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Title: Uncovering the Local Magnesium Environment in the Metal–Organic Framework Mg 2 (dobpdc) Using 25 Mg NMR Spectroscopy

Abstract

The incorporation of N,N'-dimethylethylenediamine into an expanded MOF-74 framework has yielded a material (mmen-Mg2(dobpdc)) exhibiting “step-shaped” CO2 adsorption isotherms. The coordination of mmen at the Mg open metal center is essential for the unique cooperative adsorption mechanism elucidated for this material. Despite its importance for carbon capture, there is as yet no experimental structure determination available for the underlying metal– organic framework Mg2(dobpdc). Our 25Mg solid-state NMR data unravel the local Mg environments in several Mg2(dobpdc) samples, unambiguously confirming the formation of fivecoordinate Mg centers in the activated material and six-coordinate Mg centers in the solvent- or diamine-loaded samples, such as mmen-Mg2(dobpdc). A fraction of the Mg centers are locally disordered due to the framework deformation accompanied by the guest distributions and dynamics.

Authors:
ORCiD logo; ORCiD logo [1];  [2]; ; ORCiD logo; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1];  [4]
  1. Institute for Molecules and Materials, Radboud University, Heyendaalsweg 135, 6525 AJ Nijmegen, The Netherlands
  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States
  3. Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion, Switzerland
  4. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1406782
Report Number(s):
PNNL-SA-128407
Journal ID: ISSN 1932-7447; 47804; 48697; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 121; Journal Issue: 36
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Environmental Molecular Sciences Laboratory

Citation Formats

Xu, Jun, Blaakmeer, E. S. Merijn, Lipton, Andrew S., McDonald, Thomas M., Liu, Yifei Michelle, Smit, Berend, Long, Jeffrey R., Kentgens, Arno P. M., and Reimer, Jeffrey A. Uncovering the Local Magnesium Environment in the Metal–Organic Framework Mg 2 (dobpdc) Using 25 Mg NMR Spectroscopy. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b07809.
Xu, Jun, Blaakmeer, E. S. Merijn, Lipton, Andrew S., McDonald, Thomas M., Liu, Yifei Michelle, Smit, Berend, Long, Jeffrey R., Kentgens, Arno P. M., & Reimer, Jeffrey A. Uncovering the Local Magnesium Environment in the Metal–Organic Framework Mg 2 (dobpdc) Using 25 Mg NMR Spectroscopy. United States. doi:10.1021/acs.jpcc.7b07809.
Xu, Jun, Blaakmeer, E. S. Merijn, Lipton, Andrew S., McDonald, Thomas M., Liu, Yifei Michelle, Smit, Berend, Long, Jeffrey R., Kentgens, Arno P. M., and Reimer, Jeffrey A. 2017. "Uncovering the Local Magnesium Environment in the Metal–Organic Framework Mg 2 (dobpdc) Using 25 Mg NMR Spectroscopy". United States. doi:10.1021/acs.jpcc.7b07809.
@article{osti_1406782,
title = {Uncovering the Local Magnesium Environment in the Metal–Organic Framework Mg 2 (dobpdc) Using 25 Mg NMR Spectroscopy},
author = {Xu, Jun and Blaakmeer, E. S. Merijn and Lipton, Andrew S. and McDonald, Thomas M. and Liu, Yifei Michelle and Smit, Berend and Long, Jeffrey R. and Kentgens, Arno P. M. and Reimer, Jeffrey A.},
abstractNote = {The incorporation of N,N'-dimethylethylenediamine into an expanded MOF-74 framework has yielded a material (mmen-Mg2(dobpdc)) exhibiting “step-shaped” CO2 adsorption isotherms. The coordination of mmen at the Mg open metal center is essential for the unique cooperative adsorption mechanism elucidated for this material. Despite its importance for carbon capture, there is as yet no experimental structure determination available for the underlying metal– organic framework Mg2(dobpdc). Our 25Mg solid-state NMR data unravel the local Mg environments in several Mg2(dobpdc) samples, unambiguously confirming the formation of fivecoordinate Mg centers in the activated material and six-coordinate Mg centers in the solvent- or diamine-loaded samples, such as mmen-Mg2(dobpdc). A fraction of the Mg centers are locally disordered due to the framework deformation accompanied by the guest distributions and dynamics.},
doi = {10.1021/acs.jpcc.7b07809},
journal = {Journal of Physical Chemistry. C},
number = 36,
volume = 121,
place = {United States},
year = 2017,
month = 9
}