Relaxation processes of water confined to AIMCM-41 molecular sieves. Influence of the hydroxyl groups of the pore surface.
A series of AlMCM-41 molecular sieves was prepared with constant composition (Si/Al = 14.7) and presumably same pore structure but different pore diameters (from 2.3 to 4.6 nm). The pore size distribution is narrow for each sample. The rotational fluctuations of water molecules confined inside the pores were investigated applying broadband dielectric spectroscopy (10(-2)-10(7) Hz) over a large temperature interval (213-333 K). A relaxation process, slower than that expected for bulk water, was observed which is assigned to water molecules forming a surface layer on the pore walls. The estimated relaxation time has an unusual non-monotonic temperature dependence, which is rationalized and modeled assuming two competing processes: rotational fluctuations of constrained water molecules and defect formation (Ryabov model). This paper focuses on the defects and notably the influence of the hydroxyl groups of the pore walls. The Ryabov model is fitted to the data and characteristic parameters are obtained. Their dependence on pore diameter is considered for the first time. The found results are compared with those obtained for other types of molecular sieves and related materials.
Frunza
L
L
National Institute of Materials Physics, R-077125 Magurele, Romania. lfrunza@infim.ro
Schönhals
A
A
Kosslick
H
H
Frunza
S
S
D000327:Adsorption; D001703:Biophysics / Q000379:methods*; D004563:Electrochemistry / Q000379:methods; D008422:Materials Testing; D008958:Models, Molecular; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry; D049329:Nanostructures / Q000737:chemistry; D036103:Nanotechnology / Q000379:methods; D043942:Nanotubes / Q000737:chemistry; D016062:Porosity; D013499:Surface Properties; D013696:Temperature; D014867:Water / Q000737:chemistry*
D014867:Water