CO adsorption on a mixed-valence ruthenium metal-organic framework studied by UHV-FTIR spectroscopy and DFT calculations

Heshmat Noei; Olesia Kozachuk; Saeed Amirjalayer; Sareeya Bureekaew; Max Kauer; Rochus Schmid; Bernd Marler; Martin Muhler; Roland A. Fischer; Yuemin Wang

doi:10.1021/jp3056366

CO adsorption on a mixed-valence ruthenium metal-organic framework studied by UHV-FTIR spectroscopy and DFT calculations

Heshmat Noei, Olesia Kozachuk, Saeed Amirjalayer, Sareeya Bureekaew, Max Kauer, Rochus Schmid, Bernd Marler, Martin Muhler, Roland A. Fischer, Yuemin Wang

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

43 Scopus citations

Abstract

The mixed-valence metal-organic framework [Ru₃ ^II,III(btc)₂Cl_1.5] (Ru-MOF) was synthesized by the controlled SBU approach and characterized by combined powder XRD, XPS, and FTIR methods. The interaction of CO molecules with Ru-MOF was studied by a novel instrumentation for ultra-high-vacuum (UHV) FTIR spectroscopy. The high-quality IR data demonstrate the presence of two different CO species within the framework: a strongly bonded CO showing a low-lying band at 2137 cm^-1 and a second CO species at 2171 cm^-1 with a lower binding energy. It was found that these IR bands cannot be assigned in a straightforward manner to CO molecules adsorbed on the coordinatively unsaturated Ru^II site (CUS) and Ru^III site connected to an additional Cl^- ion for charge compensation. The accurate DFT calculations reveal that the structural and electronic properties of the mixed-valence Ru-MOF are much more complex than expected. One of the Cl^- counterions could be transferred to a neighboring paddle-wheel, forming an anionic SBU blocked by two Cl^- counterions, whereas the other positively charged paddle-wheel with a Ru₂^II,III dimer exposes two "free" CUS, which can bind two CO molecules with different frequencies and binding energies.

Original language	English
Pages (from-to)	5658-5666
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	117
Issue number	11
DOIs	https://doi.org/10.1021/jp3056366
State	Published - 21 Mar 2013
Externally published	Yes

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@article{b7175234e24749d3a0ad81661b6473a4,

title = "CO adsorption on a mixed-valence ruthenium metal-organic framework studied by UHV-FTIR spectroscopy and DFT calculations",

abstract = "The mixed-valence metal-organic framework [Ru3 II,III(btc)2Cl1.5] (Ru-MOF) was synthesized by the controlled SBU approach and characterized by combined powder XRD, XPS, and FTIR methods. The interaction of CO molecules with Ru-MOF was studied by a novel instrumentation for ultra-high-vacuum (UHV) FTIR spectroscopy. The high-quality IR data demonstrate the presence of two different CO species within the framework: a strongly bonded CO showing a low-lying band at 2137 cm-1 and a second CO species at 2171 cm-1 with a lower binding energy. It was found that these IR bands cannot be assigned in a straightforward manner to CO molecules adsorbed on the coordinatively unsaturated RuII site (CUS) and RuIII site connected to an additional Cl- ion for charge compensation. The accurate DFT calculations reveal that the structural and electronic properties of the mixed-valence Ru-MOF are much more complex than expected. One of the Cl- counterions could be transferred to a neighboring paddle-wheel, forming an anionic SBU blocked by two Cl- counterions, whereas the other positively charged paddle-wheel with a Ru2II,III dimer exposes two {"}free{"} CUS, which can bind two CO molecules with different frequencies and binding energies.",

author = "Heshmat Noei and Olesia Kozachuk and Saeed Amirjalayer and Sareeya Bureekaew and Max Kauer and Rochus Schmid and Bernd Marler and Martin Muhler and Fischer, {Roland A.} and Yuemin Wang",

year = "2013",

month = mar,

day = "21",

doi = "10.1021/jp3056366",

language = "English",

volume = "117",

pages = "5658--5666",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

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TY - JOUR

T1 - CO adsorption on a mixed-valence ruthenium metal-organic framework studied by UHV-FTIR spectroscopy and DFT calculations

AU - Noei, Heshmat

AU - Kozachuk, Olesia

AU - Amirjalayer, Saeed

AU - Bureekaew, Sareeya

AU - Kauer, Max

AU - Schmid, Rochus

AU - Marler, Bernd

AU - Muhler, Martin

AU - Fischer, Roland A.

AU - Wang, Yuemin

PY - 2013/3/21

Y1 - 2013/3/21

N2 - The mixed-valence metal-organic framework [Ru3 II,III(btc)2Cl1.5] (Ru-MOF) was synthesized by the controlled SBU approach and characterized by combined powder XRD, XPS, and FTIR methods. The interaction of CO molecules with Ru-MOF was studied by a novel instrumentation for ultra-high-vacuum (UHV) FTIR spectroscopy. The high-quality IR data demonstrate the presence of two different CO species within the framework: a strongly bonded CO showing a low-lying band at 2137 cm-1 and a second CO species at 2171 cm-1 with a lower binding energy. It was found that these IR bands cannot be assigned in a straightforward manner to CO molecules adsorbed on the coordinatively unsaturated RuII site (CUS) and RuIII site connected to an additional Cl- ion for charge compensation. The accurate DFT calculations reveal that the structural and electronic properties of the mixed-valence Ru-MOF are much more complex than expected. One of the Cl- counterions could be transferred to a neighboring paddle-wheel, forming an anionic SBU blocked by two Cl- counterions, whereas the other positively charged paddle-wheel with a Ru2II,III dimer exposes two "free" CUS, which can bind two CO molecules with different frequencies and binding energies.

AB - The mixed-valence metal-organic framework [Ru3 II,III(btc)2Cl1.5] (Ru-MOF) was synthesized by the controlled SBU approach and characterized by combined powder XRD, XPS, and FTIR methods. The interaction of CO molecules with Ru-MOF was studied by a novel instrumentation for ultra-high-vacuum (UHV) FTIR spectroscopy. The high-quality IR data demonstrate the presence of two different CO species within the framework: a strongly bonded CO showing a low-lying band at 2137 cm-1 and a second CO species at 2171 cm-1 with a lower binding energy. It was found that these IR bands cannot be assigned in a straightforward manner to CO molecules adsorbed on the coordinatively unsaturated RuII site (CUS) and RuIII site connected to an additional Cl- ion for charge compensation. The accurate DFT calculations reveal that the structural and electronic properties of the mixed-valence Ru-MOF are much more complex than expected. One of the Cl- counterions could be transferred to a neighboring paddle-wheel, forming an anionic SBU blocked by two Cl- counterions, whereas the other positively charged paddle-wheel with a Ru2II,III dimer exposes two "free" CUS, which can bind two CO molecules with different frequencies and binding energies.

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U2 - 10.1021/jp3056366

DO - 10.1021/jp3056366

M3 - Article

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SN - 1932-7447

VL - 117

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JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

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ER -

CO adsorption on a mixed-valence ruthenium metal-organic framework studied by UHV-FTIR spectroscopy and DFT calculations

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