We report single-atom doping of gold nanoclusters (NCs), and its drastic effects on the optical, electronic, and catalytic properties, using the 25-atom system as a model. In our synthetic approach, a mixture of Pt(1)Au(24)(SC(2)H(4)Ph)(18) and Au(25)(SC(2)H(4)Ph)(18) was produced via a size-focusing process, and then Pt(1)Au(24)(SC(2)H(4)Ph)(18) NCs were obtained by selective decomposition of Au(25)(SC(2)H(4)Ph)(18) in the mixture with concentrated H(2)O(2) followed by purification via size-exclusion chromatography. Experimental and theoretical analyses confirmed that Pt(1)Au(24)(SC(2)H(4)Ph)(18) possesses a Pt-centered icosahedral core capped by six Au(2)(SC(2)H(4)Ph)(3) staples. The Pt(1)Au(24)(SC(2)H(4)Ph)(18) cluster exhibits greatly enhanced stability and catalytic activity relative to Au(25)(SC(2)H(4)Ph)(18) but a smaller energy gap (E(g) ≈ 0.8 eV vs 1.3 eV for the homogold cluster).
Defect
engineering is widely applied in transition metal dichalcogenides
(TMDs) to achieve electrical, optical, magnetic, and catalytic regulation.
Vacancies, regarded as a type of extremely delicate defect, are acknowledged
to be effective and flexible in general catalytic modulation. However,
the influence of vacancy states in addition to concentration on catalysis
still remains vague. Thus, via high throughput calculations, the optimized
sulfur vacancy (S-vacancy) state in terms of both concentration and
distribution is initially figured out among a series of MoS2 models for the hydrogen evolution reaction (HER). In order to realize
it, a facile and mild H2O2 chemical etching
strategy is implemented to introduce homogeneously distributed single
S-vacancies onto the MoS2 nanosheet surface. By systematic
tuning of the etching duration, etching temperature, and etching solution
concentration, comprehensive modulation of the S-vacancy state is
achieved. The optimal HER performance reaches a Tafel slope of 48
mV dec–1 and an overpotential of 131 mV at a current
density of 10 mA cm–2, indicating the superiority
of single S-vacancies over agglomerate S-vacancies. This is ascribed
to the more effective surface electronic structure engineering as
well as the boosted electrical transport properties. By bridging the
gap, to some extent, between precise design from theory and practical
modulation in experiments, the proposed strategy extends defect engineering
to a more sophisticated level to further unlock the potential of catalytic
performance enhancement.
Bifunctional electrocatalysts that can boost energy-related reactions are urgently in demand for pursual of dual and even multiple targets towards practical applications such as energy conversion, clean fuel production and pollution treatment.
The applications of any two-dimensional (2D) semiconductor devices cannot bypass the control of metal-semiconductor interfaces, which can be severely affected by complex Fermi pinning effects and defect states. Here, we report a near-ideal rectifier in the all-2D Schottky junctions composed of the 2D metal 1 T′-MoTe2 and the semiconducting monolayer MoS2. We show that the van der Waals integration of the two 2D materials can efficiently address the severe Fermi pinning effect generated by conventional metals, leading to increased Schottky barrier height. Furthermore, by healing original atom-vacancies and reducing the intrinsic defect doping in MoS2, the Schottky barrier width can be effectively enlarged by 59%. The 1 T′-MoTe2/healed-MoS2 rectifier exhibits a near-unity ideality factor of ~1.6, a rectifying ratio of >5 × 105, and high external quantum efficiency exceeding 20%. Finally, we generalize the barrier optimization strategy to other Schottky junctions, defining an alternative solution to enhance the performance of 2D-material-based electronic devices.
Monolayer 2D semiconductors (e.g., MoS2) are of considerable interest for atomically thin transistors but generally limited by insufficient carrier mobility or driving current. Minimizing the lattice defects in 2D semiconductors represents a common strategy to improve their electronic properties, but has met with limited success to date. Herein, a hidden benefit of the atomic vacancies in monolayer 2D semiconductors to push their performance limit is reported. By purposely tailoring the sulfur vacancies (SVs) to an optimum density of 4.7% in monolayer MoS2, an unusual mobility enhancement is obtained and a record‐high carrier mobility (>115 cm2 V−1 s−1) is achieved, realizing monolayer MoS2 transistors with an exceptional current density (>0.60 mA µm−1) and a record‐high on/off ratio >1010, and enabling a logic inverter with an ultrahigh voltage gain >100. The systematic transport studies reveal that the counterintuitive vacancy‐enhanced transport originates from a nearest‐neighbor hopping conduction model, in which an optimum SV density is essential for maximizing the charge hopping probability. Lastly, the vacancy benefit into other monolayer 2D semiconductors is further generalized; thus, a general strategy for tailoring the charge transport properties of monolayer materials is defined.
Graphene (Gr) has many unique properties including gapless band structure, ultrafast carrier dynamics, high carrier mobility and flexibility, making it appealing for ultrafast, broadband and flexible optoelectronics. To overcome its intrinsic limit of low absorption, hybrid structures have been exploited to improve the device performance. Particularly, van der Waals (vdW) heterostructures with different photosensitive materials and photonic structures are very effective for improving photodetection and modulation efficiency. With the hybrid structures, Gr hybrid photodetectors can operate from ultraviolet (UV) to terahertz (THz), with significantly improved R (up to 10 9 A W -1 ) and bandwidth (up to 128 GHz). Furthermore, integration of Gr with silicon (Si) complementary metal-oxide-semiconductor (CMOS) circuits, the human body, and soft tissues has been successfully demonstrated, opening promising opportunities for wearable sensors and biomedical electronics. Here, the recent progress in using Gr hybrid structures towards highperformance photodetectors and integrated optoelectronic applications is reviewed.
Copper-incorporated α-Ni(OH)2 nanoarrays with a unique hierarchical wire-on-sheet structure and local Ni3+ species are explored as efficient trifunctional electrocatalysts for urea oxidation and water electrolysis.
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