Role of Bi3+ ion substitution on the piezocatalytic degradation performance of lead-free BaTi0.89Sn0.11O3 at low vibrational energy
Harnessing low ultrasonic vibration energy to drive piezocatalytic reactions has attracted increasing attention in response to current environmental and energy challenges. In this study, we investigate the effect of heterovalent bismuth doping on the piezocatalytic degradation of Rhodamine B (RhB) under low-power ultrasonic excitation. Bismuth ions (Bi$^{3+}$) were substituted into the lead-free ferroelectric BaTi${0.89}$Sn${0.11}$O$_3$, yielding BTSn11-xBi with x = 0, 0.02, and 0.04. The powders were synthesized by the sol-gel method as submicron cubes. The structural, morphological, optical, and piezocatalytic properties were strongly influenced by the Bi content. Compared with pristine BTSn11 and BTSn11-0.04Bi, the BTSn11-0.02Bi sample exhibited the lowest band gap (3.22 eV), the smallest particle size (283 nm), the highest piezoelectric current (approximately 8 microA cm$^{-2}$), and the lowest coercive field required to obtain piezoresponse force microscopy hysteresis loops. As a result, BTSn11-0.02Bi showed the highest RhB degradation efficiency and the largest apparent kinetic rate constant, confirming its superior piezocatalytic performance. Total organic carbon measurements revealed significant mineralization of RhB. In addition, BTSn11-0.02Bi demonstrated good reusability and stability, maintaining high degradation efficiency over three consecutive cycles. These results highlight the potential of Bi-doped BTSn11 ferroelectric materials, particularly BTSn11-0.02Bi, as efficient piezocatalysts for environmental remediation.