Part I: determination of a structure/property transformation mechanism responsible for changes in the point of zero change of anatase titania with decreasing particle size

Abstract

Below a diameter of approximately 28 nm, the surface crystal structure of anatase titania is known to change. These changes include surface bond lengths and crystal lattice parameter expansion/contractions. Concurrent with these structure changes, the materials point of zero charge (PZC) has been observed to shift toward lower pH values. Therefore, the objective of this work was to determine if a correlation exists between these known structural changes and the shift in the materials PZC values with decreasing particle size. To achieve this a method was developed to identify and minimize the effect of all known variables, save particle size, affecting the materials pH_PZC. This led to the discovery of two regions for point of zero charge. Above the average spherical primary particle diameter ≅ 29 nm for anatase titania, denoted as Region I, PZC values remain constant. In Region I the materials surface crystal structure and properties were also found to remain constant. Below the average spherical primary particle diameter ≅29 nm is the second zone, defined as Region II, where pH_PZC values decrease almost linearly. An examination of possible surface structure factors and properties responsible for the shift in these PZC values (Region II) identified three underlying causes. These being changes in the materials band gap (i.e. surface bond lengths), lattice parameters and bond ionic content.