Spatially Separated Redox Cocatalysts on Ferroelectric Nanoplates for Improved Piezophotocatalytic CO2 Reduction and H2O Oxidation.

Abstract

Utilizing solar and mechanical vibration energy for catalytic CO2 reduction and H2O oxidation is emerging as a promising way to simultaneously generate renewable energy and mitigate climate change, making it possible to integrate two energy resources into a reaction system for artificial piezophotosynthesis. However, the practical applications are hindered by undesirable charge recombination and sluggish surface reaction in the photocatalytic and piezocatalytic processes. This study proposes a dual cocatalyst strategy to overcome these obstacles and improve the piezophotocatalytic performance of ferroelectrics in overall redox reactions. With the photodeposition of AuCu reduction and MnOx oxidation cocatalysts on oppositely poled facets of PbTiO3 nanoplates, band bending occurs along with the formation of built-in electric fields on the semiconductor-cocatalyst interfaces, which, together with an intrinsic ferroelectric field, piezoelectric polarization field, and band tilting in the bulk of PbTiO3, provide strong driving forces for the directional drift of piezo- and photogenerated electrons and holes toward AuCu and MnOx, respectively. Besides, AuCu and MnOx enrich the active sites for surface reactions, significantly reducing the rate-determining barrier for CO2-to-CO and H2O-to-O2 transformation, respectively. Benefiting from these features, AuCu/PbTiO3/MnOx delivers remarkably improved charge separation efficiencies and significantly enhanced piezophotocatalytic activities in CO and O2 generation. This strategy opens a door for the better coupling of photocatalysis and piezocatalysis to promote the conversion of CO2 with H2O.