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 the implementation of hydrogen production. The present work demonstrates
the potential to overcome these shortcomings through piezo-photocatalysis
of seawater using defective BaTiO3–x
(BTO) nanoparticles. This material was made piezoelectrically active
by a straightforward annealing process under different atmospheres,
including O2, N2, Ar, or H2, the
latter of which caused Ti4+ → Ti(4–x)+ multiple reductions and structural distortions
that stabilize piezoelectric tetragonal domains. A suite of experimental
techniques was employed to reveal the effects of reduction on the
energy band structure. A substantial piezoelectric effect and the
presence of self-polarization were confirmed by piezoresponse force
microscopy, while simulation work clarified the role of vibrations
on band bending deriving from the self-polarization. The hydrogen
evolution through photocatalysis, piezocatalysis, and piezo-photocatalysis
over the defective BaTiO3–x
nanoparticles
was characterized with deionized (DI) water, simulated seawater, and
natural seawater. A promising HER with a rate of 132.4 μmol/g/h
was achieved using DI water through piezo-photocatalysis without a
cocatalyst. In contrast, a substantial HER rate of 48.7 μmol/g/h
was obtained for natural seawater, despite the deleterious impact
of dissolved ions. The present work offers new perspectives for large-scale
green H2 production using abundant natural resources with
a conventional piezoelectric material that is readily available but
still affected by the ions dissolved in seawater.