Photocatalytic
H2 evolution and organic pollutant oxidation
have witnessed a radical surge in recent times. However, this integration
demands spatial charge separation and unique interface properties
for a trade-off between oxidation and reduction reactions. In the
current work, defect engineering of NiO/SnO2 nanoparticles
aided in altering the optoelectronics and interface properties and
enhanced photocatalytic activity. After annealing the catalysts in
a N2 atmosphere, the hydroxyl groups were replaced by water
molecules through surface modification. The photoexcited holes accumulated
on SnO2 break the water molecules and facilitate the reduction
of protons on NiO; this is known as spatial separation. Meanwhile,
direct hole oxidation, an oxygen reduction reaction, ensures the degradation
activity in this 2-fold system. By defect engineering, the limitations
of SnO2 such as higher H2O adsorption, wide
bandgap (reduced from 3.02 to 1.88 eV), and electronic properties
were addressed. The H2 production in the current work has
attained a value of 3732 μmol/(g h), which is 2.9 times that
of the previous best reported under sunlight. Recyclability tests
confirmed the stability of vacancies by promoting the reoxidation
of defect states during photocatalytic activity. Additionally, efforts
were made to study the effect of defect density on the photocurrent,
the electrical resistance, and the mechanism of photocatalytic reactions.
Electrochemical characterizations, UPS, XPS, UV-DRS, and PL were employed
to understand the influence of defects on the bandgap, charge recombination,
charge transport, charge carrier lifetime, and the interface properties
that are responsible for photocatalytic activity. In this regard,
it was understood that maintaining the optimal defect concentration
is important for higher photocatalytic efficiencies, as the defect
optimality preserves key photocatalytic properties. Apart from characterizations,
the photocatalytic results suggest that excess defect density triggers
the undesired thermodynamically favored back reactions, which greatly
hampered the H2 yield of the process.