Oxygen vacancy (OV)-enriched black TiO2 (BTO)
is a promising material for supporting well-studied noble metals in
the hydrogen evolution reaction (HER). Blackening TiO2 by
incorporating OVs substantially changes the electronic
state of BTO and enhances HER catalytic performance compared to pristine
TiO2. Furthermore, the incorporation of vacancies leads
to deviation from a single anatase phase on a localized scale and
creates a heterojunction by promoting the occurrence of localized
rutile segments. Hence, synthesizing biphasic (rutile and anatase)
BTO with abundant OVs and optimized Pt-metallic clusters
substantially improves the electrochemical HER kinetics, though it
demands a complicated multistep synthesis. Conversely, herein, a solvent-free,
single-pot green synthesis route is corroborated using a pulse laser
irradiation technique to achieve the desired Ov-enriched
BTO structure. Controlled irradiation of anatase TiO2 with
a Pt precursor under optimized parameters in an air environment creates
OVs and decorates the metal oxide with Pt nanoclusters.
This defect formation decreases the activation energy of BTO, favoring
the anatase phase and forming a localized rutile phase, which enhances
HER activity through localized heterojunctions. The combined impacts
of Pt nanoclusters and OVs revealed an outstanding specimen
achieving a HER overpotential of 169 mV at 10 mA/cm2 and
a Tafel slope of 73.3 mV/dec Importantly, long-term stability during
overall water splitting was further achieved. This approach offers
valuable perceptions into designing highly competent catalysts and
their supporting structures for various energy-associated solicitations.