Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5

Mudit Dixit; Tuhina Adit Maark; Sourav Pal

doi:10.1016/j.ijhydene.2011.05.165

Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5

Mudit Dixit, Tuhina Adit Maark, Sourav Pal

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Abstract

The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M₂:nH₂ and MOF-5:M₂:nH₂, where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G (*) and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H ₂ molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H₂-MOF-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively.

Original language	English
Pages (from-to)	10816-10827
Number of pages	12
Journal	International Journal of Hydrogen Energy
Volume	36
Issue number	17
DOIs	https://doi.org/10.1016/j.ijhydene.2011.05.165
State	Published - Aug 2011
Externally published	Yes

Bibliographical note

Funding Information:
The authors acknowledge the computational facilities of the Center of Excellence in Scientific Computing at National Chemical Laboratory, Pune. The authors also thank the FP7-NMP-EU-India-2 collaborative project HYPOMAP on “New materials for hydrogen powered mobile applications” for providing financial support. One of the authors (M.D.) thanks UGC, India for grant of Junior Research Fellowship and Bhakti Kulkarni for their help during the work. T.A.M. acknowledges the Swedish Institute for the scholarship for postdoctoral studies. S.P. acknowledges the J. C. Bose Fellowship grant of DST, India toward completion of this work.

Keywords

Ab initio calculations
Density functional theory
Hydrogen binding energies
Hydrogen storage
Metal-Pi-Arene interactions

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.ijhydene.2011.05.165

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title = "Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5",

abstract = "The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M2:nH2 and MOF-5:M2:nH2, where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G (*) and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H 2 molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H2-MOF-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively.",

keywords = "Ab initio calculations, Density functional theory, Hydrogen binding energies, Hydrogen storage, Metal-Pi-Arene interactions",

author = "Mudit Dixit and Maark, {Tuhina Adit} and Sourav Pal",

note = "Funding Information: The authors acknowledge the computational facilities of the Center of Excellence in Scientific Computing at National Chemical Laboratory, Pune. The authors also thank the FP7-NMP-EU-India-2 collaborative project HYPOMAP on “New materials for hydrogen powered mobile applications” for providing financial support. One of the authors (M.D.) thanks UGC, India for grant of Junior Research Fellowship and Bhakti Kulkarni for their help during the work. T.A.M. acknowledges the Swedish Institute for the scholarship for postdoctoral studies. S.P. acknowledges the J. C. Bose Fellowship grant of DST, India toward completion of this work. ",

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AU - Maark, Tuhina Adit

AU - Pal, Sourav

N1 - Funding Information: The authors acknowledge the computational facilities of the Center of Excellence in Scientific Computing at National Chemical Laboratory, Pune. The authors also thank the FP7-NMP-EU-India-2 collaborative project HYPOMAP on “New materials for hydrogen powered mobile applications” for providing financial support. One of the authors (M.D.) thanks UGC, India for grant of Junior Research Fellowship and Bhakti Kulkarni for their help during the work. T.A.M. acknowledges the Swedish Institute for the scholarship for postdoctoral studies. S.P. acknowledges the J. C. Bose Fellowship grant of DST, India toward completion of this work.

PY - 2011/8

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N2 - The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M2:nH2 and MOF-5:M2:nH2, where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G (*) and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H 2 molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H2-MOF-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively.

AB - The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M2:nH2 and MOF-5:M2:nH2, where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G (*) and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H 2 molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H2-MOF-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively.

KW - Ab initio calculations

KW - Density functional theory

KW - Hydrogen binding energies

KW - Hydrogen storage

KW - Metal-Pi-Arene interactions

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SN - 0360-3199

VL - 36

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EP - 10827

JO - International Journal of Hydrogen Energy

JF - International Journal of Hydrogen Energy

IS - 17

ER -

Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5

Abstract

Bibliographical note

Keywords

UN SDGs

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