Transition metal (TM) sulfides belong to the class of 2D materials with a wide application range. Various methods, including solvothermal, hydrothermal, chemical vapor deposition, and quartz ampoule-based approaches, have been employed for the synthesis of TM sulfides. Some of them face limitations due to the low stability of TM sulfides and their susceptibility to oxidation, and others require more sophisticated equipment or complex and rare precursors or are not scalable. In this work, we propose an alternative approach for the synthesis of 2D TM sulfides by sulfurization of corresponding metal oxides in the vapor of CS2 at elevated temperature. Subsequent treatment in liquid nitrogen allows exfoliation of created sulfides to a 2D structure. A proposed approach was successfully applied to nine transition metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. The resulting materials were extensively characterized using various analytical techniques with a focus on their crystalline structure and 2D nature. Our approach offers several advantages including the use of simple precursors (CS2 and metal oxides), universality (in all cases, the sulfides were obtained), equipment simplicity (tube furnace and quartz reactor), short preparation time (3 h), and the ability of morphology and phase tuning (in particular cases) of the created materials by adjusting the temperature. In addition, gram-scale bulk materials can be obtained in the entry-level laboratories using the proposed approach.

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• Journal Article MeSH

Among 2D materials, transition-metal dichalcogenides (TMDCs) of group 5 metals recently have attracted substantial interest due to their superior electrocatalytic activity toward hydrogen evolution reaction (HER). However, a straightforward and efficient synthesis of the TMDCs which can be easily scaled up is missing. Herein, we report an innovative, simple, and scalable method for tantalum disulfide (TaS2) synthesis, involving CS2 as a sulfurizing agent and Ta2O5 as a metal precursor. The structure of the created TaS2 flakes was analyzed by Raman, XRD, XPS, SEM, and HRTEM techniques. It was demonstrated that a tuning between 1T (metallic) and 3R (semiconductor) TaS2 phases can be accomplished by varying the reaction conditions. The created materials were tested for HER, and the electrocatalytic activity of both phases was significantly enhanced by electrochemical self-activation, up to that comparable with the Pt one. The final values of the Tafel slopes of activated TaS2 were found to be 35 and 43 mV/dec for 3R-TaS2 and 1T-TaS2, respectively, with the corresponding overpotentials of 63 and 109 mV required to reach a current density of 10 mA/cm2. We also investigated the mechanism of flake activation, which can be attributed to the changes in the flake morphology and surface chemistry. Our work provides a scalable and simple synthesis method to produce transition-metal sulfides which could replace the platinum catalyst in water splitting technology.

• Keywords
• CS2, TaS2, electrochemical activation, flakes, hydrogen evolution reaction, sulfurization, transition-metal dichalcogenides,
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• Journal Article MeSH

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 H2SO4 [at 0.8 V vs reversible hydrogen electrode (RHE)], 4.6 mA W-1 in 1 M Na2SO4 (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.

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• Journal Article MeSH

Perovskite solar cells (PSCs) have proved their potential for delivering high power conversion efficiencies (PCE) alongside low fabrication cost and high versatility. The stability and the PCE of PSCs can readily be improved by implementing engineering approaches that entail the incorporation of two-dimensional (2D) materials across the device's layered configuration. In this work, two-dimensional (2D) 6R-TaS2 flakes were exfoliated and incorporated as a buffer layer in inverted PSCs, enhancing the device's PCE, lifetime and thermal stability. A thin buffer layer of 6R-TaS2 flakes was formed on top of the electron transport layer to facilitate electron extraction, thus improving the overall device performance. The optimized devices reach a PCE of 18.45%, representing a 12% improvement compared to the reference cell. The lifetime stability measurements of the devices under ISOS-L2, ISOS-D1, ISOS-D1I and ISOS-D2I protocols revealed that the TaS2 buffer layer retards the intrinsic, thermally activated degradation processes of the PSCs. Notably, the devices retain more than the 80% of their initial PCE over 330 h under continuous 1 Sun illumination at 65 °C.

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• Journal Article MeSH