Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy

Kortright, Jeffrey B.; Marti, Anne M.; Culp, Jeffrey T.; Venna, Surendar; Hopkinson, David

doi:10.1021/acs.jpcc.7b02623

Title: Active Response of Six-Coordinate Cu²⁺ on CO₂ Uptake in Cu(dpa)₂ SiF₆ - i from in Situ X-ray Absorption Spectroscopy

Abstract

Interpenetrated metal organic framework (MOF) Cu(dpa)₂SiF₆-i (dpa = dipyridyl acetylene) with 6-coordinate copper takes up CO₂ with isosteric heat of sorption Qst ≅ 40 kJ/mol, comparable to MOFs designed to have specific, strong chemisorption interactions. Although small pore size contributes to this high Qst, any preferred microscopic physisorption mechanisms were incompletely understood. We present in situ X-ray absorption spectroscopy results sensitive to local electronic structure around copper, fluorine, and nitrogen to look for signatures of CO₂ interaction with and near ionic species in Cu(dpa)₂SiF₆-i. No changes in F or N K edge spectra imply no structural or electronic distortions to SiF62– or dpa molecules on CO₂ uptake. Cu L_2,3 edge spectra confirm Cu²⁺ valence and show weak systematic CO₂-induced effects that result from distortions of the copper coordination shell. Finally, we suggest that electrostatic interaction between Cu²⁺ and axially aligned CO₂ quadrupole moments contributes to the large Qst.

Authors:

^[1]; Marti, Anne M. ^[2]; Culp, Jeffrey T. ^[3];

^[3]; Hopkinson, David ^[4]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); AECOM, Pittsburgh, PA (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)

Publication Date:: Wed May 10 00:00:00 EDT 2017

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1388917

Grant/Contract Number:: SC0001015; AC02-05CH11231; FE0004000

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 21; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats


                    Kortright, Jeffrey B., Marti, Anne M., Culp, Jeffrey T., Venna, Surendar, and Hopkinson, David. Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.jpcc.7b02623.

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                    Kortright, Jeffrey B., Marti, Anne M., Culp, Jeffrey T., Venna, Surendar, & Hopkinson, David. Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy.  United States.  https://doi.org/10.1021/acs.jpcc.7b02623

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                    Kortright, Jeffrey B., Marti, Anne M., Culp, Jeffrey T., Venna, Surendar, and Hopkinson, David. Wed .  
"Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy".  United States.  https://doi.org/10.1021/acs.jpcc.7b02623.  https://www.osti.gov/servlets/purl/1388917.

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@article{osti_1388917,

  title        = {Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy},

  author       = {Kortright, Jeffrey B. and Marti, Anne M. and Culp, Jeffrey T. and Venna, Surendar and Hopkinson, David},

  abstractNote = {Interpenetrated metal organic framework (MOF) Cu(dpa)2SiF6-i (dpa = dipyridyl acetylene) with 6-coordinate copper takes up CO2 with isosteric heat of sorption Qst ≅ 40 kJ/mol, comparable to MOFs designed to have specific, strong chemisorption interactions. Although small pore size contributes to this high Qst, any preferred microscopic physisorption mechanisms were incompletely understood. We present in situ X-ray absorption spectroscopy results sensitive to local electronic structure around copper, fluorine, and nitrogen to look for signatures of CO2 interaction with and near ionic species in Cu(dpa)2SiF6-i. No changes in F or N K edge spectra imply no structural or electronic distortions to SiF62– or dpa molecules on CO2 uptake. Cu L2,3 edge spectra confirm Cu2+ valence and show weak systematic CO2-induced effects that result from distortions of the copper coordination shell. Finally, we suggest that electrostatic interaction between Cu2+ and axially aligned CO2 quadrupole moments contributes to the large Qst.},

  doi          = {10.1021/acs.jpcc.7b02623},

  journal      = {Journal of Physical Chemistry. C},

  number       = 21,

  volume       = 121,

  place        = {United States},

  year         = {Wed May 10 00:00:00 EDT 2017},

  month        = {Wed May 10 00:00:00 EDT 2017}

}

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Works referencing / citing this record:

From IR to x-rays: gaining molecular level insights on metal-organic frameworks through spectroscopy
journal, August 2019

Hanna, Lauren; Lockard, Jenny V.
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Title: Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2 SiF6 - i from in Situ X-ray Absorption Spectroscopy

Abstract

Citation Formats

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Title: Active Response of Six-Coordinate Cu²⁺ on CO₂ Uptake in Cu(dpa)₂ SiF₆ - i from in Situ X-ray Absorption Spectroscopy

Porous materials with optimal adsorption thermodynamics and kinetics for CO₂ separation
journal, February 2013

Computational Studies of CO ₂ Sorption and Separation in an Ultramicroporous Metal–Organic Material
journal, August 2013

Theoretical Investigations of CO ₂ and H ₂ Sorption in an Interpenetrated Square-Pillared Metal–Organic Material
journal, May 2013

Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture
journal, June 2014

Hydrophobic pillared square grids for selective removal of CO ₂ from simulated flue gas
journal, January 2015

Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks
journal, January 2017

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites
journal, November 2009

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

Probing Adsorption Interactions in Metal–Organic Frameworks using X-ray Spectroscopy
journal, November 2013

Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
journal, March 2015

Gas cell for in situ soft X-ray transmission-absorption spectroscopy of materials
journal, July 2014

Studies of copper valence states with Cu $L_{3}$ x-ray-absorption spectroscopy
journal, January 1989

Evidence of Effective Potential Barriers in the X‐Ray Absorption Spectra of Molecules
journal, May 1972

Resonances in the K shell excitation spectra of benzene and pyridine: Gas phase, solid, and chemisorbed states
journal, December 1985

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journal, August 2019