Figure 12 A) Schematic representation of photocatalytic
H2 generation on MoS2-CdS nanorods. B)
H2 evolution rates of MoS2-CdS nanorods
with different MoS2 content. C) Comparison of
H2 evolution rates between CdS nanorods, 1 wt.% Pt/CdS
nanorods, 3.5 wt.% MoS2 /CdS nanorods, 3.5 wt.%
MoS2-CdS nanorods, and 3.5% Pt/CdS nanorods. D)
Bright-field TEM image of CdSe-seeded CdS nanorods (length 60 nm). E)
MoS3 deposition on a CdSe-seeded CdS nanorod, with
photocatalytic hydrogen production in the visible range using
triethanolamine (TEOA) as a sacrificial reductant. F) A typical gas
chromatogram observed for a MoS3-coated CdS/CdSe nanorod
using 450 nm light with an induction period of approximately 50 min.
0.07 nmol of rods were used with 5.0 mL 0.1m tris buffer (pH 7.0) and
0.20 mL TEOA. The inset shows the measurement over a period of four
hours. The activities are derived from the maximum rate of
H2 produced, as indicated by the arrows. G)-H) Wide-area
TEM images of ZAIS nanodumbbells prepared when xp=0.5
and corresponding ZAIS nanoellipsoids simultaneously formed as a
byproduct. ZAIS nanocrystals of each shape were separated from
as-prepared mixture nanocrystals by a size-selective precipitation
technique. I) Schematic illustration of the formation mechanism of ZAIS
nanodumbbells and nanoellipsoids. J) Dependence of R(H2)
on the kind of ZAIS nanocrystals used. Samples were (i) ZAIS(x/0.24/x)
nanodumbbells, (ii) ZAIS(x) nanoellipsoids, (iii) ZAIS(0.24) nanorods,
and (iv) mixtures of ZAIS(0.24) nanorods and ZAIS(x) nanoellipsoids
(1:2). The scale bar is 20 nm. A-C) Reproduced with
permission.[35] Copyright 2016, Wiley-VCH. D-F)
Reproduced with permission.[36] Copyright 2011,
Wiley-VCH. G-J) Reproduced with permission.[37]Copyright 2018, American Chemical Society.
3. Conclusion and outlook
This Review presents a variety of strategies to engineer the
metal-semiconductor nanorods hybrid nanostructures so that their
electronic properties could be tuned to perform optimal photocatalytic
functions in solar-driven water splitting. While the scope of this
engineering is broad and the photocatalytic properties of derived hybrid
nanomaterials are impressive, this area of research still faces
significant challenges before the full potential of the hybrid
nanomaterials is realized. One challenge is to expand these engineering
strategies from cadmium-based 1D hybrid structures to additional
semiconductor materials, in particular to heavy-metal-free earth
abundant systems. This will require further development of synthetic
routes in combination with emerging engineering strategies which may
lead to less or even non-toxic “green” photocatalysts for solar-driven
fuel production through water splitting but also may provide an avenue
to sustainable and environmental friendly clean fuels. On the other
hand, the construction of multifunctional heterostructure seems to be a
promising approach for water splitting with the realization of high
hydrogen evolution efficiency and prevention from the degradation
induced by holes accumulation.
It is worth noting that this Reviews is mainly focused on
metal-semiconductor nanorods hybrid nanostructures with elongated shape.
Two-dimensional (2D) metal-semiconductor nanoplatelets hybrid
nanostructures with excitons being confined in their thickness direction
are less studies and not well developed. As the catalytic reactions are
more likely to take place on the edge atoms, selectively depositing the
metal atoms, especially the noble metal atoms, onto the edges of
semiconductor nanoplatelets will increase their exposure, which can
reduce their amount of deposition and cost. Furthermore, exploration of
the engineering strategies to this type of intriguing hybrid materials
are meaningful and exciting because studies into this area may lead to
unexpected observations and unprecedented photocatalytic performances.
To summarize, metal-semiconductor hybrid nanoparticles have significant
potential in solar-driven photocatalysis for clean fuel production. The
remarkable advances in the engineering strategies of these materials
alongside with the in-depth understanding the physico-chemical
principals that govern the photocatalytic reactions provide a solid
basis for their photocatalytic applications.
Acknowledgement
This work is supported by the Australian Research Council (ARC) Future
Fellowship Scheme (FT210100509), ARC Discovery Project (DP220101959),
the Hebrew University of Jerusalem - Zelman Cowen Academic Initiatives
(ZCAI) Joint Projects 2021, the Innovation and Technology Commission
(grant no. MHP/104/21), Shenzhen Science Technology and Innovation
Commission (grant no. 20210324125612035), and City University of Hong
Kong (grant no. 9360140).
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