Direct Hydrogen Production from Water/Seawater by Irradiation/Vibration-Activated Using Defective Ferroelectric BaTiO3-x Nanoparticles

Hydrogen is a promising fossil-fuel alternative fuel owing to its environmentally neutral emissions and high energy density. However, the need for purified water and external power are critical hindrances to implementation of hydrogen production. The present work reveals the potential to overcome these shortcomings through piezo-photocatalysis of seawater using BaTiO3-x (BTO) nanoparticles. This material was made piezoelectrically active by annealing under different atmospheres, including O2, N2, Ar, and H2, the latter of which caused Ti4+ to Ti(4-x)+ multiple reductions and structural expansions that stabilized piezoelectric tetragonal BTO domains. The resultant defect equilibria combine ionic and electron effects, including Ti redox reactions, charge-compensating surface oxygen vacancy formation, and color centre alterations. Further, variety of experimental techniques revealed the effects of reduction on the energy band structure. A strong piezoelectric effect and the presence of self-polarization were confirmed by piezoresponse force microscopy, while simulation work clarified the role of vibration on band bending deriving from the former. The performance data contrasted H2 evolution using deionized (DI) water, simulated seawater, and natural seawater subjected to photocatalysis, piezocatalysis, and piezo-photocatalysis. An efficient H2 evolution rate of 132.4 micromol/g/h was achieved from DI water using piezo-photocatalysis for 5 h. In contrast, piezocatalysis for 2 h followed by piezo-photocatalysis for 3 h resulted in H2 evolution rates of 100.7 micromol/g/h for DI water, 63.4 micromol/g/h for simulated seawater, and 48.7 micromol/g/h for natural seawater. This work provides potential new strategies for large-scale green H2 production using abundant natural resources with conventional piezoelectric material while leveraging the effects of ions dissolved in seawater.