Porous lanthanide-organic frameworks: Synthesis, characterization, and unprecedented gas adsorption properties

Long Pan; Kristie M. Adams; Hayden E. Hernandez; Xiaotai Wang; Chong Zheng; Yoshiyuki Hattori; Katsumi Kaneko

doi:10.1021/ja028996w

Porous lanthanide-organic frameworks: Synthesis, characterization, and unprecedented gas adsorption properties

Long Pan
, Kristie M. Adams
, Hayden E. Hernandez
, Xiaotai Wang^*
, Chong Zheng
, Yoshiyuki Hattori
, Katsumi Kaneko

^*Corresponding author for this work

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

663 Citations (Scopus)

Abstract

The reactions of Ln(NO₃)₃ (Ln = La, Er) with 1,4-phenylendiacetic acid (H₂PDA) under hydrothermal conditions produce isostructural lanthanide coordination polymers with the empirical formula [Ln₂(PDA)₃(H₂O)]·2H₂O. The extended structure of [Ln₂(PDA)₃(H₂O)]·2H₂O consists of Ln-COO triple helixes cross-linked through the -CH₂C₆H₄CH₂- spacers of the PDA anions, showing 1D open channels along the crystallographic c axis that accommodate the guest and coordinated water molecules. Evacuation of [Er₂(PDA)₃(H₂O)]·2H₂O at room temperature and at 200 ·C, respectively, generates [Er₂(PDA)₃(H₂O)] and [Er₂(PDA)₃], both of which give powder X-ray diffraction patterns consistent with that of [Er₂(PDA)₃(H₂O)]· 2H₂O. The porosity of [Er₂(PDA)₃(H₂O)] and [Er₂(PDA)₃] is further demonstrated by their ability to adsorb water vapor to form [Er₂(PDA)₃(H₂O)]·2H₂O quantitatively. Thermogravimetric analyses show that [Er₂-(PDA)₃] remains stable up to 450 °C. The effective pore window size in [Er₂(PDA)₃] is estimated at 3.4 Å. Gas adsorption measurements indicate that [Er₂(PDA)₃] adsorbs CO₂ into its pores and shows nonporous behavior toward Ar or N₂. There is a general correlation between the pore size and the kinetic diameters of the adsorbates (CO₂ = 3.3 Å, Ar = 3.40 Å, and N₂ = 3.64 Å). That the adsorption favors CO₂ over Ar is unprecedented and may arise from the combined differentiations on size and on host-guest interactions.

Original language	English
Pages (from-to)	3062-3067
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	125
Issue number	10
DOIs	https://doi.org/10.1021/ja028996w
Publication status	Published - 12 Mar 2003
Externally published	Yes

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@article{ae89dacd474a4e5cb90ef9c7997b9d15,

title = "Porous lanthanide-organic frameworks: Synthesis, characterization, and unprecedented gas adsorption properties",

abstract = "The reactions of Ln(NO3)3 (Ln = La, Er) with 1,4-phenylendiacetic acid (H2PDA) under hydrothermal conditions produce isostructural lanthanide coordination polymers with the empirical formula [Ln2(PDA)3(H2O)]·2H2O. The extended structure of [Ln2(PDA)3(H2O)]·2H2O consists of Ln-COO triple helixes cross-linked through the -CH2C6H4CH2- spacers of the PDA anions, showing 1D open channels along the crystallographic c axis that accommodate the guest and coordinated water molecules. Evacuation of [Er2(PDA)3(H2O)]·2H2O at room temperature and at 200 ·C, respectively, generates [Er2(PDA)3(H2O)] and [Er2(PDA)3], both of which give powder X-ray diffraction patterns consistent with that of [Er2(PDA)3(H2O)]· 2H2O. The porosity of [Er2(PDA)3(H2O)] and [Er2(PDA)3] is further demonstrated by their ability to adsorb water vapor to form [Er2(PDA)3(H2O)]·2H2O quantitatively. Thermogravimetric analyses show that [Er2-(PDA)3] remains stable up to 450 °C. The effective pore window size in [Er2(PDA)3] is estimated at 3.4 {\AA}. Gas adsorption measurements indicate that [Er2(PDA)3] adsorbs CO2 into its pores and shows nonporous behavior toward Ar or N2. There is a general correlation between the pore size and the kinetic diameters of the adsorbates (CO2 = 3.3 {\AA}, Ar = 3.40 {\AA}, and N2 = 3.64 {\AA}). That the adsorption favors CO2 over Ar is unprecedented and may arise from the combined differentiations on size and on host-guest interactions.",

author = "Long Pan and Adams, \{Kristie M.\} and Hernandez, \{Hayden E.\} and Xiaotai Wang and Chong Zheng and Yoshiyuki Hattori and Katsumi Kaneko",

year = "2003",

month = mar,

day = "12",

doi = "10.1021/ja028996w",

language = "English",

volume = "125",

pages = "3062--3067",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "10",

}

TY - JOUR

T1 - Porous lanthanide-organic frameworks

T2 - Synthesis, characterization, and unprecedented gas adsorption properties

AU - Pan, Long

AU - Adams, Kristie M.

AU - Hernandez, Hayden E.

AU - Wang, Xiaotai

AU - Zheng, Chong

AU - Hattori, Yoshiyuki

AU - Kaneko, Katsumi

PY - 2003/3/12

Y1 - 2003/3/12

N2 - The reactions of Ln(NO3)3 (Ln = La, Er) with 1,4-phenylendiacetic acid (H2PDA) under hydrothermal conditions produce isostructural lanthanide coordination polymers with the empirical formula [Ln2(PDA)3(H2O)]·2H2O. The extended structure of [Ln2(PDA)3(H2O)]·2H2O consists of Ln-COO triple helixes cross-linked through the -CH2C6H4CH2- spacers of the PDA anions, showing 1D open channels along the crystallographic c axis that accommodate the guest and coordinated water molecules. Evacuation of [Er2(PDA)3(H2O)]·2H2O at room temperature and at 200 ·C, respectively, generates [Er2(PDA)3(H2O)] and [Er2(PDA)3], both of which give powder X-ray diffraction patterns consistent with that of [Er2(PDA)3(H2O)]· 2H2O. The porosity of [Er2(PDA)3(H2O)] and [Er2(PDA)3] is further demonstrated by their ability to adsorb water vapor to form [Er2(PDA)3(H2O)]·2H2O quantitatively. Thermogravimetric analyses show that [Er2-(PDA)3] remains stable up to 450 °C. The effective pore window size in [Er2(PDA)3] is estimated at 3.4 Å. Gas adsorption measurements indicate that [Er2(PDA)3] adsorbs CO2 into its pores and shows nonporous behavior toward Ar or N2. There is a general correlation between the pore size and the kinetic diameters of the adsorbates (CO2 = 3.3 Å, Ar = 3.40 Å, and N2 = 3.64 Å). That the adsorption favors CO2 over Ar is unprecedented and may arise from the combined differentiations on size and on host-guest interactions.

AB - The reactions of Ln(NO3)3 (Ln = La, Er) with 1,4-phenylendiacetic acid (H2PDA) under hydrothermal conditions produce isostructural lanthanide coordination polymers with the empirical formula [Ln2(PDA)3(H2O)]·2H2O. The extended structure of [Ln2(PDA)3(H2O)]·2H2O consists of Ln-COO triple helixes cross-linked through the -CH2C6H4CH2- spacers of the PDA anions, showing 1D open channels along the crystallographic c axis that accommodate the guest and coordinated water molecules. Evacuation of [Er2(PDA)3(H2O)]·2H2O at room temperature and at 200 ·C, respectively, generates [Er2(PDA)3(H2O)] and [Er2(PDA)3], both of which give powder X-ray diffraction patterns consistent with that of [Er2(PDA)3(H2O)]· 2H2O. The porosity of [Er2(PDA)3(H2O)] and [Er2(PDA)3] is further demonstrated by their ability to adsorb water vapor to form [Er2(PDA)3(H2O)]·2H2O quantitatively. Thermogravimetric analyses show that [Er2-(PDA)3] remains stable up to 450 °C. The effective pore window size in [Er2(PDA)3] is estimated at 3.4 Å. Gas adsorption measurements indicate that [Er2(PDA)3] adsorbs CO2 into its pores and shows nonporous behavior toward Ar or N2. There is a general correlation between the pore size and the kinetic diameters of the adsorbates (CO2 = 3.3 Å, Ar = 3.40 Å, and N2 = 3.64 Å). That the adsorption favors CO2 over Ar is unprecedented and may arise from the combined differentiations on size and on host-guest interactions.

UR - https://www.scopus.com/pages/publications/0037433599

U2 - 10.1021/ja028996w

DO - 10.1021/ja028996w

M3 - Article

AN - SCOPUS:0037433599

SN - 0002-7863

VL - 125

SP - 3062

EP - 3067

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 10

ER -

Porous lanthanide-organic frameworks: Synthesis, characterization, and unprecedented gas adsorption properties

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