Are hydrogen supramolecular structures being suppressed upon nanoscale confinement? The case of monohydroxy alcohols

Agnieszka Talik; Magdalena Tarnacka; Monika Geppert-Rybczyńska; Barbara Hachuła; Roksana Bernat; Agnieszka Chrzanowska; Kamil Kaminski; Marian Paluch

doi:10.1016/j.jcis.2020.04.084

Are hydrogen supramolecular structures being suppressed upon nanoscale confinement? The case of monohydroxy alcohols

J Colloid Interface Sci. 2020 Sep 15:576:217-229. doi: 10.1016/j.jcis.2020.04.084. Epub 2020 May 4.

Authors

Agnieszka Talik¹, Magdalena Tarnacka², Monika Geppert-Rybczyńska³, Barbara Hachuła³, Roksana Bernat³, Agnieszka Chrzanowska⁴, Kamil Kaminski⁵, Marian Paluch²

Affiliations

¹ Institute of Physics, University of Silesia in Katowice, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland; Silesian Center of Education and Interdisciplinary Research, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland. Electronic address: agnieszka.talik@smcebi.edu.pl.
² Institute of Physics, University of Silesia in Katowice, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland; Silesian Center of Education and Interdisciplinary Research, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland.
³ Institute of Chemistry, University of Silesia in Katowice, Szkolna 9, 40-006 Katowice, Poland.
⁴ Department of Physical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, M. Curie-Sklodowska Sq. 3, 20-031, Lublin, Poland.
⁵ Institute of Physics, University of Silesia in Katowice, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland; Silesian Center of Education and Interdisciplinary Research, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland. Electronic address: kamil.kaminski@us.edu.pl.

PMID: 32417683
DOI: 10.1016/j.jcis.2020.04.084

Abstract

In this paper, the molecular dynamics, H-bonding pattern and wettability of the primary and secondary monohydroxyalcohols, 2-ethyl-1-hexanol (2E1H), 2-ethyl-1-butanol (2E1B) and 5-methyl-3-heptanol (5M3H) infiltrated into native and functionalized silica and alumina pores having pore diameters, d = 4 nm and d = 10 nm, have been studied with the use of Broadband Dielectric (BDS) and Fourier Transform InfraRed (FTIR) spectroscopies, as well as contact angle measurements. We found significant differences in the behavior of alcohols forming chain- (2E1H, 2E1B) or micelle-like (5M3H) supramolecular structures despite of their similarities in the wettability and interfacial energy. It turned out that nanoassociates as well as H-bonds are more or less affected by the confinement dependently on the chemical structure and alcohol order. Moreover, a peculiar behavior of the self-assemblies at the interface was noted in the latter material (5M3H). Finally, it was found that irrespectively to the sample, type of pores, functionalization, the temperature evolution of Debye relaxation times, τ_D, of the confined systems deviates from the bulk behavior always at similar τ_D due to vitrification of the interfacial layer. This finding is a clear indication that unexpectedly dynamics (mobility) of the supramolecular structures close to the hydrophilic and hydrophobic surfaces is similar in each system.

Keywords: Confinement; Dielectric spectroscopy; Hydrogen bonds; Infrared spectroscopy; Interfacial energy; Monohydroxy alcohols; Self-assembly; Surface effects; Surface tension.