RESUMEN
A thiomolybdate [Mo3S13]2- nanocluster is a promising catalyst for hydrogen evolution reaction (HER) due to the high number of active edge sites. In this work, thiomolybdate cluster films are prepared by spin-coating of a (NH4)2Mo3S13 solution both on FTO glass substrates as hydrogen evolving electrodes and on highly 00.1-textured WSe2 for photoelectrochemical water splitting. As an electrocatalyst, [Mo3S13]2- clusters demonstrate a low overpotential of 220 mV at 10 mA cm-2 in 0.5 M H2SO4 electrolyte (pH 0.3) and remain structurally stable during the electrochemical cycling as revealed by in situ Raman spectroscopy. Moreover, as a co-catalyst on WSe2, [Mo3S13]2- clusters enhance the photocurrent substantially by more than two orders of magnitude (from 0.02 to 2.8 mA cm-2 at 0 V vs RHE). The synergistic interactions between the photoelectrode and catalyst, i.e., surface passivation and band bending modification by the [Mo3S13]2- cluster film, promoted HER catalytic activity of [Mo3S13]2- clusters influenced by the WSe2 support, are revealed by intensity-modulated photocurrent spectroscopy and density functional theory calculations, respectively. The band alignment of the WSe2/[Mo3S13]2- heterojunction, which facilitates the electron injection, is determined by correlating UV-vis with photoelectron yield spectroscopy results.
RESUMEN
Hydrogen produced from solar energy has the potential to replace petroleum in the future. To this respect, there is a need in the abandoned and efficient materials that can continuously split water molecules using solar energy. In this report, an ammonium thiomolybdate (ATM: (NH4)2Mo3S13) is evaluated as a p-type semiconductor film photocathode for hydrogen evolution reaction. The ATM thin films are prepared by spin-coating on fluorine-doped tin oxide substrates, and their structural, morphological, optical, photoelectrical, and photoelectrochemical (PEC) properties are studied. Transient surface photovoltage (TSPV) spectroscopy and spectroscopic ellipsometry indicate the band gap Eg = 1.9 eV for the ATM thin films. Furthermore, the photovoltage of the ATM thin films measured by TSPV is correlated to the photocurrents measured by the PEC characterization that can be used to evaluate the material potential for hydrogen generation. The films exhibit a low photocurrent density of 46 µA cm-2 at 0 VRHE. However, its combination with WSe2 thin-film photocathodes results in a significant increase in photocurrent density up to 4.6 mA cm-2 at 0 VRHE (100 times). The reason for such a strong charge carrier transfer effect for ATM/WSe2 heterojunction photocathodes is studied by TSPV spectroscopy that allows a comprehensive evaluation of potential photovoltaic materials toward PEC hydrogen production. Furthermore, the photovoltage generated by a WSe2 thin film is 30 times lower than that of its single crystal, which indicates that the quality of WSe2 thin films should be improved for faster PEC hydrogen evolution.
RESUMEN
Silver nanowire (AgNW) networks have attracted particular attention as transparent conductive films (TCF) due to their high conductivity, flexibility, transparency, and large scale processing compatible synthesis. As-prepared AgNW percolating networks typically suffer from high contact resistance, requiring additional post-synthetic processing. In this report, large area irradiation with 200 ns short intense pulsed ion beam (IPIB) was used to anneal and enhance the conductivity of AgNW network, deposited on temperature-sensitive polyethylene terephthalate (PET) substrate. A TCF sheet resistance shows irradiation dose dependence, decreasing by four orders of magnitude and reaching a value of 70 Ω/sq without damaging the polymer substrate, which retained a transparency of 94%. The IPIB irradiation fused AgNW network into the PET substrate, resulting in a great adhesion enhancement. Heat transfer simulations show that the heat originates at the near-surface layer of the TCF and lasts an ultra-short period of time. Obtained experimental and simulation results indicate that the irradiation with IPIBs opens new perspectives in the low-temperature annealing of nanomaterials deposited on temperature-sensitive substrates.
RESUMEN
In this report, an improvement of the electrical performance and stability of a silver nanowire (AgNW) transparent conductive coating (TCC) is presented. The TCC stability against oxidation is achieved by coating the AgNWs with a polyvinyl alcohol (PVA) layer. As a result, a UV/ozone treatment has not affected the morphology of the AgNWs network and the PVA protection layer, unlike non-passivated TCC, which showed severe degradation. The irradiation with an intense pulsed ion beam (IPIB) of 200 ns duration and a current density of 30 A/cm2 is used to increase the conductivity of the AgNWs network without degradation of the temperature-resistant PVA coating and decrease in the TCC transparency. Simulations have shown that, although the sample temperature reaches high values, the ultra-high heating and cooling rates, together with local annealing, enable the delicate thermal processing. The developed coatings and irradiation strategies are used to prepare and enhance the performance of AgNW-based transparent heaters. A single irradiation pulse increases the operating temperature of the transparent heater from 92 to 160 °C at a technologically relevant voltage of 12 V. The proposed technique shows a great promise in super-fast, low-temperature annealing of devices with temperature-sensitive components.
RESUMEN
A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.
RESUMEN
Highly (001)-textured, photoactive WSe2 thin films have been prepared by an amorphous solid-liquid-crystalline solid process promoted by palladium. By increasing the thickness of the Pd promoter film (≥10 nm) the structure and texture of the WSe2 films can be improved significantly. However, these as-crystallized WSe2 films are only weakly photoactive in a 0.5 Ð H2SO4 electrolyte under AM 1.5 solar irradiation which we attribute to an inefficient photogenerated charge transfer across the WSe2/electrolyte interface via the prevailing van der Waals planes of the WSe2 crystallites. In this work photochemically deposited platinum on the p-type WSe2 photocathode is used for an efficient electron transfer thus inducing the hydrogen evolution reaction. Upon illuminating the WSe2 photocathodes in a Pt-ion containing electrolyte, the photogenerated electrons reduce Pt+ to Pt leading to the precipitation of Pt islands, preferentially at edge steps of the WSe2, i.e. at the grain boundaries of the WSe2 crystallites. The increasing amount of Pt islands at the grain boundaries linearly enhances the photocurrent density up to 2.5 mA cm-2 at 0 VRHE in sulfuric acid, the highest reported value up to now for WSe2 thin films.
