Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF

P.L. Llewellyn; M. Garcia-Rates; L. Gaberová; Stuart R Miller; T. Devic; J.-C. Lavalley; S. Bourrelly; E. Bloch; Y. Filinchuk; P.A. Wright; C. Serre; A. Vimont; G. Maurin

doi:10.1021/jp512596u

Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF

P.L. Llewellyn, M. Garcia-Rates, L. Gaberová, Stuart R Miller, T. Devic, J.-C. Lavalley, S. Bourrelly, E. Bloch, Y. Filinchuk, P.A. Wright, C. Serre, A. Vimont, G. Maurin

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

Abstract

The adsorption of CO₂, CH₄, and N₂ at 303 K by MIL-91(Al), one of the few porous phosphonate-based-MOFs, has been investigated by combining advanced experimental and computational tools. Whereas CH₄ and N₂ adsorption isotherms exhibit type I behavior, the reversible CO₂ isotherm displays an unusual inflection point at low pressure. In situ X-ray powder diffraction and infrared spectroscopy showed structural changes of this small-pore MOF upon CO₂ adsorption. Grand canonical Monte Carlo simulations delivered a detailed picture of the adsorption mechanisms at the microscopic level. The so-predicted arrangements of the confined CO₂molecules were supported by analysis of the in situ diffraction and infrared experiments. It was shown that while adsorbed CH₄ and N₂ are located mainly in the center of the pores, CO₂ molecules interact with the hydrogen-bonded POH–N acid–base pairs. This results in a relatively high adsorption enthalpy for CO₂ of ca. −40 kJ mol^–1, which suggests that this material might be of interest for CO₂ capture at low pressure (postcombustion).

Original language	English
Pages (from-to)	4208-4216
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	119
Issue number	8
Early online date	4 Feb 2015
DOIs	https://doi.org/10.1021/jp512596u
Publication status	Published - 26 Feb 2015

Access to Document

10.1021/jp512596u

Cite this

Llewellyn, P. L., Garcia-Rates, M., Gaberová, L., Miller, S. R., Devic, T., Lavalley, J.-C., Bourrelly, S., Bloch, E., Filinchuk, Y., Wright, P. A., Serre, C., Vimont, A., & Maurin, G. (2015). Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF. Journal of Physical Chemistry C, 119(8), 4208-4216. https://doi.org/10.1021/jp512596u

@article{e156aa056474418fabc9ee4c77570665,

title = "Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF",

abstract = "The adsorption of CO2, CH4, and N2 at 303 K by MIL-91(Al), one of the few porous phosphonate-based-MOFs, has been investigated by combining advanced experimental and computational tools. Whereas CH4 and N2 adsorption isotherms exhibit type I behavior, the reversible CO2 isotherm displays an unusual inflection point at low pressure. In situ X-ray powder diffraction and infrared spectroscopy showed structural changes of this small-pore MOF upon CO2 adsorption. Grand canonical Monte Carlo simulations delivered a detailed picture of the adsorption mechanisms at the microscopic level. The so-predicted arrangements of the confined CO2 molecules were supported by analysis of the in situ diffraction and infrared experiments. It was shown that while adsorbed CH4 and N2 are located mainly in the center of the pores, CO2 molecules interact with the hydrogen-bonded POH–N acid–base pairs. This results in a relatively high adsorption enthalpy for CO2 of ca. −40 kJ mol–1, which suggests that this material might be of interest for CO2 capture at low pressure (postcombustion).",

author = "P.L. Llewellyn and M. Garcia-Rates and L. Gaberov{\'a} and Miller, {Stuart R} and T. Devic and J.-C. Lavalley and S. Bourrelly and E. Bloch and Y. Filinchuk and P.A. Wright and C. Serre and A. Vimont and G. Maurin",

note = "The research leading to these results has received funding from the European Community{\textquoteright}s Seventh Framework Program (FP7/2007-2013) under grant agreement no. 228862 (Macademia project) and from the FP6-Specific Targeted Research Project DeSANNS (SES6-020133).",

year = "2015",

month = feb,

day = "26",

doi = "10.1021/jp512596u",

language = "English",

volume = "119",

pages = "4208--4216",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society (ACS)",

number = "8",

}

TY - JOUR

T1 - Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF

AU - Llewellyn, P.L.

AU - Garcia-Rates, M.

AU - Gaberová, L.

AU - Miller, Stuart R

AU - Devic, T.

AU - Lavalley, J.-C.

AU - Bourrelly, S.

AU - Bloch, E.

AU - Filinchuk, Y.

AU - Wright, P.A.

AU - Serre, C.

AU - Vimont, A.

AU - Maurin, G.

N1 - The research leading to these results has received funding from the European Community’s Seventh Framework Program (FP7/2007-2013) under grant agreement no. 228862 (Macademia project) and from the FP6-Specific Targeted Research Project DeSANNS (SES6-020133).

PY - 2015/2/26

Y1 - 2015/2/26

N2 - The adsorption of CO2, CH4, and N2 at 303 K by MIL-91(Al), one of the few porous phosphonate-based-MOFs, has been investigated by combining advanced experimental and computational tools. Whereas CH4 and N2 adsorption isotherms exhibit type I behavior, the reversible CO2 isotherm displays an unusual inflection point at low pressure. In situ X-ray powder diffraction and infrared spectroscopy showed structural changes of this small-pore MOF upon CO2 adsorption. Grand canonical Monte Carlo simulations delivered a detailed picture of the adsorption mechanisms at the microscopic level. The so-predicted arrangements of the confined CO2 molecules were supported by analysis of the in situ diffraction and infrared experiments. It was shown that while adsorbed CH4 and N2 are located mainly in the center of the pores, CO2 molecules interact with the hydrogen-bonded POH–N acid–base pairs. This results in a relatively high adsorption enthalpy for CO2 of ca. −40 kJ mol–1, which suggests that this material might be of interest for CO2 capture at low pressure (postcombustion).

AB - The adsorption of CO2, CH4, and N2 at 303 K by MIL-91(Al), one of the few porous phosphonate-based-MOFs, has been investigated by combining advanced experimental and computational tools. Whereas CH4 and N2 adsorption isotherms exhibit type I behavior, the reversible CO2 isotherm displays an unusual inflection point at low pressure. In situ X-ray powder diffraction and infrared spectroscopy showed structural changes of this small-pore MOF upon CO2 adsorption. Grand canonical Monte Carlo simulations delivered a detailed picture of the adsorption mechanisms at the microscopic level. The so-predicted arrangements of the confined CO2 molecules were supported by analysis of the in situ diffraction and infrared experiments. It was shown that while adsorbed CH4 and N2 are located mainly in the center of the pores, CO2 molecules interact with the hydrogen-bonded POH–N acid–base pairs. This results in a relatively high adsorption enthalpy for CO2 of ca. −40 kJ mol–1, which suggests that this material might be of interest for CO2 capture at low pressure (postcombustion).

UR - http://pubs.acs.org/doi/suppl/10.1021/jp512596u

U2 - 10.1021/jp512596u

DO - 10.1021/jp512596u

M3 - Article

AN - SCOPUS:84923974506

SN - 1932-7447

VL - 119

SP - 4208

EP - 4216

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 8

ER -

Structural origin of unusual CO adsorption behavior of a small-pore aluminum bisphosphonate MOF

Abstract

Access to Document

Other files and links

Fingerprint

Cite this