Chemical sensing with 2D materials

During the last decade, two-dimensional materials (2DMs) have attracted great attention due to their unique chemical and physical properties, which make them appealing platforms for diverse applications in opto-electronic devices, energy generation and storage, and sensing. Among their various extraordinary properties, 2DMs possess high surface area-to-volume ratios and ultra-high surface sensitivity to the environment, which are key characteristics for applications in chemical sensing. Furthermore, 2DMs’ superior electrical and optical properties, combined with their excellent mechanical characteristics such as robustness and flexibility, make these materials ideal components for the fabrication of a new generation of high-performance chemical sensors. Depending on the specific device, 2DMs can be tailored to interact with various chemical species at the non-covalent level, making them powerful platforms for fabricating devices exhibiting a high sensitivity towards detection of various analytes including gases, ions and small biomolecules. Here, we will review the most enlightening recent advances in the field of chemical sensors based on atomically-thin 2DMs and we will discuss the opportunities and the challenges towards the realization of novel hybrid materials and sensing devices

Graphene Oxide Hybrid with Sulfur–Nitrogen Polymer for High-Performance Pseudocapacitors

Toward the introduction of fast faradaic pseudocapacitive behavior and the increase of the specific capacitance of carbon-based electrodes, we covalently functionalized graphene oxide with a redox active thiourea-formaldehyde polymer, yielding a multifunctional hybrid system. The multiscale physical and chemical characterization of the novel 3-dimensional hybrid revealed high material porosity with high specific surface area (402 m2 g–1) and homogeneous element distribution. The presence of multiple functional groups comprising sulfur, nitrogen, and oxygen provide additional contribution of Faradaic redox reaction in supercapacity performance, leading to a high effective electrochemical pseudocapacitance. Significantly, our graphene-based 3-dimensional thiourea-formaldehyde hybrid exhibited specific capacitance as high as 400 F g–1, areal capacitance of 160 mF cm–2, and an energy density of 11.1 mWh cm–3 at scan rate of 1 mV s–1 with great capacitance retention (100%) after 5000 cycles at scan rate of 100 mV s–1

Polyacetylenes from Sardinian Oenanthe fistulosa: A Molecular Clue to risus sardonicus

An investigation of Oenanthe fistulosa from Sardinia afforded oenanthotoxin (1a) and dihydrooenanthotoxin (1b) from the roots and the diacetylenic epoxydiol 2 from the seeds. The absolute configuration of 1a and 1b was established as R by the modified Mosher's method, and the structure of 2 by chemical correlation with (+)-(3R,8S)-falcarindiol. Oenanthotoxin (1a) and dihydrooenanthotoxin (1b) were found to potently block GABAergic responses, providing a molecular rationale for the symptoms of poisoning from water-dropwort (Oenanthe crocata) and related plants. These observations bear relevance for a series of historical and ethnopharmacological observations on the identification of the Sardonic herb and the molecular details of the facial muscular contraction caused by its ingestion (risus sardonicus)

Reduced graphene oxide–silsesquioxane hybrid as a novel supercapacitor electrode

Supercapacitor energy storage devices recently garnered considerable attention due to their cost-effectiveness, eco-friendly nature, high power density, moderate energy density, and long-term cycling stability. Such figures of merit render supercapacitors unique energy sources to power portable electronic devices. Among various energy storage materials, graphene-related materials have established themselves as ideal electrodes for the development of elite supercapacitors because of their excellent electrical conductivity, high surface area, outstanding mechanical properties combined with the possibility to tailor various physical and chemical properties via chemical functionalization. Increasing the surface area is a powerful strategy to improve the performance of supercapacitors. Here, modified polyhedral oligosilsesquioxane (POSS) is used to improve the electrochemical performance of reduced graphene oxide (rGO) through the enhancement of porosity and the extension of interlayer space between the sheets allowing efficient electrolyte transport. rGO–POSS hybrids exhibited a high specific capacitance of 174 F g−1, power density reaching 2.25 W cm−3, and high energy density of 41.4 mW h cm−3 endowed by the introduction of POSS spacers. Moreover, these electrode materials display excellent durability reaching >98% retention after 5000 cycles

Synthesis and characterization of ultralong copper sulfide nanowires and their electrical properties

We report the synthesis of ultralong copper sulfide nanowires (Cu2−xSNWs) through the sulphidation reaction of metallic copper nanowires (CuNWs) by thiourea under mild conditions. The multiscale characterization of Cu2−xSNWs revealed the presence of a core shell structure made up of an external covellite layer coating a roxbyite core. The Cu2−xSNWs, exhibiting lengths as high as 200 μm, can be easily dispersed in ethanol and deposited onto arbitrary substrates such as glass or plastic. The resulting films are readily conducting without the need for post-treatments and exhibit a sheet resistance of 4.1 kΩ sq−1at 73.7% transmittance (at 550 nm), by virtue of the high aspect ratio of the Cu2−xSNWs. The multiscale electrical characterization down to the single Cu2−xSNWs revealed a low resistivity of 6.9 × 10−6Ω m and perfect Ohmic conductivity. Interestingly, the conductivity of Cu2−xSNW films supported on polyethylene naphthalate sheets remained almost unaltered (4% decrease) after 10 000 bending cycles. In addition, Cu2−xSNWs have shown excellent chemical stability towards a strong oxidant like FeCl3as well as in an acidic environment. Finally, Cu2−xSNWs have been employed as active materials in symmetric supercapacitors revealing good pseudocapacitive behaviour, with specific capacity as high as 324 F g−1(at 5 mV s−1) and 70% retention of the initial capacitance after 5000 cycles (at 100 mV s−1)

Graphene oxide-branched polyethylenimine foams for efficient removal of toxic cations from water

Highly porous foams based on graphene oxide functionalized with polyethylenimine are generated and used with unprecedented efficiency for adsorbing heavy metal ions. A multiscale analysis of the GO-BPEI nanocomposite provided evidence for the covalent grafting of BPEI on GO and the formation of low crystalline porous foams. The uptake experiments revealed that the GO-BPEI's adsorption of toxic cations is strongly dependent on the pH in range from 2 to 10, as a result of the different interactions at the supramolecular level between the metal ions and the GO-BPEI foam. The maximum uptake capacities for Cu(ii), Cd(ii) and Pb(ii) are achieved at pH = 5 and exhibit values as high as 1096, 2051 and 3390 mg g-1, respectively, being ca. over 20 times greater than standard sorbents like activated carbon. The GO-BPEI composite can be easily regenerated as proven by performing adsorption cycles. Also, the thermodynamic parameters including standard Gibbs free energy (ΔGo), the enthalpy change (ΔHo) and entropy change (ΔSo) revealed the exothermic and spontaneous nature of the adsorption process