Search

Cadmium sulfide (CdS) is a semiconducting absorber for photoelectrochemical (PEC) hydrogen production with suitable electronic band structures. However, it suffers from severe photocorrosion and rapid charge recombination during the desired PEC reactions. Herein, we describe the identification of the optimal junction thickness of CdS/MoS 2 core/sheath heterojunction nanostructures by employing atomic layer deposition (ALD) techniques. ALD-grown MoS 2 sheath layers with different thicknesses were realized on single-crystalline CdS nanorod (NR) arrays on transparent conducting oxide substrates. We further monitored the resulting solar H 2 evolution performance with our heterojunction photoanodes. The results showed that the junction thickness of MoS 2 plays a key role in the reduction of photocorrosion and the enhanced photocurrent density by optimizing the charge separation. A better saturation photocurrent (∼46%) was obtained with the 7 nm-thick MoS 2 @CdS NRs than that with the bare CdS NRs. Moreover, the external quantum efficiency was increased twofold over that of the pristine CdS NRs. The ALD-grown MoS 2 @CdS heterojunction structures provides an efficient and versatile platform for hydrogen production when combining ALD-grown MoS 2 with ideal semiconducting absorbers.

Single-crystalline gold nanowires (Au NWs) are directly synthesized by the photocatalytic reduction of an aqueous HAuCl 4 solution inside high-aspect-ratio TiO 2 nanotubes (NTs). Crystalline TiO 2 (anatase) NTs are prepared by the template-assisted atomic layer deposition technique with a subsequent annealing. Under the irradiation of ultraviolet light, photoexcited electrons are formed on the surfaces of TiO 2 NTs and could reduce Au ions to create nuclei without using any surfactant, reducing agent, and/or seed. Once nucleation occurred, high-aspect-ratio Au NWs are grown inside the TiO 2 NTs in a diffusion-controlled manner. As the solution pH increased, the nucleation/growth rate decreased and twin-free (or not observed), single-crystalline Au NWs are formed. At a pH above 6, the nucleation/growth rates increased and Au nanoparticles are observed both inside and outside of the TiO 2 NTs. The confined nanoscale geometries of the interior of the TiO 2 NTs are found to play a key role in the controlled diffusion of Au species and in determining the crystal morphology of the resulting Au NWs.

We describe the direct preparation of crystalline Ni 3 S 2 thin films via atomic layer deposition (ALD) techniques at temperatures as low as 250 °C without postthermal treatments. A new ALD chemistry is proposed using bis(1-dimethylamino-2-methyl-2-butoxy) nickel(II) [Ni(dmamb) 2 ] and H 2 S as precursors. Homogeneous and conformal depositions of Ni 3 S 2 films were achieved on 4 in. wafers (both metal and oxide substrates, including Au and SiO 2 ). The resulting crystalline Ni 3 S 2 layers exhibited highly efficient and stable performance as electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solutions, with a low overpotential of 300 mV and a high turnover frequency for HER and an overpotential of 400 mV for OER (at a current density of 10 mA/cm 2 ). Using our Ni 3 S 2 films as both the cathode and the anode, two-electrode full-cell electrolyzers were constructed, which showed stable operation for 100 h at a current density of 10 mA/cm 2 . The proposed ALD electrocatalysts on planar surfaces exhibited the best performance among Ni 3 S 2 materials for overall water splitting recorded to date.

Surface decoration strategy for one-dimensional nanostructures will improve their electrical, optical, mechanical, and electrochemical performances dramatically. Heterogeneous growth/deposition on surfaces, however, may create undesired junction interfaces in the system. Here we report a procedure during which amorphous titania nanotubes are readily self-branched with crystalline titanate nanorods at room temperature. The starting amorphous titania nanotubes were prepared by low-temperature atomic layer deposition combined with the template-directed approach. We routinely observed the self-branching phenomenon of crystalline titanate nanorods with a few nanometers in diameter onto the surfaces of the amorphous titania nanotubes in mild alkali solutions. The resulting structures were analyzed by field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and electron energy loss spectroscopy. The reactivity of the hierarchical titania nanotube arrays was observed to be improved as a Li secondary battery electrode. Upon complete consumption of the amorphous body of titania nanotubes, in addition, titanate nanosheets/layers consisting of single TiO(2) layers with unit-cell thickness were obtained, elucidating the formation mechanism of layered titanate materials by alkali treatment.