Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases

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Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases. / Wharmby, Michael T.; Pearce, Gordon M.; Mowat, John P. S. et al.
In: Microporous and Mesoporous Materials, Vol. 157, 15.07.2012, p. 3-17.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Wharmby, MT, Pearce, GM, Mowat, JPS, Griffin, JM, Ashbrook, SE, Wright, PA, Schilling, L-H, Lieb, A, Stock, N, Chavan, S, Bordiga, S, Garcia, E, Pirngruber, GD, Vreeke, M & Gora, L 2012, 'Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases', Microporous and Mesoporous Materials, vol. 157, pp. 3-17. https://doi.org/10.1016/j.micromeso.2011.12.003

APA

Wharmby, M. T., Pearce, G. M., Mowat, J. P. S., Griffin, J. M., Ashbrook, S. E., Wright, P. A., Schilling, L-H., Lieb, A., Stock, N., Chavan, S., Bordiga, S., Garcia, E., Pirngruber, G. D., Vreeke, M., & Gora, L. (2012). Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases. Microporous and Mesoporous Materials, 157, 3-17. https://doi.org/10.1016/j.micromeso.2011.12.003

Vancouver

Wharmby MT, Pearce GM, Mowat JPS, Griffin JM, Ashbrook SE, Wright PA et al. Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases. Microporous and Mesoporous Materials. 2012 Jul 15;157:3-17. doi: 10.1016/j.micromeso.2011.12.003

Author

Wharmby, Michael T. ; Pearce, Gordon M. ; Mowat, John P. S. et al. / Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases. In: Microporous and Mesoporous Materials. 2012 ; Vol. 157. pp. 3-17.

Bibtex

@article{e3fbf0c28fbf4c2aa17b7aef6ac665b5,

title = "Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases",

abstract = "The crystal chemistry of divalent metal N,N'-piperazinebis(methylenephosphonates) of the STA-12 family, (M-2(H2O)(2)(O3PCH2NC4H8NCH2PO3)center dot xH(2)O, M = Mg, Mn, Fe, Co, Ni) is compared. The different metal analogues are isostructural in the hydrated forms, possessing 123 symmetry, but their reversible dehydration behaviour and resultant porosity are strongly dependent on the metal cation. Whereas the Co and Ni forms change symmetry to triclinic upon dehydration, giving permanent porosity to N-2 of 0.14 cm(3) g(-1) and 0.27 cm(3) g(-1), respectively, the Mn and Fe forms remain rhombohedral but exhibit a strong decrease in unit cell volume (e.g. 23% for STA-12(Mn)). Structure determination of dehydrated STA-12(Mn) indicates a topotactic transformation with a change in coordination of the phosphonate O atoms. Negligible permanent porosity is observed in either dehydrated STA-12(Mn) or (Fe), suggesting the presence of non-crystallographic pore blocking. Dehydration of STA-12(Mg) results in loss of some long range order, preventing structural determination of the fully dehydrated form, but does give appreciable permanent porosity for N-2 of 0.20 cm(3) g(-1). Infrared spectroscopy (and for STA-12(Mg) solid-state NMR spectroscopy) have been used to follow the changes upon dehydration. Applications of the most porous and stable STA-12 structure, the Ni form, have also been investigated. CO2 adsorption selectivity over CH4 and CO has been measured via analysis of breakthrough curves, and a Porous Layer Open Tubular (PLOT) gas chromatographic column has been prepared and used to separate a mixture of low molecular weight alkanes. (C) 2011 Elsevier Inc. All rights reserved.",

keywords = "Phosphonate MOFs, Dehydration behaviour, Adsorption, Breakthrough curves, GC PLOT column, ORGANIC-FRAMEWORK, CARBON-DIOXIDE, CHROMATOGRAPHIC SEPARATION, COORDINATION POLYMER, BUILDING UNITS, POROUS SOLIDS, ADSORPTION, SITES, CAVITIES, COLUMNS",

author = "Wharmby, {Michael T.} and Pearce, {Gordon M.} and Mowat, {John P. S.} and Griffin, {John M.} and Ashbrook, {Sharon E.} and Wright, {Paul A.} and Lars-Hendrik Schilling and Alexandra Lieb and Norbert Stock and Sachin Chavan and Silvia Bordiga and Edder Garcia and Pirngruber, {Gerhard D.} and Martin Vreeke and Leszek Gora",

year = "2012",

month = jul,

day = "15",

doi = "10.1016/j.micromeso.2011.12.003",

language = "English",

volume = "157",

pages = "3--17",

journal = "Microporous and Mesoporous Materials",

issn = "1387-1811",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Synthesis and crystal chemistry of the STA-12 family of metal N,N '-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases

AU - Wharmby, Michael T.

AU - Pearce, Gordon M.

AU - Mowat, John P. S.

AU - Griffin, John M.

AU - Ashbrook, Sharon E.

AU - Wright, Paul A.

AU - Schilling, Lars-Hendrik

AU - Lieb, Alexandra

AU - Stock, Norbert

AU - Chavan, Sachin

AU - Bordiga, Silvia

AU - Garcia, Edder

AU - Pirngruber, Gerhard D.

AU - Vreeke, Martin

AU - Gora, Leszek

PY - 2012/7/15

Y1 - 2012/7/15

N2 - The crystal chemistry of divalent metal N,N'-piperazinebis(methylenephosphonates) of the STA-12 family, (M-2(H2O)(2)(O3PCH2NC4H8NCH2PO3)center dot xH(2)O, M = Mg, Mn, Fe, Co, Ni) is compared. The different metal analogues are isostructural in the hydrated forms, possessing 123 symmetry, but their reversible dehydration behaviour and resultant porosity are strongly dependent on the metal cation. Whereas the Co and Ni forms change symmetry to triclinic upon dehydration, giving permanent porosity to N-2 of 0.14 cm(3) g(-1) and 0.27 cm(3) g(-1), respectively, the Mn and Fe forms remain rhombohedral but exhibit a strong decrease in unit cell volume (e.g. 23% for STA-12(Mn)). Structure determination of dehydrated STA-12(Mn) indicates a topotactic transformation with a change in coordination of the phosphonate O atoms. Negligible permanent porosity is observed in either dehydrated STA-12(Mn) or (Fe), suggesting the presence of non-crystallographic pore blocking. Dehydration of STA-12(Mg) results in loss of some long range order, preventing structural determination of the fully dehydrated form, but does give appreciable permanent porosity for N-2 of 0.20 cm(3) g(-1). Infrared spectroscopy (and for STA-12(Mg) solid-state NMR spectroscopy) have been used to follow the changes upon dehydration. Applications of the most porous and stable STA-12 structure, the Ni form, have also been investigated. CO2 adsorption selectivity over CH4 and CO has been measured via analysis of breakthrough curves, and a Porous Layer Open Tubular (PLOT) gas chromatographic column has been prepared and used to separate a mixture of low molecular weight alkanes. (C) 2011 Elsevier Inc. All rights reserved.

AB - The crystal chemistry of divalent metal N,N'-piperazinebis(methylenephosphonates) of the STA-12 family, (M-2(H2O)(2)(O3PCH2NC4H8NCH2PO3)center dot xH(2)O, M = Mg, Mn, Fe, Co, Ni) is compared. The different metal analogues are isostructural in the hydrated forms, possessing 123 symmetry, but their reversible dehydration behaviour and resultant porosity are strongly dependent on the metal cation. Whereas the Co and Ni forms change symmetry to triclinic upon dehydration, giving permanent porosity to N-2 of 0.14 cm(3) g(-1) and 0.27 cm(3) g(-1), respectively, the Mn and Fe forms remain rhombohedral but exhibit a strong decrease in unit cell volume (e.g. 23% for STA-12(Mn)). Structure determination of dehydrated STA-12(Mn) indicates a topotactic transformation with a change in coordination of the phosphonate O atoms. Negligible permanent porosity is observed in either dehydrated STA-12(Mn) or (Fe), suggesting the presence of non-crystallographic pore blocking. Dehydration of STA-12(Mg) results in loss of some long range order, preventing structural determination of the fully dehydrated form, but does give appreciable permanent porosity for N-2 of 0.20 cm(3) g(-1). Infrared spectroscopy (and for STA-12(Mg) solid-state NMR spectroscopy) have been used to follow the changes upon dehydration. Applications of the most porous and stable STA-12 structure, the Ni form, have also been investigated. CO2 adsorption selectivity over CH4 and CO has been measured via analysis of breakthrough curves, and a Porous Layer Open Tubular (PLOT) gas chromatographic column has been prepared and used to separate a mixture of low molecular weight alkanes. (C) 2011 Elsevier Inc. All rights reserved.

KW - Phosphonate MOFs

KW - Dehydration behaviour

KW - Adsorption

KW - Breakthrough curves

KW - GC PLOT column

KW - ORGANIC-FRAMEWORK

KW - CARBON-DIOXIDE

KW - CHROMATOGRAPHIC SEPARATION

KW - COORDINATION POLYMER

KW - BUILDING UNITS

KW - POROUS SOLIDS

KW - ADSORPTION

KW - SITES

KW - CAVITIES

KW - COLUMNS

U2 - 10.1016/j.micromeso.2011.12.003

DO - 10.1016/j.micromeso.2011.12.003

M3 - Journal article

VL - 157

SP - 3

EP - 17

JO - Microporous and Mesoporous Materials

JF - Microporous and Mesoporous Materials

SN - 1387-1811

ER -

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