Enhanced photoelectrochemical hydrogen production efficiency of MoS2-Si heterojunction.

Photoelectrochemical water splitting is one of the viable approaches to produce clean hydrogen energy from water. Herein, we report MoS2/Si-heterojunction (HJ) photocathode for PEC H2 production. The MoS2/Si-HJ photocathode exhibits exceptional PEC H2 production performance with a maximum photocurrent density of 36.33 mA/cm2, open circuit potential of 0.5 V vs. RHE and achieves improved long-term stability up to 10 h of reaction time. The photocurrent density achieved by MoS2/Si-HJ photocathode is significantly higher than most of the MoS2 coupled Si-based photocathodes reported elsewhere, indicating excellent PEC H2 production performance.

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm2 at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 µmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Spontaneous solar water splitting with decoupling of light absorption and electrocatalysis using silicon back-buried junction.

Converting sunlight into a storable form of energy by spontaneous water splitting is of great interest but the difficulty in simultaneous management of optical, electrical, and catalytic properties has limited the efficiency of photoelectrochemical (PEC) devices. Herein, we implemented a decoupling scheme of light harvesting and electrocatalysis by employing a back-buried junction (BBJ) PEC cell design, which enables >95% front side light-harvesting, whereas the electrochemical reaction in conjunction with carrier separation/transport/collection occurs on the back side of the PEC cell. The resultant silicon BBJ-PEC half-cell produces a current density of 40.51 mA cm-2 for hydrogen evolution by minimizing optical, electrical, and catalytic losses (as low as 6.11, 1.76, and 1.67 mA cm-2, respectively). Monolithic fabrication also enables three BBJ-PEC cells to be connected in series as a single module, enabling unassisted solar water-splitting with a solar-to-hydrogen conversion efficiency of 15.62% and a hydrogen generation rate of 240 µg cm-2 h-1.

An efficient and stable photoelectrochemical system with 9% solar-to-hydrogen conversion efficiency via InGaP/GaAs double junction.

Despite III-V semiconductors demonstrating extraordinary solar-to-hydrogen (STH) conversion efficiencies, high cost and poor stability greatly impede their practical implementation in photoelectrochemical (PEC) water splitting applications. Here, we present a simple and efficient strategy for III-V-based photoelectrodes that functionally and spatially decouples the light harvesting component of the device from the electrolysis part that eliminates parasitic light absorption, reduces the cost, and enhances the stability without any compromise in efficiency. The monolithically integrated PEC cell was fabricated by an epitaxial lift-off and transfer of inversely grown InGaP/GaAs to a robust Ni-substrate and the resultant photoanode exhibits an STH efficiency of ~9% with stability ~150 h. Moreover, with the ability to access both sides of the device, we constructed a fully-integrated, unassisted-wireless "artificial leaf" system with an STH efficiency of ~6%. The excellent efficiency and stability achieved herein are attributed to the light harvesting/catalysis decoupling scheme, which concurrently improves the optical, electrical, and electrocatalytic characteristics.

Highly Efficient and Stable Photoelectrochemical Hydrogen Evolution with 2D-NbS2/Si Nanowire Heterojunction.

In recent days, 2-dimensional (2D) niobium disulfide (NbS2) with near-zero Gibbs free energy and superlative acid electrolyte stability has provoked a great deal of interest toward hydrogen evolution reaction (HER) electrocatalyst due to its active basal and edge sulfur sites. Herein, we developed a single step method for the direct deposition of 2D-NbS2 on high-aspect-ratio topographies of silicon nanowires (NWs) by chemical vapor deposition for the applications in HER electrocatalyst. The resultant 2D-NbS2 electrocatalyst demonstrates the HER overpotential of ∼74 mV vs RHE (reversible hydrogen electrode) @ 1 mA/cm2 under acidic conditions and stable for more than 20 h. More importantly, we developed the Si NWs array based photoelectrochemical water-splitting system with the direct deposition of 2D-NbS2 as HER catalyst. The resultant 2D-NbS2-Si NWs photocathode system demonstrates improved charge transfer characteristics at the Si-NbS2 interfaces that leads to an enhanced turn on potential (from 0.06 to 0.34 V vs RHE) with the current density of -28 mA/cm2 at the 0 V vs RHE. The results evidence the synergistic effect of 2D-NbS2 electrocatalysts that addresses poor surface kinetics of Si toward solar water electrolysis. Our comprehensive studies reveal NbS2 as a new class of photoelectrochemical cocatalyst for efficient solar HER performance by promoting the charge transfer process with prolonged acid stability.

Heteroatom-Mediated Interactions between Ruthenium Single Atoms and an MXene Support for Efficient Hydrogen Evolution.

A titanium carbide (Ti3 C2 Tx ) MXene is employed as an efficient solid support to host a nitrogen (N) and sulfur (S) coordinated ruthenium single atom (RuSA ) catalyst, which displays superior activity toward the hydrogen evolution reaction (HER). X-ray absorption fine structure spectroscopy and aberration corrected scanning transmission electron microscopy reveal the atomic dispersion of Ru on the Ti3 C2 Tx MXene support and the successful coordination of RuSA with the N and S species on the Ti3 C2 Tx MXene. The resultant RuSA -N-S-Ti3 C2 Tx catalyst exhibits a low overpotential of 76 mV to achieve the current density of 10 mA cm-2 . Furthermore, it is shown that integrating the RuSA -N-S-Ti3 C2 Tx catalyst on n+ np+ -Si photocathode enables photoelectrochemical hydrogen production with exceptionally high photocurrent density of 37.6 mA cm-2 that is higher than the reported precious Pt and other noble metals catalysts coupled to Si photocathodes. Density functional theory calculations suggest that RuSA coordinated with N and S sites on the Ti3 C2 Tx MXene support is the origin of this enhanced HER activity. This work would extend the possibility of using the MXene family as a solid support for the rational design of various single atom catalysts.

Raman selection rule for surface optical phonons in ZnS nanobelts.

We report Raman scattering results for high-quality wurtzite ZnS nanobelts (NBs) grown by chemical vapor deposition. In the Raman spectrum, the ensembles of ZnS NBs exhibit first order phonon modes at 274 cm(-1) and 350 cm(-1), corresponding to A1/E1 transverse optical and A1/E1 longitudinal optical phonons, in addition to a strong surface optical (SO) phonon mode at 329 cm(-1). The existence of the SO band is confirmed by its shift with different surrounding dielectric media. Polarization dependent Raman spectra were recorded on a single ZnS NB and for the first time a SO phonon band has been detected on a single nanobelt. Different selection rules for the SO phonon mode are shown from their corresponding E1/A1 phonon modes, and were attributed to the breaking of anisotropic translational symmetry on the NB surface.