Ternary BaCaZrTi perovskite oxide piezocatalysts dancing for efficient hydrogen peroxide generation

Piezocatalysis is capable of converting mechanical vibrations into chemical energy, portraying a promising alternative technology for hydrogen peroxide (H2O2) production. Environmentally benign lead-free barium titanate piezocatalyst has received particular attention due to its ferroelectric property. However, the reported H2O2 yield is not ideal and one of the reasons is the undesirable piezoelectricity. Herein, a series of lead-free perovskite oxides consisting of (1-x)Ba(Zr0.2Ti0.8)O-3-x(Ba0.7Ca0.3)TiO3 solid solutions are developed for H2O2 production by introducing more favorable crystal phases to increase the piezoelectricity. The prepared perovskite oxides were characterized by significantly enhanced piezoeletricities owing to the coexistence of the ternary (orthorhombic, tetragonal and rhombohedral) phases with reduced energy barrier for polarization rotation. Benefiting from the notably improved piezoelectric property and appropriate oxygen vacancy concentration, the optimal composition of 0.5Ba(Zr0.2Ti0.8)O-3-0.5(Ba0.7Ca0.3)TiO3 exhibits an outstanding H2O2 selective generation and long-lasting stability. Under ultrasonic irradiation, a superior H2O2 yield of 692 mu mol g-1 h-1 with a selectivity of 80% was attained, showing the enhancement by the factors of 3.3, 4.1 and 8.7 compared to Ba0.7Ca0.3TiO3, BaZr0.2Ti0.8O3 and BaTiO3, respectively. Furthermore, the catalyst is highly stable by delivering a H2O2 productivity of 3313 mu mol g(-1) in 14 h of piezocatalysis. Mechanism study suggests that H2O2 generation stems from an efficient O-2 reduction via a two-electron transfer pathway, during which the piezopotential is of primary importance to provide driving force for the carrier separation and transportation. Moreover, the green and non-toxic piezocatalysis system based on the BaCaZrTi solid solutions can be applied for efficient water disinfection. This study offers guidance towards the rational design of lead-free piezocatalyst and reaction system for H2O2 generation and its application.

Automated summary

Piezocatalysis has the potential to convert mechanical vibrations into chemical energy for hydrogen peroxide (H2O2) production. This study developed lead-free perovskite oxide catalysts to enhance the piezoelectric property and achieved an outstanding H2O2 yield and long-term stability. The catalyst also showed promise for efficient water disinfection.