Nature of active surface centers of saponites of the Tashkiv deposit of Ukraine

Abstract

The paper discusses the results of saponite research from the Tashkiv deposit of Ukraine. X-ray structural analysis proved the necessity of preliminary cleaning of saponites from mineral impurities. The study of the morphology, nanoprofile and topography of the surface of saponite by the methods of SEM-microscopy and Atomic Force Microscopy revealed that the mineral is represented by aggregates of nano- and microparticles of a pyramidal shape. Its characteristic feature is the heterogeneity of isomorphic substitutions of ions in the tetrahedral and octahedral sheets of the structural elementary package. According to X-ray fluorescence analysis, saponite contains a significant amount of Fe3+, which isomorphically replaces magnesium Mg2+ and, accordingly, is located mastly in the octahedral sheet of the structural package with a charge from +0.37 to +0.35. The number and mechanism of isomorphic substitutions determine the presence of a total negative charge of the crystal lattice (from –0.38 to –0.3), the value of which ensures intensive interaction with water molecules of the interpacket space with the formation of surface OH groups. Accordingly, both acidic and alkaline Lewis and Brønsted centers are present on the surface with a predominance of acidic ones, so the acidity function is 5.82, and the point of zero proton charge is pH = 5.5. During dispersion in water, a part of the alkaline centers of the side surface are transformed into Brønsted acid centers as a result of their protonation, which causes an increase in the pH of the dispersion medium to pH = 8–8.6. Accordingly, the isoionic state is reached at pH = 7.5. The difference in pH values characterizing the isoionic state of the surface and the point of zero net proton charge (PZNPC) indicates the presence of weak acid-alkaline centers on the surface. The study of the adsorption of acid-alkaline dyes showed the adsorption of alkaline (pK = 1¸3) and acid (pK = 7¸14) dyes on saponites. The latter is significantly reduced due to the preliminary hydration of the solid surface - mainly the lateral edges of the particles. Acidic dyes are not adsorbed from a dispersion medium with pH < 5.5 (PZNPC), and basic dyes are adsorbed at pH > 5,5( PZNPC).