Probing Gas Adsorption in Metal–Organic Framework ZIF-8 by EPR of Embedded Nitroxides | Sciact - CRIS-system of Boreskov Institute of Catalysis

Probing Gas Adsorption in Metal–Organic Framework ZIF-8 by EPR of Embedded Nitroxides Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2017, Volume: 121, Number: 36, Pages: 19880-19886 Pages count : 7 DOI: 10.1021/acs.jpcc.7b06884

Tags

ELECTRON-PARAMAGNETIC-RESONANCE; CARBON-DIOXIDE; FORCE-FIELD; MOLECULAR-DYNAMICS; IMIDAZOLATE; CO2; MEMBRANES; HYDROGEN; H-2; SELECTIVITY

Authors

Sheveleva A.M. ^1,2 , Anikeenko A.V. ^2,3 , Poryvaev A.S. ^1,2 , Kuzmina D.L. ^1,2 , Shundrina I.K. ⁴ , Kolokolov D.I. ^2,5 , Stepanov A.G. ^2,5 , Fedin M.V. ^1,2

Affiliations

1	International Tomography Center SB RAS, 630090, Novosibirsk, Russia
2	Novosibirsk State University, 630090, Novosibirsk, Russia
3	Voevodsky Institute of Chemical Kinetics and Combustion, 630090, Novosibirsk, Russia
4	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 630090, Novosibirsk, Russia
5	Boreskov Institute of Catalysis SB RAS, Lavrentiev av. 5, 630090, Novosibirsk, Russia

Funding (3)

1	Russian Science Foundation	14-13-00826
2	Federal Agency for Scientific Organizations	V.44.1.8. (0333-2016-0001)
3	The Ministry of Education and Science of the Russian Federation	МК-3272.2017.3

Metal–organic frameworks (MOFs) are being increasingly considered as promising materials for gas separation and storage, yet specific interactions between gas molecules and the inner surface of pores are still not well understood. In this work, we propose a new approach for investigation of such interactions by Electron Paramagnetic Resonance (EPR). We use stable nitroxide radicals as multifunctional agents embedded into the pores of a MOF prior to the gas sorption. They act as EPR-active reporters, and simultaneously as competitor molecules during the gas adsorption process. We exemplify this approach using a ZIF-8 framework, nitroxide TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl), and CO2, N2, and O2 gases. The mobility of nitroxide monitored by continuous wave EPR behaves differently upon adsorption of each of these gases. In particular, a noticeable increase of mobility in the presence of CO2 reveals the weakening of guest–host interactions TEMPO–MOF induced by CO2, which was qualitatively supported by molecular dynamic calculations. The nitroxides can be embedded in MOFs postsynthetically, and their negligible amounts (≤1 per 1000 cells) are required due to a high sensitivity of EPR. Therefore, the proposed approach is sufficiently versatile and might find broad applications for various MOFs.

Sheveleva A.M. , Anikeenko A.V. , Poryvaev A.S. , Kuzmina D.L. , Shundrina I.K. , Kolokolov D.I. , Stepanov A.G. , Fedin M.V.
Probing Gas Adsorption in Metal–Organic Framework ZIF-8 by EPR of Embedded Nitroxides
The Journal of Physical Chemistry C. 2017. V.121. N36. P.19880-19886. DOI: 10.1021/acs.jpcc.7b06884 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Jul 13, 2017
Accepted:	Aug 18, 2017
Published online:	Sep 5, 2017
Published print:	Sep 14, 2017

Web of science:	WOS:000411171800035
Scopus:	2-s2.0-85029536713
Elibrary:	31062685
Chemical Abstracts:	2017:1364264
OpenAlex:	W2747747429

DB	Citing
Web of science	18
Scopus	19
Elibrary	20
OpenAlex	18