Photocatalysis
is a perennial solution that promises to resolve
deep-rooted challenges related to environmental pollution and energy
deficit through harvesting the inexhaustible and renewable solar energy.
To date, a cornucopia of photocatalytic materials has been investigated
with the research wave presently steered by the development of novel,
affordable, and effective metal-free semiconductors with fascinating
physicochemical and semiconducting characteristics. Coincidentally,
the recently emerged red phosphorus (RP) semiconductor finds itself
fitting perfectly into this category ascribed to its earth abundant,
low-cost, and metal-free nature. More notably, the renowned red allotrope
of the phosphorus family is spectacularly bestowed with strengthened
optical absorption features, propitious electronic band configuration,
and ease of functionalization and modification as well as high stability.
Comprehensively detailing RP’s roles and implications in photocatalysis,
this review article will first include information on different RP
allotropes and their chemical structures, followed by the meticulous
scrutiny of their physicochemical and semiconducting properties such
as electronic band structure, optical absorption features, and charge
carrier dynamics. Besides that, state-of-the-art synthesis strategies
for developing various RP allotropes and RP-based photocatalytic systems
will also be outlined. In addition, modification or functionalization
of RP with other semiconductors for promoting effective photocatalytic
applications will be discussed to assess its versatility and feasibility
as a high-performing photocatalytic system. Lastly, the challenges
facing RP photocatalysts and future research directions will be included
to propel the feasible development of RP-based systems with considerably
augmented photocatalytic efficiency. This review article aspires to
facilitate the rational development of multifunctional RP-based photocatalytic
systems by widening the cognizance of rational engineering as well
as to fine-tune the electronic, optical, and charge carrier properties
of RP.
ZnIn2S4 (ZIS) is an efficient photocatalyst for solar hydrogen (H2) generation from water splitting owing to its suitable band gap, excellent photocatalytic behaviour and high stability. Nevertheless, modifications are still necessary to further enhance the photocatalytic performance of ZIS for practical applications. This has led to our interest in exploring phosphorus doping on ZIS for photocatalytic water splitting, which has not been studied till date. Herein, phosphorus-doped ZnIn2S4 (P-ZIS) was modelled via Density Functional Theory to investigate the effects of doping phosphorus on the structural and electronics properties of ZIS as well as its performance toward photocatalytic water splitting. This work revealed that the replacement of S3 atom by substitutional phosphorus gave rise to the most stable P-ZIS structure. In addition, P-ZIS was observed to experience a reduction in band gap energy, an upshift of valence band maximum (VBM), an increase in electron density near VBM and a reduction of H* adsorption–desorption barrier, all of which are essential for the enhancement of the hydrogen evolution reaction. In overall, detailed theoretical analysis carried out in this work could provide critical insights towards the development of P-ZIS-based photocatalysts for efficient H2 generation via solar water splitting.
Photocatalytic reduction of CO 2 has attracted enormous interest as a sustainable and renewable source of energy. In the past decade, numerous bulk-type semiconductors have been developed, but the existing designs suffer many limitations, namely rapid recombination of charge carriers and weak light absorption ability. Herein, a bottom-up approach was developed to design atomically thin sulfur-doped Bi 2 WO 6 perovskite nanosheets (S-BWO) with improved reduction ability, extended visible light absorption, prolonged lifetime of charge carriers, enhanced adsorption of CO 2 , and reduced work function. Compared with pristine Bi 2 WO 6 (P-BWO), S-BWO nanosheets exhibited a 3-fold improvement in photocatalytic reduction of CO 2 under simulated sunlight irradiation. Experimental studies and density functional theory calculations revealed the synergistic roles of atomically thin nanosheets and S atoms in promoting photocatalytic efficiency.
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