TY - JOUR
T1 - Correlating vibrational properties with temperature and pressure dependent CO2 adsorption in zeolitic imidazolate frameworks
AU - Kontos, Athanassios G.
AU - Romanos, George Em
AU - Veziri, Charitomeni M.
AU - Gotzias, Anastasios
AU - Arfanis, Michalis K.
AU - Kouvelos, Evangelos
AU - Likodimos, Vlassis
AU - Karanikolos, Georgios N.
AU - Falaras, Polycarpos
N1 - Funding Information:
We acknowledge support of this work by the project MIS 5002567, implemented under the “Action for the Strategic Development on the Research and Technological Sector”, funded by the Operational Programme “ Competitiveness, Entrepreneurship and Innovation ” (NSRF 2014-2020) and co-financed by Greece and the European Union ( European Regional Development Fund ). GNK acknowledges support by Khalifa University, United Arab Emirates (Award No. RC2-2019-007). We thank N. Moustakas for assistance in the angle-dependent Raman experiments and Y.S. Raptis for helpful discussions.
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/11/1
Y1 - 2020/11/1
N2 - Zeolitic imidazolate frameworks (ZIFs) feature a rigid porous structure where the interplay of pore merits and wall functionality, determined by the different imidazolate functional groups, results in superior CO2 capture ability. In this work, the vibrational properties of ZIF-68 and ZIF-69, two characteristic complex gmelinite (GME) type ZIFs comprising of benzimidazolate (bIm) and chloro-benzimidazolate (cbIm) linkers, respectively, were investigated by micro-Raman spectroscopy as a function of CO2 pressure and temperature, in combination with macroscopic adsorption experiments and extended molecular simulations, in order to explore the underlying host-guest interactions and particularly the variation of the framework lattice dynamics and flexibility to CO2 loading. The CO2 isosteric heat of adsorption (Qst) was quantitatively determined by the temperature dependence of the CO2 Fermi dyad intensity at constant pressure. ZIF-69 was consistently found to present higher Qst than ZIF-68 due to the cbIm polar functionality, in close agreement with macroscopic CO2 adsorption experiments and Monte Carlo analysis. More importantly, high CO2 uptake was found to cause significant blue shifts and enhancement of the frequency shift temperature gradients of several low-frequency Raman modes, which according to detailed polarization analysis of ZIF microcrystals, arise from free breathing vibrations of the functionalized ligands in the large ZIF pores. Low-frequency micro-Raman spectroscopy may accordingly constitute a sensitive spectroscopic tool for unveiling lattice dynamics upon CO2 sorption in ZIFs.
AB - Zeolitic imidazolate frameworks (ZIFs) feature a rigid porous structure where the interplay of pore merits and wall functionality, determined by the different imidazolate functional groups, results in superior CO2 capture ability. In this work, the vibrational properties of ZIF-68 and ZIF-69, two characteristic complex gmelinite (GME) type ZIFs comprising of benzimidazolate (bIm) and chloro-benzimidazolate (cbIm) linkers, respectively, were investigated by micro-Raman spectroscopy as a function of CO2 pressure and temperature, in combination with macroscopic adsorption experiments and extended molecular simulations, in order to explore the underlying host-guest interactions and particularly the variation of the framework lattice dynamics and flexibility to CO2 loading. The CO2 isosteric heat of adsorption (Qst) was quantitatively determined by the temperature dependence of the CO2 Fermi dyad intensity at constant pressure. ZIF-69 was consistently found to present higher Qst than ZIF-68 due to the cbIm polar functionality, in close agreement with macroscopic CO2 adsorption experiments and Monte Carlo analysis. More importantly, high CO2 uptake was found to cause significant blue shifts and enhancement of the frequency shift temperature gradients of several low-frequency Raman modes, which according to detailed polarization analysis of ZIF microcrystals, arise from free breathing vibrations of the functionalized ligands in the large ZIF pores. Low-frequency micro-Raman spectroscopy may accordingly constitute a sensitive spectroscopic tool for unveiling lattice dynamics upon CO2 sorption in ZIFs.
KW - Breathing vibrations
KW - Carbon dioxide
KW - Gas adsorption
KW - Raman scattering
KW - Simulations
UR - http://www.scopus.com/inward/record.url?scp=85087280650&partnerID=8YFLogxK
U2 - 10.1016/j.apsusc.2020.147058
DO - 10.1016/j.apsusc.2020.147058
M3 - Article
AN - SCOPUS:85087280650
SN - 0169-4332
VL - 529
JO - Applied Surface Science
JF - Applied Surface Science
M1 - 147058
ER -