Piezocatalytic reactions are generally excited by ultrasonication
and, as such, should occur simultaneously with other catalytic reactions
caused by different mechanisms such as sonocatalysis or tribocatalysis.
One of the main challenges is how to discriminate between these effects
in a catalysis experiment and quantify each contribution. In order
to distinguish these effects, we use nano- and micro-particles of
piezoelectric barium titanate (BaTiO3) and then compare
their catalytic properties below and close to the piezoelectric to
non-piezoelectric phase transition temperature at which the crystalline
structure changes from the low-temperature tetragonal, piezoelectric
phase to the higher-temperature cubic, non-piezoelectric phase. All
other parameters, such as particle size, surface termination, etc.,
remain unaltered. The phase transition in bulk occurs at about 120
°C, but the transition temperature decreases as a function of
particle size and reaches room temperature for particle sizes of about
20 nm. Transmission electron microscopy and X-ray diffraction were
used to characterize the morphology and crystalline phase of the nanoparticles,
respectively. Since the piezoelectric properties and the lattice dynamics
are closely related, temperature-dependent Raman spectroscopy provides
an even better insight into the nano- and micro-structural properties,
allowing the ferroelectric phase transition temperature to be estimated.
The catalytic activities of the BaTiO3 nanoparticles were
determined by monitoring the optical absorption of a solution containing
the model pollutant methyl orange, after ultrasonication of the solution
to which were added the dispersed piezoelectric BaTiO3 particles
as catalysts. An exponential-like correlation has been found between
the catalytic reaction rates and the tetragonal distortion of the
crystal structure of the BaTiO3 particles. Our study has
also established that while 10% of the catalytic reaction of BaTiO3 is related to either sonocatalysis or tribocatalysis, the
remaining 90% of the overall catalytic activity is ascribed to the
piezocatalytic contribution.