphous MOFs: {[Ln₂(CO₃)(ox)₂(H₂O)₂]·3H₂O}_n (Ln³⁺ = Ce³⁺(2), Pr³⁺(3), Nd³⁺(4), Tb³⁺(5)) also are structurally and functionally characterized, and compounds 2-5 exhibit proton conductivity above 10^-3 S cm^-1 in room air and without additional humidity.

Original language	English
Pages (from-to)	9020-9027
Number of pages	8
Journal	Inorganic Chemistry
Volume	57
Issue number	15
DOIs	https://doi.org/10.1021/acs.inorgchem.8b01023
State	Published - 6 Aug 2018

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10.1021/acs.inorgchem.8b01023

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@article{7f7184baaf324b78a5f9256d3a65cd2b,

title = "A Multifunctional Lanthanide Carbonate Cluster Based Metal-Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change",

abstract = "A novel multifunctional, three-dimensional (3D) lanthanide carbonate cluster based metal-organic framework (MOF) with the general formula \{[Gd2(CO3)(ox)2(H2O)2]·3H2O\}n (1) has been synthesized via self-assembly of gadolinium (Gd) carbonate and oxalate under hydrothermal conditions. Single-crystal X-ray diffraction reveals that the compound 1 consists of the Gd carbonate cluster with oxalic acid ligands, which form a 3D framework structure with an ordered one-dimensional (1D) pore channel along the a-axis. The coordination water molecules of Gd3+ ions point to the interior of the pore and form a 1D hydrogen bond pathway with oxygen atoms in adjacent oxalic acid that is stable at high temperature (up to 150 °C). The compound 1 features multiple hydrogen-bonding walls and good thermal stabilities, and shows the highest proton conductivity of 1.98 × 10-3 S cm-1 at T = 150 °C and in room air without additional humidity. Magnetic investigations of compound 1 demonstrate that weak antiferromagnetic couplings between adjacent Gd3+ ions bring about large cryogenic magnetocaloric effects. Remarkably, the maximum entropy change (-ΔSm) of compound 1 reaches 58.5 J kg-1 K-1 at 2 K for a moderate field change (ΔH = 7 T). Moreover, the isomorphous MOFs: \{[Ln2(CO3)(ox)2(H2O)2]·3H2O\}n (Ln3+ = Ce3+(2), Pr3+(3), Nd3+(4), Tb3+(5)) also are structurally and functionally characterized, and compounds 2-5 exhibit proton conductivity above 10-3 S cm-1 in room air and without additional humidity.",

author = "Qun Tang and Yang, \{Yan Li\} and Ning Zhang and Zheng Liu and Zhang, \{Shu Hua\} and Tang, \{Fu Shun\} and Hu, \{Jia Yi\} and Zheng, \{Yan Zhen\} and Liang, \{Fu Pei\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = aug,

day = "6",

doi = "10.1021/acs.inorgchem.8b01023",

language = "英语",

volume = "57",

pages = "9020--9027",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "15",

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TY - JOUR

T1 - A Multifunctional Lanthanide Carbonate Cluster Based Metal-Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change

AU - Tang, Qun

AU - Yang, Yan Li

AU - Zhang, Ning

AU - Liu, Zheng

AU - Zhang, Shu Hua

AU - Tang, Fu Shun

AU - Hu, Jia Yi

AU - Zheng, Yan Zhen

AU - Liang, Fu Pei

PY - 2018/8/6

Y1 - 2018/8/6

N2 - A novel multifunctional, three-dimensional (3D) lanthanide carbonate cluster based metal-organic framework (MOF) with the general formula {[Gd2(CO3)(ox)2(H2O)2]·3H2O}n (1) has been synthesized via self-assembly of gadolinium (Gd) carbonate and oxalate under hydrothermal conditions. Single-crystal X-ray diffraction reveals that the compound 1 consists of the Gd carbonate cluster with oxalic acid ligands, which form a 3D framework structure with an ordered one-dimensional (1D) pore channel along the a-axis. The coordination water molecules of Gd3+ ions point to the interior of the pore and form a 1D hydrogen bond pathway with oxygen atoms in adjacent oxalic acid that is stable at high temperature (up to 150 °C). The compound 1 features multiple hydrogen-bonding walls and good thermal stabilities, and shows the highest proton conductivity of 1.98 × 10-3 S cm-1 at T = 150 °C and in room air without additional humidity. Magnetic investigations of compound 1 demonstrate that weak antiferromagnetic couplings between adjacent Gd3+ ions bring about large cryogenic magnetocaloric effects. Remarkably, the maximum entropy change (-ΔSm) of compound 1 reaches 58.5 J kg-1 K-1 at 2 K for a moderate field change (ΔH = 7 T). Moreover, the isomorphous MOFs: {[Ln2(CO3)(ox)2(H2O)2]·3H2O}n (Ln3+ = Ce3+(2), Pr3+(3), Nd3+(4), Tb3+(5)) also are structurally and functionally characterized, and compounds 2-5 exhibit proton conductivity above 10-3 S cm-1 in room air and without additional humidity.

AB - A novel multifunctional, three-dimensional (3D) lanthanide carbonate cluster based metal-organic framework (MOF) with the general formula {[Gd2(CO3)(ox)2(H2O)2]·3H2O}n (1) has been synthesized via self-assembly of gadolinium (Gd) carbonate and oxalate under hydrothermal conditions. Single-crystal X-ray diffraction reveals that the compound 1 consists of the Gd carbonate cluster with oxalic acid ligands, which form a 3D framework structure with an ordered one-dimensional (1D) pore channel along the a-axis. The coordination water molecules of Gd3+ ions point to the interior of the pore and form a 1D hydrogen bond pathway with oxygen atoms in adjacent oxalic acid that is stable at high temperature (up to 150 °C). The compound 1 features multiple hydrogen-bonding walls and good thermal stabilities, and shows the highest proton conductivity of 1.98 × 10-3 S cm-1 at T = 150 °C and in room air without additional humidity. Magnetic investigations of compound 1 demonstrate that weak antiferromagnetic couplings between adjacent Gd3+ ions bring about large cryogenic magnetocaloric effects. Remarkably, the maximum entropy change (-ΔSm) of compound 1 reaches 58.5 J kg-1 K-1 at 2 K for a moderate field change (ΔH = 7 T). Moreover, the isomorphous MOFs: {[Ln2(CO3)(ox)2(H2O)2]·3H2O}n (Ln3+ = Ce3+(2), Pr3+(3), Nd3+(4), Tb3+(5)) also are structurally and functionally characterized, and compounds 2-5 exhibit proton conductivity above 10-3 S cm-1 in room air and without additional humidity.

UR - https://www.scopus.com/pages/publications/85051237015

U2 - 10.1021/acs.inorgchem.8b01023

DO - 10.1021/acs.inorgchem.8b01023

M3 - 文章

C2 - 30004680

AN - SCOPUS:85051237015

SN - 0020-1669

VL - 57

SP - 9020

EP - 9027

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 15

ER -

A Multifunctional Lanthanide Carbonate Cluster Based Metal-Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change

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