Microporous metal-organic frameworks incorporating 1,4- benzeneditetrazolate: Syntheses, structures, and hydrogen storage properties

Mircea Dincâ; Anta F. Yu; Jeffrey R. Long

doi:10.1021/ja061716i

Microporous metal-organic frameworks incorporating 1,4- benzeneditetrazolate: Syntheses, structures, and hydrogen storage properties

Mircea Dincâ, Anta F. Yu, Jeffrey R. Long

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638 Scopus citations

Abstract

The potential of tetrazolate-based ligands for forming metal-organic frameworks of utility in hydrogen storage is demonstrated with the use of 1,4-benzeneditetrazolate (BDT²) to generate a series of robust, microporous materials. Reaction of H²BDT with MnCl ₂·4H₂O and Mn(NO₃)2·4H ₂O in N,N-diethylformamide (DEF) produces the two-dimensional framework solids Mn₃(BDT)₂Cl₂(DEF)₆ (1) and Mn₄-(BDT)₃(NO₃)₂(DEF) ₆ (2), whereas reactions with hydrated salts of Mn²⁺, Cu²⁺, and Zn₂₊ in a mixture of methanol and DMF afford the porous, three-dimensional framework solids Zn₃(BDT) ₃(DMF)₄(H₂O)₂-3.5CH₃-OH (3), Mn₃(BDT)₃(DMF)₄(H₂O) ₂-3CH₃OH-2H₂O·DMF (4), Mn ₂(BDT)Cl₂(DMF)₂·1.5CH ₃OH·H₂O (5), and Cu-(BDT) (DMF)·CH ₃OH-0.25DMF (6). It is shown that the method for desolvating such compounds can dramatically influence the ensuing gas sorption properties. When subjected to a mild evacuation procedure, compounds 3-6 exhibit permanent porosity, with BET surface areas in the range 200-640 m²/g. The desolvated forms of 3-5 store between 0.82 and 1.46 wt % H₂ at 77 K and 1 atm, with enthalpies of adsorption in the range 6.0-8.8 kJ/mol, among the highest so far reported for metal-organic frameworks. In addition, the desolvated form of 6 exhibits preferential adsorption of O₂ over H₂ and N2, showing promise for gas separation and purification applications.

Original language	English (US)
Pages (from-to)	8904-8913
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	128
Issue number	27
DOIs	https://doi.org/10.1021/ja061716i
State	Published - Jul 12 2006
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja061716i

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@article{0ad759d8ebde4f598e56f73c3c6886f1,

title = "Microporous metal-organic frameworks incorporating 1,4- benzeneditetrazolate: Syntheses, structures, and hydrogen storage properties",

abstract = "The potential of tetrazolate-based ligands for forming metal-organic frameworks of utility in hydrogen storage is demonstrated with the use of 1,4-benzeneditetrazolate (BDT2) to generate a series of robust, microporous materials. Reaction of H2BDT with MnCl 2·4H2O and Mn(NO3)2·4H 2O in N,N-diethylformamide (DEF) produces the two-dimensional framework solids Mn3(BDT)2Cl2(DEF)6 (1) and Mn4-(BDT)3(NO3)2(DEF) 6 (2), whereas reactions with hydrated salts of Mn2+, Cu2+, and Zn2+ in a mixture of methanol and DMF afford the porous, three-dimensional framework solids Zn3(BDT) 3(DMF)4(H2O)2-3.5CH3-OH (3), Mn3(BDT)3(DMF)4(H2O) 2-3CH3OH-2H2O·DMF (4), Mn 2(BDT)Cl2(DMF)2·1.5CH 3OH·H2O (5), and Cu-(BDT) (DMF)·CH 3OH-0.25DMF (6). It is shown that the method for desolvating such compounds can dramatically influence the ensuing gas sorption properties. When subjected to a mild evacuation procedure, compounds 3-6 exhibit permanent porosity, with BET surface areas in the range 200-640 m2/g. The desolvated forms of 3-5 store between 0.82 and 1.46 wt \% H2 at 77 K and 1 atm, with enthalpies of adsorption in the range 6.0-8.8 kJ/mol, among the highest so far reported for metal-organic frameworks. In addition, the desolvated form of 6 exhibits preferential adsorption of O2 over H2 and N2, showing promise for gas separation and purification applications.",

author = "Mircea Dinc{\^a} and Yu, \{Anta F.\} and Long, \{Jeffrey R.\}",

year = "2006",

month = jul,

day = "12",

doi = "10.1021/ja061716i",

language = "English (US)",

volume = "128",

pages = "8904--8913",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Microporous metal-organic frameworks incorporating 1,4- benzeneditetrazolate

T2 - Syntheses, structures, and hydrogen storage properties

AU - Dincâ, Mircea

AU - Yu, Anta F.

AU - Long, Jeffrey R.

PY - 2006/7/12

Y1 - 2006/7/12

N2 - The potential of tetrazolate-based ligands for forming metal-organic frameworks of utility in hydrogen storage is demonstrated with the use of 1,4-benzeneditetrazolate (BDT2) to generate a series of robust, microporous materials. Reaction of H2BDT with MnCl 2·4H2O and Mn(NO3)2·4H 2O in N,N-diethylformamide (DEF) produces the two-dimensional framework solids Mn3(BDT)2Cl2(DEF)6 (1) and Mn4-(BDT)3(NO3)2(DEF) 6 (2), whereas reactions with hydrated salts of Mn2+, Cu2+, and Zn2+ in a mixture of methanol and DMF afford the porous, three-dimensional framework solids Zn3(BDT) 3(DMF)4(H2O)2-3.5CH3-OH (3), Mn3(BDT)3(DMF)4(H2O) 2-3CH3OH-2H2O·DMF (4), Mn 2(BDT)Cl2(DMF)2·1.5CH 3OH·H2O (5), and Cu-(BDT) (DMF)·CH 3OH-0.25DMF (6). It is shown that the method for desolvating such compounds can dramatically influence the ensuing gas sorption properties. When subjected to a mild evacuation procedure, compounds 3-6 exhibit permanent porosity, with BET surface areas in the range 200-640 m2/g. The desolvated forms of 3-5 store between 0.82 and 1.46 wt % H2 at 77 K and 1 atm, with enthalpies of adsorption in the range 6.0-8.8 kJ/mol, among the highest so far reported for metal-organic frameworks. In addition, the desolvated form of 6 exhibits preferential adsorption of O2 over H2 and N2, showing promise for gas separation and purification applications.

AB - The potential of tetrazolate-based ligands for forming metal-organic frameworks of utility in hydrogen storage is demonstrated with the use of 1,4-benzeneditetrazolate (BDT2) to generate a series of robust, microporous materials. Reaction of H2BDT with MnCl 2·4H2O and Mn(NO3)2·4H 2O in N,N-diethylformamide (DEF) produces the two-dimensional framework solids Mn3(BDT)2Cl2(DEF)6 (1) and Mn4-(BDT)3(NO3)2(DEF) 6 (2), whereas reactions with hydrated salts of Mn2+, Cu2+, and Zn2+ in a mixture of methanol and DMF afford the porous, three-dimensional framework solids Zn3(BDT) 3(DMF)4(H2O)2-3.5CH3-OH (3), Mn3(BDT)3(DMF)4(H2O) 2-3CH3OH-2H2O·DMF (4), Mn 2(BDT)Cl2(DMF)2·1.5CH 3OH·H2O (5), and Cu-(BDT) (DMF)·CH 3OH-0.25DMF (6). It is shown that the method for desolvating such compounds can dramatically influence the ensuing gas sorption properties. When subjected to a mild evacuation procedure, compounds 3-6 exhibit permanent porosity, with BET surface areas in the range 200-640 m2/g. The desolvated forms of 3-5 store between 0.82 and 1.46 wt % H2 at 77 K and 1 atm, with enthalpies of adsorption in the range 6.0-8.8 kJ/mol, among the highest so far reported for metal-organic frameworks. In addition, the desolvated form of 6 exhibits preferential adsorption of O2 over H2 and N2, showing promise for gas separation and purification applications.

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U2 - 10.1021/ja061716i

DO - 10.1021/ja061716i

M3 - Article

C2 - 16819886

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SN - 0002-7863

VL - 128

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 27

ER -

Microporous metal-organic frameworks incorporating 1,4- benzeneditetrazolate: Syntheses, structures, and hydrogen storage properties

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