Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudodirect optical gap. Theoretical studies predict that its 2D form is a potential photocatalyst for water splitting reactions. Herein, the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single‐/few‐layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media is reported. In 0.5 m H2SO4, the GaSe photoelectrodes display the best PEC performance, corresponding to a ratiometric power‐saved metric for HER (Φsaved,HER) of 0.09% and a ratiometric power‐saved metric for OER (Φsaved,OER) of 0.25%. When used as PEC‐type photodetectors, GaSe photoelectrodes show a responsivity of ≈0.16 A W−1 upon 455 nm illumination at a light intensity of 63.5 µW cm−2 and applied potential of −0.3 V versus reversible hydrogen electrode (RHE). Stability tests of GaSe photodetectors demonstrated a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 m H2SO4 for HER. In contrast, degradation of photoelectrodes occurred in both alkaline and anodic operation due to the highly oxidizing environment and O2‐induced (photo)oxidation effects. The results provide new insight into the PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC‐type photodetectors, and (bio)sensors.

Photoelectrochemical (PEC) systems represent powerful tools to convert electromagnetic radiation into chemical fuels and electricity. In this context, two-dimensional (2D) materials are attracting enormous interest as potential advanced photo(electro)catalysts and, recently, 2D group-IVA metal monochalcogenides have been theoretically predicted to be water splitting photocatalysts. In this work, we use density functional theory calculations to theoretically investigate the photocatalytic activity of single-/few-layer GeSe nanoflakes for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in pH conditions ranging from 0 to 14. Our simulations show that GeSe nanoflakes with different thickness can be mixed in the form of nanoporous films to act as nanoscale tandem systems, in which the flakes, depending on their thickness, can operate as HER-and/or OER photocatalysts. On the basis of theoretical predictions, we report the first experimental characterization of the photo(electro)catalytic activity of single-/few-layer GeSe flakes in different aqueous media, ranging from acidic to alkaline solutions: 0.5 M H 2 SO 4 (pH 0.3), 1 M KCl (pH 6.5), and 1 M KOH (pH 14). The films of the GeSe nanoflakes are fabricated by spray coating GeSe nanoflakes dispersion in 2-propanol obtained through liquid-phase exfoliation of synthesized orthorhombic (Pnma) GeSe bulk crystals. The PEC properties of the GeSe nanoflakes are used to design PEC-type photodetectors, reaching a responsivity of up to 0.32 AW −1 (external quantum efficiency of 86.3%) under 455 nm excitation wavelength in acidic electrolyte. The obtained performances are superior to those of several self-powered and low-voltage solution-processed photodetectors, approaching that of self-powered commercial UV−Vis photodetectors. The obtained results inspire the use of 2D GeSe in proof-of-concept water photoelectrolysis cells.

Two-dimensional (2D) transition-metal monochalcogenides have been recently predicted to be potential photo(electro)catalysts for water splitting and photoelectrochemical (PEC) reactions. Differently from the most established InSe, GaSe, GeSe, and many other monochalcogenides, bulk GaS has a large band gap of ∼2.5 eV, which increases up to more than 3.0 eV with decreasing its thickness due to quantum confinement effects. Therefore, 2D GaS fills the void between 2D small-band-gap semiconductors and insulators, resulting of interest for the realization of van der Waals type-I heterojunctions in photocatalysis, as well as the development of UV light-emitting diodes, quantum wells, and other optoelectronic devices. Based on theoretical calculations of the electronic structure of GaS as a function of layer number reported in the literature, we experimentally demonstrate, for the first time, the PEC properties of liquid-phase exfoliated GaS nanoflakes. Our results indicate that solution-processed 2D GaS-based PEC-type photodetectors outperform the corresponding solid-state photodetectors. In fact, the 2D morphology of the GaS flakes intrinsically minimizes the distance between the photogenerated charges and the surface area at which the redox reactions occur, limiting electron–hole recombination losses. The latter are instead deleterious for standard solid-state configurations. Consequently, PEC-type 2D GaS photodetectors display a relevant UV-selective photoresponse. In particular, they attain responsivities of 1.8 mA W –1 in 1 M H 2 SO 4 [at 0.8 V vs reversible hydrogen electrode (RHE)], 4.6 mA W –1 in 1 M Na 2 SO 4 (at 0.9 V vs RHE), and 6.8 mA W –1 in 1 M KOH (at 1.1. V vs RHE) under 275 nm illumination wavelength with an intensity of 1.3 mW cm –2 . Beyond the photodetector application, 2D GaS-based PEC-type devices may find application in tandem solar PEC cells in combination with other visible-sensitive low-band-gap materials, including transition-metal monochalcogenides recently established for PEC solar energy conversion applications.

Carbon perovskite solar cells (C-PSCs), using carbon-based counter electrodes (C-CEs), promise to mitigate instability issues while providing solution-processed and low-cost device configurations. In this work, we report the fabrication and characterization of efficient paintable C-PSCs obtained by depositing a low-temperature-processed graphene-based carbon paste atop prototypical mesoscopic and planar n–i–p structures. Small-area (0.09 cm 2 ) mesoscopic C-PSCs reach a power conversion efficiency (PCE) of 15.81% while showing an improved thermal stability under the ISOS-D-2 protocol compared to the reference devices based on Au CEs. The proposed graphene-based C-CEs are applied to large-area (1 cm 2 ) mesoscopic devices and low-temperature-processed planar n–i–p devices, reaching PCEs of 13.85 and 14.06%, respectively. To the best of our knowledge, these PCE values are among the highest reported for large-area C-PSCs in the absence of back-contact metallization or additional stacked conductive components or a thermally evaporated barrier layer between the charge-transporting layer and the C-CE (strategies commonly used for the record-high efficiency C-PSCs). In addition, we report a proof-of-concept of metallized miniwafer-like area C-PSCs (substrate area = 6.76 cm 2 , aperture area = 4.00 cm 2 ), reaching a PCE on active area of 13.86% and a record-high PCE on aperture area of 12.10%, proving the metallization compatibility with our C-PSCs. Monolithic wafer-like area C-PSCs can be feasible all-solution-processed configurations, more reliable than prototypical perovskite solar (mini)modules based on the serial connection of subcells, since they mitigate hysteresis-induced performance losses and hot-spot-induced irreversible material damage caused by reverse biases.

The development of high-power density vanadium redox flow batteries (VRFBs) with high energy efficiencies (EEs) is crucial for the widespread dissemination of this energy storage technology. In this work, we report the production of novel hierarchical carbonaceous nanomaterials for VRFB electrodes with high catalytic activity toward the vanadium redox reactions (VO 2+ /VO 2 + and V 2+ /V 3+ ). The electrode materials are produced through a rapid (minute timescale) low-pressure combined gas plasma treatment of graphite felts (GFs) in an inductively coupled radio frequency reactor. By systematically studying the effects of either pure gases (O 2 and N 2 ) or their combination at different gas plasma pressures, the electrodes are optimized to reduce their kinetic polarization for the VRFB redox reactions. To further enhance the catalytic surface area of the electrodes, single-/few-layer graphene, produced by highly scalable wet-jet milling exfoliation of graphite, is incorporated into the GFs through an infiltration method in the presence of a polymeric binder. Depending on the thickness of the proton-exchange membrane (Nafion 115 or Nafion XL), our optimized VRFB configurations can efficiently operate within a wide range of charge/discharge current densities, exhibiting energy efficiencies up to 93.9%, 90.8%, 88.3%, 85.6%, 77.6%, and 69.5% at 25, 50, 75, 100, 200, and 300 mA cm –2 , respectively. Our technology is cost-competitive when compared to commercial ones (additional electrode costs < 100 € m –2 ) and shows EEs rivalling the record-high values reported for efficient systems to date. Our work remarks on the importance to study modified plasma conditions or plasma methods alternative to those reported previously (e.g., atmospheric plasmas) to improve further the electrode performances of the current VRFB systems.

Gallium selenide (GaSe), a layered semiconductor of Group‐III monochalcogenides, has been recognized by the scientific community in recent years as an appealing material in the fields of photonics and (opto)electronics. Thanks to its pseudodirect bandgap and its thickness‐dependent (opto)electronic properties, GaSe has emerged as a promising candidate for the implementation of thin‐film transistors (TFTs) and photodetectors with fast response and high sensitivity. Solution processing of 2D materials provides low‐cost inks that allow the design and realization of printed electronic devices, enabling this technology to move from the laboratory to the industry. In this work, a solution‐processed GaSe‐based light‐driven transistor is presented. Liquid phase exfoliation (LPE) is used to exfoliate bulk GaSe in isopropanol, formulating a functional ink that is subsequently deposited by spray coating onto Si/SiO2 substrates. The GaSe phototransistor exhibits a p‐channel behavior with a high on/off ratio (≈103) that is gate‐voltage dependent. Moreover, the device response also depends on the illumination with a maximum responsivity of 13 A W–1 to UV–visible light and a fast response time of 35 ms. This study demonstrates that liquid phase exfoliated GaSe is a promising candidate for the design and realization of next‐generation (opto)electronic devices.

We explore the broadband excitation spectrum of bulk PtTe2 using electron energy loss spectroscopy and density functional theory. In addition to infrared modes related to intraband 3D Dirac plasmon and interband transitions between the 3D Dirac bands, we observe modes at 3.9, 7.5 and 19.0 eV in the ultraviolet region. The comparison of the excitation spectrum with the calculated orbital-resolved density of states allows us to ascribe spectral features to transitions between specific electronic states. Additionally, we study the thickness dependence of the high-energy plasmon in the PtTe2 thin films. We show that, unlike graphene, the high-energy plasmon in PtTe2 thin film gets red-shifted by ∼2.5 eV with increasing thickness. arXiv:1808.08947v1 [cond-mat.mes-hall]

We report an extensive structural characterization of the surface of 1T-PtTe2 crystals by means of helium atom scattering (HAS) and ultra-high resolution scanning tunnelling microscopy (STM). HAS reveals that this bi-dimensional surface presents a large structural corrugation (∼) in direction. The surface lattice constant of PtTe2 derived from the positions of the helium diffraction peaks up to fifth order was found to be , in agreement with STM and x-ray diffraction measurements. This value remains unchanged in the temperature range between 90 and 580 K. These findings suggest that 1T-PtTe2 behaves similarly to graphene on a weakly-interacting substrate, for which the surface thermal expansion coefficient is zero within experimental error. The electron–phonon coupling constant has been determined by recording the thermal attenuation of the elastic diffraction peaks of PtTe2. Based on a recently developed quantum theoretical method adapted to layered degenerate semiconductors we find that lies between 0.38–0.42.