As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4, (2) modification strategies of g-C3N4, (3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories: (1) Type I heterojunction, (2) Type II heterojunction, (3) p-n heterojunction, (4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.
The preparation of noble metal-semiconductor hybrid nanocrystals with controlled morphologies has received intensive interest in recent years. In this study, facile one-pot reactions have been developed for the synthesis of Au-ZnO hybrid nanocrystals with different interesting morphologies, including petal-like and urchin-like nanoflowers, nanomultipods and nanopyramids. In the synthesis strategy, oleylamine-containing solution serves as the reaction medium, and the in situ generated Au seeds play an important role in the subsequently induced growth of ZnO nanocrystals. With the aid of several surfactants, hybrid nanocrystals with different morphologies that have considerable influences on their optical and photocatalytic activities are readily achieved. Through high-resolution transmission electron microscopy measurements, an observed common orientation relationship between ZnO and Au is that ZnO nanocrystals prefer to grow with their polar {001} facets on the {111} facets of Au nanocrystals, and well-defined interfaces are evident. Surface plasmon resonance bands of Au with different positions are observed in the UV-vis spectra, and the UV and visible emissions of ZnO are found to be dramatically reduced. Finally, the as-prepared Au-ZnO nanocrystals exhibit excellent photocatalytic activity for the photodegradation of rhodamine B compared with pure ZnO nanocrystals. The Au-ZnO hybrid nanopyramids show the highest catalytic efficiency, which is correlated with the exposed crystal facets, crystallinity and the formation of hybrid nanostructures. The as-prepared Au-ZnO hybrid nanocrystals are expected to find diverse potential applications in the fields such as photocatalysis, solar energy conversion, sensing and biological detection.
Sub-5 nm ultra-fine iron phosphide
(FeP) nano-dots-modified porous graphitic carbon nitride (g-C3N4) heterojunction nanostructures are successfully
prepared through the gas-phase phosphorization of Fe3O4/g-C3N4 nanocomposites. The incorporation
of zero-dimensional (0D) ultra-small FeP nanodots co-catalysts not
only effectively facilitate charge separation but also serve as reaction
active sites for hydrogen (H2) evolution. Herein, the strongly
coupled FeP/g-C3N4 hybrid systems are employed
as precious-metal-free photocatalysts for H2 production
under visible-light irradiation. The optimized FeP/g-C3N4 sample displays a maximum H2 evolution rate
of 177.9 μmol h–1 g–1 with
the apparent quantum yield of 1.57% at 420 nm. Furthermore, the mechanism
of photocatalytic H2 evolution using 0D/2D FeP/g-C3N4 heterojunction interfaces is systematically
corroborated by steady-state photoluminescence (PL), time-resolved
PL spectroscopy, and photoelectrochemical results. Additionally, an
increased donor density in FeP/g-C3N4 is evidenced
from the Mott–Schottky analysis in comparison with that of
parent g-C3N4, signifying the enhancement of
electrical conductivity and charge transport owing to the emerging
role of FeP. The density functional theory calculations reveal that
the FeP/g-C3N4 hybrids could act as a promising
catalyst for the H2 evolution reaction. Overall, this work
not only paves a new path in the engineering of monodispersed FeP-decorated
g-C3N4 0D/2D robust nanoarchitectures but also
elucidates potential insights for the utilization of noble-metal-free
FeP nanodots as remarkable co-catalysts for superior photocatalytic
H2 evolution.
Colloidally synthesized Ni12P5 nanoparticles were embedded into g-C3N4 nanosheets via a solution-phase approach. The Ni12P5/g-C3N4 photocatalysts manifested significantly improved noble-metal-free H2 evolution.
Herein, we introduce a facile electrostatic attraction approach to produce zinc-silver citrate hollow microspheres, followed by thermal heating treatment in argon to ingeniously synthesize sandwich-like Ag-C@ZnO-C@Ag-C hybrid hollow microspheres. The 3D carbon conductive framework in the hybrids derives from the in situ carbonation of carboxylate acid groups in zinc-silver citrate hollow microspheres during heating treatment, and the continuous and homogeneous Ag nanoparticles on the outer and inner surfaces of hybrid hollow microspheres endow the shells with the sandwiched configuration (Ag-C@ZnO-C@Ag-C). When applied as the anode materials for lithium ion batteries, the fabricated hybrid hollow microspheres with sandwich-like shells reveal a very large reversible capacity of 1670 mAh g(-1) after 200 cycles at a current density of 0.2 A g(-1). Even at the very large current densities of 1.6 and 10.0 A g(-1), the high specific capacities of about 1063 and 526 mAh g(-1) can be retained, respectively. The greatly enhanced electrochemical properties of Ag-C@ZnO-C@Ag-C hybrid microspheres are attributed to their special structural features such as the hollow structures, the sandwich-like shells, and the nanometer-sized building blocks.
A highly efficient visible-light-driven photocatalyst is urgently necessary for photocatalytic hydrogen generation through water splitting. Herein, ZnIn S hierarchical architectures assembled as ultrathin nanosheets were synthesized by a facile one-pot polyol approach. Subsequently, the two-dimensional-network-like MoSe was successfully hybridized with ZnIn S by taking advantage of their analogous intrinsic layered morphologies. The noble-metal-free ZnIn S /MoSe heterostructures show enhanced photocatalytic H evolution compared to pure ZnIn S . It is noteworthy that the optimum nanocomposite of ZnIn S /2 % MoSe photocatalyst displays a high H generation rate of 2228 μmol g h and an apparent quantum yield (AQY) of 21.39 % at 420 nm. This study presents an unprecedented ZnIn S /MoSe metal-sulfide-metal-selenide hybrid system for H evolution. Importantly, the present efficient hybridization strategy reveals the potential of hierarchical nanoarchitectures for a multitude of energy storage and solar energy conversion applications.
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