Comparative Study in Acidic and Alkaline Media of the Effects of pH and Crystallinity on the Hydrogen-Evolution Reaction on MoS_2 and MoSe_2

Single crystals of n-type MoS_2 and n-MoSe_2 showed higher electrocatalytic activity for the evolution of H_2(g) in alkaline solutions than in acidic solutions. The overpotentials required to drive hydrogen evolution at −10 mA cm^(–2) of current density for MoS^2 samples were −0.76 ± 0.13 and −1.03 ± 0.21 V when in contact with 1.0 M NaOH(aq) and 1.0 M H_2SO_4(aq), respectively. For MoSe_2 samples, the overpotentials at −10 mA cm^(–2) were −0.652 ± 0.050 and −0.709 ± 0.073 V in contact with 1.0 M KOH(aq) and 1.0 M H_2SO_4(aq), respectively. Single crystals from two additional sources were also tested, and the absolute values of the measured overpotentials were consistently less (by 460 ± 250 mV) in alkaline solutions than in acidic solutions. When electrochemical etching was used to create edge sites on the single crystals, the kinetics improved in acid but changed little in alkaline media. The overpotentials measured for polycrystalline thin films (PTFs) and amorphous forms of MoS_2 showed less sensitivity to pH and edge density than was observed for single crystals and showed enhanced kinetics in acid when compared to alkaline solutions. These results suggest that the active sites for hydrogen evolution on MoS_2 and MoSe_2 are different in alkaline and acidic media. Thus, while edges are known to serve as active sites in acidic media, in alkaline media it is more likely that terraces function in this role

Microwave Near-Field Imaging of Two-Dimensional Semiconductors

Optimizing new generations of two-dimensional devices based on van der Waals materials will require techniques capable of measuring variations in electronic properties in situ and with nanometer spatial resolution. We perform scanning microwave microscopy (SMM) imaging of single layers of MoS_2 and n- and p-doped WSe_2. By controlling the sample charge carrier concentration through the applied tip bias, we are able to reversibly control and optimize the SMM contrast to image variations in electronic structure and the localized effects of surface contaminants. By further performing tip bias-dependent point spectroscopy together with finite element simulations, we distinguish the effects of the quantum capacitance and determine the local dominant charge carrier species and dopant concentration. These results underscore the capability of SMM for the study of 2D materials to image, identify, and study electronic defects

A scanning probe investigation of the role of surface motifs in the behavior of p-WSe_2 photocathodes

The spatial variation in the photoelectrochemical performance for the reduction of an aqueous one-electron redox couple, Ru(NH_3)_6^(3+/2+), and for the evolution of H_2(g) from 0.5 M H_2SO_4(aq) at the surface of bare or Pt-decorated p-type WSe_2 photocathodes has been investigated in situ using scanning photocurrent microscopy (SPCM). The measurements revealed significant differences in the charge-collection performance (quantified by the values of external quantum yields, Φ_(ext)) on various macroscopic terraces. Local spectral response measurements indicated a variation in the local electronic structure among the terraces, which was consistent with a non-uniform spatial distribution of sub-band-gap states within the crystals. The photoconversion efficiencies of Pt-decorated p-WSe_2 photocathodes were greater for the evolution of H_2(g) from 0.5 M H_2SO_4 than for the reduction of Ru(NH_3)_6^(3+/2+), and terraces that exhibited relatively low values of Φ_(ext) for the reduction of Ru(NH_3)_6^(3+/2+) could in some cases yield values of Φ_(ext) for the evolution of H_2(g) comparable to the values of Φ_(ext) yielded by the highest-performing terraces. Although the spatial resolution of the techniques used in this work frequently did not result in observation of the effect of edge sites on photocurrent efficiency, some edge effects were observed in the measurements; however the observed edge effects differed among edges, and did not appear to determine the performance of the electrodes

Microwave Near-Field Imaging of Two-Dimensional Semiconductors

Optimizing new generations of two-dimensional devices based on van der Waals materials will require techniques capable of measuring variations in electronic properties in situ and with nanometer spatial resolution. We perform scanning microwave microscopy (SMM) imaging of single layers of MoS_2 and n- and p-doped WSe_2. By controlling the sample charge carrier concentration through the applied tip bias, we are able to reversibly control and optimize the SMM contrast to image variations in electronic structure and the localized effects of surface contaminants. By further performing tip bias-dependent point spectroscopy together with finite element simulations, we distinguish the effects of the quantum capacitance and determine the local dominant charge carrier species and dopant concentration. These results underscore the capability of SMM for the study of 2D materials to image, identify, and study electronic defects

Comparative Study in Acidic and Alkaline Media of the Effects of pH and Crystallinity on the Hydrogen-Evolution Reaction on MoS_2 and MoSe_2

Single crystals of n-type MoS_2 and n-MoSe_2 showed higher electrocatalytic activity for the evolution of H_2(g) in alkaline solutions than in acidic solutions. The overpotentials required to drive hydrogen evolution at −10 mA cm^(–2) of current density for MoS^2 samples were −0.76 ± 0.13 and −1.03 ± 0.21 V when in contact with 1.0 M NaOH(aq) and 1.0 M H_2SO_4(aq), respectively. For MoSe_2 samples, the overpotentials at −10 mA cm^(–2) were −0.652 ± 0.050 and −0.709 ± 0.073 V in contact with 1.0 M KOH(aq) and 1.0 M H_2SO_4(aq), respectively. Single crystals from two additional sources were also tested, and the absolute values of the measured overpotentials were consistently less (by 460 ± 250 mV) in alkaline solutions than in acidic solutions. When electrochemical etching was used to create edge sites on the single crystals, the kinetics improved in acid but changed little in alkaline media. The overpotentials measured for polycrystalline thin films (PTFs) and amorphous forms of MoS_2 showed less sensitivity to pH and edge density than was observed for single crystals and showed enhanced kinetics in acid when compared to alkaline solutions. These results suggest that the active sites for hydrogen evolution on MoS_2 and MoSe_2 are different in alkaline and acidic media. Thus, while edges are known to serve as active sites in acidic media, in alkaline media it is more likely that terraces function in this role

Efficient and stable photoelectrochemical energy conversion using p-type WSe2 photocathodes implications

We have synthesized highly cryst. p-type WSe2 and characterized its electrochem. and photoelectrochem. behavior in a variety of aq. redox couples. Energy conversion efficiencies of > 7% with respect to the thermodn. potential for hydrogen evolution have been achieved for p-WSe2 photocathodes deposited with a mixed Ru/Pt cocatalyst under 100 mW cm^(-2) white light illumination. Addnl., these photocathodes exhibit good stability during photoredn. of Me viologen for at least two hours under illumination at pH values of 2 and 10. Spectral response measurements suggest that energy conversion efficiencies are limited by short minority-carrier diffusion lengths, but impedance spectroscopy indicates that the p-WSe2 band-edge positions are nearly ideal for attaining max. photovoltages for the hydrogen evolution reaction

Hydrogen Evolution from Pt/Ru-Coated p‑Type WSe₂ Photocathodes

Crystalline p-type WSe₂ has been grown by a chemical vapor transport method. After deposition of noble metal catalysts, p-WSe₂ photocathodes exhibited thermodynamically based photoelectrode energy-conversion efficiencies of >7% for the hydrogen evolution reaction under mildly acidic conditions, and were stable under cathodic conditions for at least 2 h in acidic as well as in alkaline electrolytes. The open circuit potentials of the photoelectrodes in contact with the H⁺/H₂ redox couple were very close to the bulk recombination/diffusion limit predicted from the Shockley diode equation. Only crystals with a prevalence of surface step edges exhibited a shift in flat-band potential as the pH was varied. Spectral response data indicated effective minority-carrier diffusion lengths of ∼1 μm, which limited the attainable photocurrent densities in the samples to ∼15 mA cm^–2 under 100 mW cm^–2 of Air Mass 1.5G illumination

Synthesis and hydrogen-evolution activity of tungsten selenide thin films deposited on tungsten foils

Thin films of WSe_2 have been deposited onto a conductive substrate (tungsten foil) using a relatively simple chemical-vapor-transport technique. X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, X-ray powder diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy indicated that the films consisted of micron-sized single crystals of WSe_2 that were oriented perpendicular to the surface of the tungsten foil substrate. Linear sweep voltammetry was used to assess the ability of the WSe_2 films to catalyze the hydrogen-evolution reaction and chronopotentiometry was used to gauge the temporal stability of the catalytic performance of the films under cathodic conditions. A 350 mV overpotential (η) was required to drive the hydrogen-evolution reaction at a current density of −10 mA cm^(−2) in aqueous 0.5 M H_2SO_4, representing a significant improvement in catalytic performance relative to the behavior of macroscopic WSe_2 single crystals. The WSe_2 thin films were relatively stable under catalytic conditions, with the overpotential changing by only ∼10 mV after one hour and exhibiting an additional change of ∼5mV after another hour of operation

Comparative Study in Acidic and Alkaline Media of the Effects of pH and Crystallinity on the Hydrogen-Evolution Reaction on MoS₂ and MoSe₂

Single crystals of n-type MoS₂ and n-MoSe₂ showed higher electrocatalytic activity for the evolution of H₂(g) in alkaline solutions than in acidic solutions. The overpotentials required to drive hydrogen evolution at −10 mA cm^–2 of current density for MoS₂ samples were −0.76 ± 0.13 and −1.03 ± 0.21 V when in contact with 1.0 M NaOH­(aq) and 1.0 M H₂SO₄(aq), respectively. For MoSe₂ samples, the overpotentials at −10 mA cm^–2 were −0.652 ± 0.050 and −0.709 ± 0.073 V in contact with 1.0 M KOH­(aq) and 1.0 M H₂SO₄(aq), respectively. Single crystals from two additional sources were also tested, and the absolute values of the measured overpotentials were consistently less (by 460 ± 250 mV) in alkaline solutions than in acidic solutions. When electrochemical etching was used to create edge sites on the single crystals, the kinetics improved in acid but changed little in alkaline media. The overpotentials measured for polycrystalline thin films (PTFs) and amorphous forms of MoS₂ showed less sensitivity to pH and edge density than was observed for single crystals and showed enhanced kinetics in acid when compared to alkaline solutions. These results suggest that the active sites for hydrogen evolution on MoS₂ and MoSe₂ are different in alkaline and acidic media. Thus, while edges are known to serve as active sites in acidic media, in alkaline media it is more likely that terraces function in this role