Exploring Structural Disorders in Aluminum-Containing Metal-Organic Frameworks: Comparison of Solid-State Al-27 NMR Powder Spectra to DFT Calculations on Bulk Periodic Structures

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F20%3A10422474" target="_blank" >RIV/00216208:11320/20:10422474 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=G91s.qsSJ0" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=G91s.qsSJ0</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcc.0c03000" target="_blank" >10.1021/acs.jpcc.0c03000</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Exploring Structural Disorders in Aluminum-Containing Metal-Organic Frameworks: Comparison of Solid-State Al-27 NMR Powder Spectra to DFT Calculations on Bulk Periodic Structures

Popis výsledku v původním jazyce

We use solid-state Al-27 NMR spectroscopy to test four aluminum-based metal-organic framework (MOF) materials-ICR-2, ICR-4, ICR-6, and ICR-7-against their structural models obtained from electron and X-ray diffraction. The lineshape MOF ICR analysis of the Al-27 NMR spectra reveals varying degrees of disorders in the Al coordination environment, depending on the NICIF ICR sample, which we were able to parameterize in terms of the extended Czjzek model (ECM) of the electric field gradient (EFG) distribution. The model&apos;s degree-of-disorder parameter epsilon was found to correlate inversely with the crystallite size of the MOFs. This suggests that the EFG distribution is related to a high surface-to-volume ratio of the particles and can be ascribed to the deviation of molecular arrangements near the surface from the bulk crystalline order. The ECM&apos;s parameters for a fixed part of the EFG tensor, a quadrupolar coupling constant C-Q,C-0 and asymmetry parameter eta(0), were compared to the EFG parameters calculated on fully periodic models using density functional theory (DFT). The DFT-calculated C-Q was found to exceed C-Q,C-0 by 25-60%, depending on the MOF. Although this result finds support in the literature, an explanation of such apparent spectral narrowing is still lacking.

Název v anglickém jazyce

Exploring Structural Disorders in Aluminum-Containing Metal-Organic Frameworks: Comparison of Solid-State Al-27 NMR Powder Spectra to DFT Calculations on Bulk Periodic Structures

Popis výsledku anglicky

We use solid-state Al-27 NMR spectroscopy to test four aluminum-based metal-organic framework (MOF) materials-ICR-2, ICR-4, ICR-6, and ICR-7-against their structural models obtained from electron and X-ray diffraction. The lineshape MOF ICR analysis of the Al-27 NMR spectra reveals varying degrees of disorders in the Al coordination environment, depending on the NICIF ICR sample, which we were able to parameterize in terms of the extended Czjzek model (ECM) of the electric field gradient (EFG) distribution. The model&apos;s degree-of-disorder parameter epsilon was found to correlate inversely with the crystallite size of the MOFs. This suggests that the EFG distribution is related to a high surface-to-volume ratio of the particles and can be ascribed to the deviation of molecular arrangements near the surface from the bulk crystalline order. The ECM&apos;s parameters for a fixed part of the EFG tensor, a quadrupolar coupling constant C-Q,C-0 and asymmetry parameter eta(0), were compared to the EFG parameters calculated on fully periodic models using density functional theory (DFT). The DFT-calculated C-Q was found to exceed C-Q,C-0 by 25-60%, depending on the MOF. Although this result finds support in the literature, an explanation of such apparent spectral narrowing is still lacking.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

—

Svazek periodika

124

Číslo periodika v rámci svazku

23

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

12569-12579

Kód UT WoS článku

000541745800043

EID výsledku v databázi Scopus

2-s2.0-85090044779