Liquid-phase exfoliation is the most suitable platform for large-scale production of two-dimensional materials. One of the main open challenges is related to the quest of green and bioderived solvents to replace state-of-the-art dispersion media, which suffer several toxicity issues. Here, we demonstrate the suitability of methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv Polarclean) for sonication-assisted liquid-phase exfoliation of layered materials for the case-study examples of WS₂, MoS₂, and graphene. We performed a direct comparison, in the same processing conditions, with liquid-phase exfoliation using N-methyl-2-pyrrolidone (NMP) solvent. The amount of few-layer flakes (with thickness <5 nm) obtained with Polarclean is increased by ∼350% with respect to the case of liquid-phase exfoliation using NMP, maintaining comparable values of the average lateral size, which even reaches ∼10 μm for the case of graphene produced by exfoliation in Polarclean, and of the yield (∼40%). Correspondingly, the density of defects is reduced by 1 order of magnitude by Polarclean-assisted exfoliation, as evidenced by the I(D)/I(G) ratio in Raman spectra of graphene as low as 0.07 ± 0.01. Considering the various advantages of Polarclean over state-of-the-art solvents, including the absence of toxicity and its biodegradability, the validation of superior performances of Polarclean in liquid-phase exfoliation paves the way for sustainable large-scale production of nanosheets of layered materials and for extending their use in application fields to date inhibited by toxicity of solvents (e.g., agri-food industry and desalination), with a subsequent superb impact on the commercial potential of their technological applications.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) and metal chalcogenides (MCs), despite their excellent gas sensing properties, are subjected to spontaneous oxidation in ambient air, negatively affecting the sensor's signal reproducibility in the long run. Taking advantage of spontaneous oxidation, we synthesized fully amorphous a-SnO₂ 2D flakes (≈30 nm thick) by annealing in air 2D SnSe₂ for two weeks at temperatures below the crystallization temperature of SnO₂ (T < 280 °C). These engineered a-SnO₂ interfaces, preserving all the precursor's 2D surface-to-volume features, are stable in dry/wet air up to 250 °C, with excellent baseline and sensor's signal reproducibility to H₂S (400 ppb to 1.5 ppm) and humidity (10-80% relative humidity (RH)) at 100 °C for one year. Specifically, by combined density functional theory and ab initio molecular dynamics, we demonstrated that H₂S and H₂O compete by dissociative chemisorption over the same a-SnO₂ adsorption sites, disclosing the humidity cross-response to H₂S sensing. Tests confirmed that humidity decreases the baseline resistance, hampers the H₂S sensor's signal (i.e., relative response (RR) = R_a/R_g), and increases the limit of detection (LOD). At 1 ppm, the H₂S sensor's signal decreases from an RR of 2.4 ± 0.1 at 0% RH to 1.9 ± 0.1 at 80% RH, while the LOD increases from 210 to 380 ppb. Utilizing a suitable thermal treatment, here, we report an amorphization procedure that can be easily extended to a large variety of TMDs and MCs, opening extraordinary applications for 2D layered amorphous metal oxide gas sensors.

The NO₂ response in the range of 200 ppb to 1 ppm of a chemoresistive WS₂-decorated rGO sensor has been investigated at operating temperatures of 25 °C and 50 °C in dry and humid air (40% RH) under dark and Purple Blue (PB) light conditions (λ = 430 nm). Few-layers WS₂, exfoliated by ball milling and sonication technique, with average dimensions of 200 nm, have been mixed with rGO flakes (average dimension 700 nm) to yield WS₂-decorated rGO, deposited on Si₃N₄ substrates, provided with platinum (30 μm gap distance) finger-type electrodes. TEM analysis showed the formation of homogeneous and well-dispersed WS₂ flakes distributed over a thin, continuous and uniform underlying layer of interconnected rGO flakes. XPS and STEM revealed a partial oxidation of WS₂ flakes leading to the formation of 18% amorphous WO₃ over the WS₂ flakes. PB-light irradiation and mild heating of the sensor at 50 °C substantially enhanced the baseline recovery yielding improved adsorption/desorption rates, with detection limit of 400 ppb NO₂ and reproducible gas responses. Cross sensitivity tests with humid air interfering vapor highlighted a negligible influence of water vapor on the NO₂ response. A charge carrier mechanism between WS₂ and rGO is proposed and discussed to explain the overall NO₂ and H₂O response of the WS₂–rGO hybrids.