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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 ca. 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.

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 (VO2+/VO2+ and V2+/V3+). 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 (O2 and N2) 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 euro 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.

The understanding of depletion layers is of major importance to control the optical and electronic properties of metal oxide (MO) nanocrystals (NCs). Here, we show that depletion layer engineering is the main mechanism of photodoping of MO NCs. We show that the introduction of different electronic interfaces induces a double-bending of the electronic bands and a distinct carrier density profile. We found that the light-induced depletion layer modulation and bending of the bands close to the surface of the nanocrystal is the main mechanism responsible for the storage of extra electrons after photodoping in MO NCs. We support our results by a combined experimental and theoretical approach in the case of Sn:In2O3/In2O3 core-shell NCs, in which we compare numerical simulations with empirical modeling and experiments. This allows not only to extract the main mechanism of photodoping in MO NCs but also to engineer the charge storage capability of MO NCs after photodoping. Our results are transferable to other core-multishell systems, opening up a novel direction to control the optoelectronic properties of nanoscale MOs by designing their energetic band profiles through depletion layer engineering.

Harvesting all sources of available clean energy is an essential strategy to contribute to healing current dependence on non-sustainable energy sources. Recently, triboelectric nanogenerators (TENGs) have gained visibility as new mechanical energy harvester offering a valid alternative to batteries, being particularly suitable for portable devices. Here, the increased capacitance of a few-layer graphene-based electrode is obtained by incorporating nitrogen-doped graphene (N_graphene), enabling a 3_fold enhancement in TENGs power output. The dependence of TENGs performance on the electronic properties of different N_graphene types, varying in the doping concentration and in the relative content of N-pyridinic and N-graphitic sites is investigated. These sites have different electron affinities, and synergistically contribute to the variation of the capacitive and resistive properties of N-graphene and consequently, TENG performance. It is demonstrated that the power enhancement of the TENG occurs when the N_graphene, an n-semiconductor, is interfaced between the positive triboelectric material and the electrode, while a deterioration of the electrical performance is observed when it is placed at the interface with the negative triboelectric material. This behavior is explained in terms of the dependence of N_graphene quantum capacitance on the electrode chemical potential which shifts according to the opposite polarization induced at the two electrodes upon triboelectrification.

Advancements in electrochemical double-layer capacitor (EDLC) technology require the concomitant use of novel efficient electrode materials and viable electrode manufacturing methods. Cost-effectiveness, scalability and sustainability are key-drivers for fulfilling product development chain accepted by worldwide legislations. Herein, we report a scalable and sprayable "green" electrode material-based ink based on activated carbon and single-/few-layer graphene (SLG/FLG) flakes. We show that, contrary to commercial reduced graphene oxide, defect-free and flat SLG/FLG flakes reduce the friction of ions over the electrode films, while spray coating deposition of our ink maximises the electrolyte accessibility to the electrode surface area. Sprayed SLG/FLG flakes-based EDLCs display superior rate capability performance (e.g., specific energies of 31.5, 23.7 and 12.5 Wh kg-1 at specific powers of 150, 7500 and 30000 W kg-1, respectively) compared to both SLG/FLG flakes-free devices and commercial-like EDLCs produced by slurry-coating method. The use of SLG/FLG flakes enables our sprayed EDLCs to operate in a wide range of temperature (-40/+100{\deg}C) compatible with ionic liquid/organic solvent-based electrolytes, overcoming the specific power limits of AC-based EDLCs. A prototype EDLCs stack consisting of multiple large-area EDLCs, each one displaying a capacitance of 25 F, demonstrates the industrial potential of our technology.

2D quantum confined hybrid materials are of great interest from a solid state physics standpoint because of the rich multibody phenomena hosted, their tunability and easy synthesis allowing to create material libraries. In addition, from a technological standpoint, 2D hybrids are promising candidates for efficient, tunable, low cost materials impacting a broad range of optoelectronic devices. Different approaches and materials have therefore been investigated, with the notable example of 2D metal halide hybrid perovskites. Despite the remarkable properties of such materials, the presence of toxic elements like lead are not desirable in applications and their ionic lattices may represent a limiting factor for stability under operating conditions. Alternative, non-ionic 2D materials made of non-toxic elements are therefore desirable. In order to expand the library of possible hybrid quantum wells materials, here we consider an alternative platform based on non-toxic, self-assembled, metal-organic chalcogenides. While the optical properties have been recently explored and some unique excitonic characters highlighted, photo-generation of carriers and their transport in these lamellar inorganic/organic nanostructures, critical optoelectronic aspects, remain totally unexplored. We hereby report the first electrical investigation of the air-stable [AgSePh] 2D coordination polymer in form of nanocrystal (NC) films readily synthesized in situ and at low temperature, compatible with flexible plastic substrates. The wavelength-dependent photo-response of the NC films suggests possible use of this materials as near-UV photodetector. We therefore built a lateral photo-detector, achieving a sensitivity of 0.8 A/W at 370 nm thanks to a photoconduction mechanism, and a cutoff frequency of ~400 Hz, and validated its reliability as air-stable UV detector on flexible substrates.

Silver benzeneselenolate [AgSePh] is a coordination polymer that hosts a hybrid quantum well structure. The recent advancements in the study of its tightly bound excitons (~300 meV) and photoconductive properties (recently employed in UV photodetection) makes it an interesting representative of a material platform that is an environmentally stable alternative to 2D metal halide perovskites in terms of optoelectronic properties. To this aim, several challenges are to be addressed, among which the lack of control over the metal-organic reaction process in the reported synthesis of the [AgSePh] nanocrystal film (NC). This issue contributed to cast doubts over the origin of its intra-bandgap electronic states. In this article we study all the steps to obtain phase pure [AgSePh] NC films, from thin silver films through its oxidation and reaction via a chemical vapor-solid with benzeneselenol, by means of UV-vis, XRD, SEM, and AFM. Raman and FTIR spectroscopy are also employed to provide vibrational peaks assignment, for the first time on this polymer. Our analysis supports an acid-base reaction scheme based on an acid attacking the metal oxide precursor, generating water as byproduct of the polymeric synthesis, speeding up the reaction by solvating the PhSeH. The reaction readily goes to completion within 30 min in a supersaturated PhSeH / N2 atmosphere at 90 {\deg}C. Our analysis suggests the absence of precursor's leftovers or oxidized species that could contribute to the intra-gap states. By tuning the reaction parameters, we gained control on film morphology to obtain substrate-parallel oriented micro-crystals showing different excitonic absorption intensities. Finally, centimeters size high quality [AgSePh] NC films could be obtained, enabling exploitation of their optoelectronic properties, such as UV photodetection, in large-area applications.

Plasmonic structures are renowned for their capability to efficiently convert light into heat at the nanoscale. However, despite the possibility to generate deep sub-wavelength electromagnetic hot spots, the formation of extremely localized thermal hot spots is an open challenge of research, simply because of the diffusive spread of heat along the whole metallic nanostructure. Here we tackle this challenge by exploiting single gold nanocones. We theoretically show how these structures can indeed realize extremely high temperature gradients within the metal, leading to deep sub-wavelength thermal hot spots, owing to their capability of concentrating light at the apex under resonant conditions even under continuous wave illumination. A three-dimensional Finite Element Method model is employed to study the electromagnetic field in the structure and subsequent thermoplasmonic behaviour, in terms of the three-dimensional temperature distribution. We show how the latter is affected by nanocone size, shape, and composition of the surrounding environment. Finally, we anticipate the use of photoinduced temperature gradients in nanocones for applications in optofluidics and thermoelectrics or for thermally induced nanofabrication.

Lead halide perovskite-based photoactive layers are nowadays employed for a large number of optoelectronic applications, from solar cells to photodetectors and light-emitting diodes, because of their excellent absorption, emission and charge-transport properties. Unfortunately, their commercialization is still hindered by an intrinsic instability towards classical environmental conditions. Water in particular promotes fast decomposition, leading to a drastic decrease in device performance. An innovative functional approach to overcome this major issue could derive from integrating water-splitting active species within charge extracting layers adjacent to the perovskite photoactive layer, converting incoming water molecules into molecular oxygen and hydrogen before they reach this last one, thus preserving device performance in time. In this work we report for the first time on a perovskite-ancillary layer based on CuSCN nanoplateletes dispersed in a p-type semiconducting polymeric matrix, combining hole extraction/transport properties with good water-oxidation activity, that transforms incoming water molecules and further triggers the in situ p-doping of the conjugated polymer by means of the produced dioxygen, further improving transport of photogenerated charges. This composite layer enables the long-term stabilization of a mixed cation lead halide perovskite within a direct solar cell architecture, maintaining a stable performance for 28 days in high-moisture simulated conditions. Our findings demonstrate that the engineering of a hole extraction layer with water-splitting active additives represent a valuable strategy to mitigate the degradation of perovskite solar cells exposed to atmospheric humidity. A similar approach could be employed in the future to improve stabilities of other optoelectronic devices based on water-sensitive species.

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NCs based optoelectronic devices such as photovoltaic cells, photodetectors and light emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide non-radiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligandexchange have been employed to improve the conductance of NC films. However, in light emitting devices, such surface modifications are more critical due to their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films, and investigate their performance in all-solution processed LEDs. The DiR films maintain high PLQY, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the PL. In the LEDs, the ligand-exchange boosted the luminance, reaching a four-fold increase from 2200 cd/m2 for native surfactants to 8500 cd/m2 for the exchanged aminoethanethiol ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 % to 5.4 %. We relate these improvements to the increased conductivity of the emissive layer, and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain deeper insight in the band alignment of the LED structure., Comment: 26 pages, 4 figures

Colloidal core/shell nanocrystals are key materials for optoelectronics, enabling control over essential properties via precise engineering of the shape, thickness, and crystal lattice structure of their shell. Here, we apply the growth protocol for CdS branched nanocrystals on CdSe nanoplatelet seeds and obtain bone-shaped heterostructures with a highly anisotropic shell. Surprisingly, the nanoplatelets withstand the high growth temperature of 350 {\deg}C and we obtain structures with a CdSe nanoplatelet core that is overcoated by a shell of cubic CdS, on top of which tetrahedral CdS structures with hexagonal lattice are formed. These complex core/shell nanocrystals show a bandedge emission around 657 nm with a photoluminescence quantum yield of ca. 42 % in solution, which is also retained in thin films. Interestingly, the nanocrystals manifest simultaneous red and green emission, and the relatively long wavelength of the green emission indicates charge recombination at the cubic/hexagonal interface of the CdS shell. The nanocrystal films show amplified spontaneous emission, random lasing, and distributed feedback lasing when the material is deposited on suitable gratings. Our work stimulates the design and fabrication of more exotic core/shell heterostructures where charge carrier delocalization, dipole moment, and other optical and electrical properties can be engineered., Comment: 26 pages, 6 figures, 1 table

The fabrication of electrochemical double-layer capacitors (EDLCs) with high areal capacitance relies on the use of elevated mass loadings of highly porous active materials. Herein, we demonstrate a high-throughput manufacturing of graphene/nanotubes hybrid EDLCs. Wet-jet milling (WJM) method is exploited to exfoliate the graphite into single/few-layer graphene flakes (WJM-G) in industrial volume (production rate ~0.5 kg/day). Commercial single/double walled carbon nanotubes (SDWCNTs) are mixed with graphene flakes in order to act as spacers between the graphene flakes during their film formation. The latter is obtained by one-step vacuum filtration, resulting in self-standing, metal- and binder-free flexible EDLC electrodes with high active material mass loadings up to 30 mg cm-2. The corresponding symmetric WJM-G/SDWCNTs EDLCs exhibit electrode energy densities of 539 uWh cm-2 at 1.3 mW cm-2 and operating power densities up to 532 mW cm-2 (outperforming most of the EDLC technologies). The EDCLs show excellent cycling stability and outstanding flexibility even under highly folded states (up to 180 degrees). The combination of industrial-like production of active materials, simplified manufacturing of EDLC electrodes, and ultrahigh areal performance of the as-produced EDLCs are promising for novel advanced EDLC designs.

Among the large family of transition metal dichalcogenides (TMDCs), recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties. These are related to its 1T distorted octahedral structure, which leads to strong in-plane anisotropy and the presence of active sites at its surface, which makes ReS2 interesting for applications such as gas sensors and catalysts for H2 production. However, the current fabrication methods for ReS2 use chemical or physical vapor deposition (CVD or PVD) processes that are costly and involve complex and lengthy fabrication procedures, therefore limiting their large-scale production and exploitation. To address this issue, we developed a colloidal synthesis approach, which allows the production of ReS2 to be attained at temperatures below 360 Celsius degrees and with reaction times < 2 h, resulting in a more cost-efficient strategy than the CVD and PVD methods. By combining the solution-based synthesis with surface functionalization strategies, we demonstrate the feasibility of colloidal ReS2 nanosheet films for gas sensing of different toxic gases, moisture and other volatile compounds with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2. In addition, the integration of the ReS2 nanosheet films in assemblies, in which they are deposited on top of networks of carbon nanotubes, allowed us to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential that is competitive with devices based on ReS2 produced by CVD, and even with MoS2, WS2 and MoSe2 electrocatalysts.

The design of efficient and cost-effective catalysts for the hydrogen evolution reaction (HER) is the key for molecular hydrogen (H2) production from electrochemical water splitting. Transition metal dichalcogenides (MX2), most notably group-6 MX2 (e.g., MoS2 and WS2), are appealing catalysts for the HER alternative to the best, but highly expensive, Pt-group elements. However, their HER activity is typically restricted to their edge sites rather than their basal plane. Furthermore, their semiconducting properties hinder an efficient electron transfer to the catalytic sites, which impedes a high rate of H2 production. Herein, we exploit liquid-phase exfoliation-produced metallic (1H, 2H and 3R) NbS2 nanoflakes, belonging to the class of metallic layered group-5 MX2, to overcome the abovementioned limitations. Both chemical treatment with hygroscopic Li salt and electrochemical in operando self-nanostructuring are exploited to improve the NbS2 nanoflake HER activity. The combination of NbS2 with other MX2, in our case MoSe2, also provides heterogeneous catalysts accelerating the HER kinetics of the individual counterparts. The designed NbS2-based catalysts exhibit an overpotential at a cathodic current of 10 mA cm-2 (n10) as low as 0.10 and 0.22 V vs. RHE in 0.5 M H2SO4 and 1 M KOH, respectively. In 0.5 M H2SO4, the HER activity of the NbS2-based catalysts is also superior to those of the Pt/C benchmark at current densities higher than 80 mA cm-2. Our work provides general guidelines for a scalable and cost-effective exploitation of NbS2, as well as the entire MX2 portfolio, for attaining a viable H2 production through electrochemical routes.

We report the first preparation of nanoporous Al-Mg alloy films by selective dissolution of Mg from a Mg-rich AlxMg1-x alloy. We show how to tune the stoichiometry, the porosity and the oxide contents in the final film by modulating the starting ratio between Al and Mg and the dealloying procedure. The obtained porous metal can be exploited for enhanced UV spectroscopy. In this respect, we experimentally demonstrate its efficacy in enhancing fluorescence and surface Raman scattering for excitation wavelengths of 360 nm and 257 nm respectively. Finally, we numerically show the superior performance of the nanoporous Al-Mg alloy in the UV range when compared to equivalent porous gold structures. The large area to surface ratio provided by this material make it a promising platform for a wide range of applications in UV/deep-UV plasmonics.

Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of beta-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g/L. Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. We demonstrate that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few um, and thicknesses ranging from 1 to 20 nm, with a max population centred at ~ 5 nm, corresponding to 4 Se-In-In-Se quaternary layers. We also show that no formation of further InSe-based compounds (such as In2Se3) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. We highlight the dependence of the InSe flakes morphologies, i.e., surface area and thickness, on the HER performances achieving best efficiencies with small flakes offering predominant edge effects. Our theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes., Comment: 39 pages

The miniaturization of energy storage units is pivotal for the development of next-generation portable electronic devices. Micro-supercapacitors (MSCs) hold a great potential to work as on-chip micro-power sources and energy storage units complementing batteries and energy harvester systems. The scalable production of supercapacitor materials with cost-effective and high-throughput processing methods is crucial for the widespread application of MSCs. Here, we report wet-jet milling exfoliation of graphite to scale-up the production of graphene as supercapacitor material. The formulation of aqueous/alcohol-based graphene inks allows metal-free, flexible MSCs to be screen-printed. These MSCs exhibit areal capacitance (Careal) values up to 1.324 mF cm-2 (5.296 mF cm-2 for a single electrode), corresponding to an outstanding volumetric capacitance (Cvol) of 0.490 F cm-3 (1.961 F cm-3 for a single electrode). The screen-printed MSCs can operate up to power density above 20 mW cm-2 at energy density of 0.064 uWh cm-2. The devices exhibit excellent cycling stability over charge-discharge cycling (10000 cycles), bending cycling (100 cycles at bending radius of 1 cm) and folding (up to angles of 180{\deg}). Moreover, ethylene vinyl acetate-encapsulated MSCs retain their electrochemical properties after a home-laundry cycle, providing waterproof and washable properties for prospective application in wearable electronics.

A novel WS2-graphite dual-ion battery (DIB) is developed by combining together a conventional graphite cathode and high-capacity few-layer WS2 flakes anode. The WS2 flakes are produced by exploiting wet-jet milling (WJM) exfoliation, which allows mass production of few-layer WS2 flakes in dispersion, with an exfoliation yield of 100%. The WS2-anodes enable DIBs, based on hexafluorophosphate (PF6-) and lithium (Li+) ions, to achieve charge specific capacities of 457, 438, 421, 403, 295 and 169 mAh g-1 at current rates of 0.1, 0.2, 0.3, 0.4, 0.8 and 1.0 A g-1, respectively, outperforming conventional DIBs. The WS2-based DIBs operate in the 0 to 4 V cell voltage range, thus extending the operating voltage window of conventional WS2-based Li-ion batteries (LIBs). These results demonstrate a new route towards the exploitation of WS2, and possibly other transition metal dichalcogenides (TMDs), for the development of next-generation energy storage devices.

Clean hydrogen production through efficient and cost-effective electrochemical water splitting is highly promising to meeting future global energy demands. The design of Earth-abundant materials with both high activity for hydrogen evolution reaction (HER) and electrochemical stability in both acidic and alkaline environments summarize the outcomes needed for practical applications. Here, we report a non-noble 3d metal Cl-chemical doping of liquid phase exfoliated single/few-layer flakes of MoSe2 for creating MoSe2 nanoflakes/3d metal oxide-hydr(oxy)oxide hybrid HER-catalysts. We propose that the electron-transfer from MoSe2 nanoflakes to metal cations and the chlorine complexation-induced both neutralization, as well as the in situ formation of metal oxide-hydr(oxy)oxides on MoSe2 nanoflake's surface, tailor the proton affinity of the derived catalysts, increasing the number and HER-kinetic of their active sites in both acidic and alkaline electrolytes. The electrochemical coupling between the doped-MoSe2 nanoflakes/metal oxide-hydr(oxy)oxide hybrids and single-walled carbon nanotubes heterostructures further accelerates the HER process. Lastly, monolithic stacking of multiple heterostructures is reported as a facile electrode assembly strategy to achieve overpotential for a cathodic current density of 10mAcm-2 of 0.081V and 0.064V in 0.5M H2SO4 and 1M KOH, respectively. This opens up new opportunities to address the current density vs. overpotential requirements targeted in pH-universal H2 production.

Interface engineering of organic-inorganic halide perovskite solar cells (PSCs) plays a pivotal role in achieving high power conversion efficiency (PCE). Graphene and related two-dimensional materials (GRMs) are promising candidates to tune on demand the interface properties of PSCs. In this work, we fully exploit the potential of GRMs by controlling the optoelectronic properties of hybrids between molybdenum disulfide (MoS2) and reduced graphene oxide (RGO) as hole transport layer (HTL) and active buffer layer (ABL) in mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite (MAPbI3)-based PSC. We show that zero-dimensional MoS2 quantum dots (MoS2 QDs), derived by liquid phase exfoliated MoS2 flakes, provide both hole-extraction and electron-blocking properties. In fact, on the one hand, intrinsic n-type doping-induced intra-band gap states effectively extract the holes through an electron injection mechanism. On the other hand, quantum confinement effects increase the optical band gap of MoS2 (from 1.4 eV for the flakes to > 3.2 for QDs), raising the minimum energy of its conduction band (from -4.3 eV for the flakes to -2.2 eV for QDs) above the one of conduction band of MAPbI3 (between -3.7 and -4 eV) and hindering electron collection. The van der Waals hybridization of MoS2 QDs with functionalized reduced graphene oxide (f-RGO), obtained by chemical silanization-induced linkage between RGO and (3-mercaptopropyl)trimethoxysilane, is effective to homogenize the deposition of HTLs or ABLs onto the perovskite film, since the two-dimensional (2D) nature of RGO effectively plug the pinholes of the MoS2 QDs films. Our graphene interface engineering (GIE) strategy based on van der Waals MoS2 QD/graphene hybrids enable MAPbI3-based PSCs to achieve PCE up to 20.12% (average PCE of 18.8%).

Two-dimensional transition metal-dichalcogenides are emerging as efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER). However, only the edge sites of their trigonal prismatic phase show HER-electrocatalytic properties, while the basal plane, which is absent of defective/unsaturated sites, is inactive. Here, we tackle the key challenge that is increasing the number of electrocatalytic sites by designing and engineering heterostructures composed of single-/few-layer MoSe2 flakes and carbon nanomaterials (graphene or single-wall carbon nanotubes (SWNTs)) produced by solution processing. The electrochemical coupling between the materials that comprise the heterostructure effectively enhances the HER-electrocatalytic activity of the native MoSe2 flakes. The optimization of the mass loading of MoSe2 flakes and their electrode assembly via monolithic heterostructure stacking provided a cathodic current density of 10mAcm-2 at overpotential of 100mV, a Tafel slope of 63mVdec-1 and an exchange current density (j0) of 0.203 Acm-2. In addition, electrode thermal annealing in a hydrogen environment and chemical bathing in n-butyllithium are exploited to texturize the basal planes of the MoSe2 flakes (through Se-vacancies creation) and to achieve in situ semiconducting-to-metallic phase conversion, respectively, thus they activate new HER-electrocatalytic sites. The as-engineered electrodes show a 4.8-fold enhancement of j0 and a decrease in the Tafel slope to 54mVdec-1.

This work reports the synthesis, the physicochemical characterization and the electrochemical studies of new electrocatalysts (ECs) for the oxygen reduction reaction (ORR) that: (i) are based on a hierarchical graphene-based support; and (ii) do not comprise platinum. The active sites of the ECs consist of Fe and Sn species stabilized in 'coordination nests' of a carbon nitride (CN) matrix. The latter exhibits a rough, microporous morphology and acts as a 'shell' covering a graphene 'core'. This paper: (i) discusses the role played by Fe as the 'active metal' in this family of ECs; and (ii) examines in detail how the physicochemical properties and, correspondingly, the electrochemical performance are affected by a suitable activation procedure A meant to boost the ORR kinetics. The results lead to an improved fundamental understanding on the features of the active sites, including the impact of both A and the pH of the environment in their performance and ORR mechanism. These insights clarify the most desirable features to be included in high-performing ECs belonging to this family, paving the way to the synthesis of next-generation, efficient ECs for the ORR that do not comprise platinum.

The synthesis of new 'Pt-free' electrocatalysts (ECs) for the oxygen reduction reaction (ORR) is reported. The ECs are characterized by a hierarchical 'core-shell' morphology; the 'core' is made of graphene, that is covered by a cratered, microporous carbon nitride (CN) 'shell'. The latter supports nanoparticles of M1 and Sn metals (M1 = Co; Ni) in 'coordination nests'. These latter are holes in the CN matrix, whose walls consist of N- and C-ligands. Two groups of ECs are studied: (i) 'pristine' ECs; and (ii) 'activated' ECs, that are obtained from the 'pristine' ECs by means of a suitable activation process (A) aimed at improving the performance in the ORR. Here is clarified the interplay existent between: (i) the chemical composition, morphology, structure and A; and (ii) the ORR performance and mechanism as a function of the pH of the environment. The resulting insights improve the fundamental understanding of this family of ECs and open the door to the devising of new preparations of 'Pt-free' ECs for the ORR, which: (i) are stabilized by a CN matrix and; (ii) exhibit an improved performance.

We designed solution-processed, flexible hybrid graphene flake/2H-MoS2 quantum dot (QD) heterostructures, showing enhanced electrocatalytic activity for the hydrogen evolution reaction (HER) with respect to their native individual components. The 2H-MoS2 QDs are produced through a scalable, environmentally friendly, one-step solvothermal approach from two-dimensional (2D) 2H-MoS2 flakes obtained by liquid phase exfoliation (LPE) of their bulk counterpart in 2-Propanol. This QDs synthesis avoids the use of high boiling point and/or toxic solvents. Graphene flakes are produced by LPE of graphite in N-Methyl-2-pyrrolidone. The electrochemical properties of 2H-MoS2 QDs and their HER-favorable chemical and electronic coupling with graphene enable to reach a current density of 10 mA/cm^2 at an overpotential of 136 mV, surpassing the performances of graphene flake/2H-MoS2 (1T-MoS2) flake heterostructures. Our approach provides a shortcut, viable and cost-effective method for enhancing the 2D materials electrocatalytic properties., Comment: 31 pages, 15 figures

Regio-regular poly(3-hexylthiophene-2,5-diyl) (rr-P3HT), the work-horse of organic photovoltaics, has been recently exploited in bulk heterojunction (BHJ) configuration with phenyl-C61-butyric acid methyl ester (PCBM) for solution-processed hydrogen-evolving photocathodes, reaching cathodic photocurrents at 0 V vs. RHE (J0V vs RHE) of up to 8 mA cm-2. The photoelectrochemical performance of these photocathodes strongly depends on the presence of the electron (ESL) and hole (HSL) selective layer. While TiO2 and its sub-stoichiometric phases are consolidated ESL materials, the currently used HSLs (e.g., MoO3, CuI, PEDOTT:PSS, WO3) suffer electrochemical degradation under hydrogen evolution reaction (HER)-working conditions. In this work, we use solution-processed graphene derivatives as HSL to boost efficiency and durability of rr-P3HT:PCBM-based photocathodes, demonstrating record-high performance. In fact, our devices show cathodic J0V vs RHE of 6.01 mA cm-2, onset potential (Vo) of 0.6 V vs. RHE, ratiometric power-saved efficiency ({\phi}saved) of 1.11% and operational activity of 20 hours in 0.5 M H2SO4 solution. Moreover, the designed photocathodes are effectively working in different pH environments ranging from acid to basic. This is pivotal for their exploitation in tandem configurations, where photoanodes operate only in restricted electrochemical conditions. Furthermore, we demonstrate the scalability of our all-solution processed approach by fabricating a large-area (~9 cm2) photocathode on flexible substrate, achieving remarkable cathodic J0V vs RHE of 2.8 mA cm-2, Vo of 0.45 V vs. RHE and {\phi}saved of 0.31%. This is the first demonstration of high-efficient rr-P3HT:PCBM flexible photocathodes based on low-cost and solution-processed manufacturing techniques.

In the past couple of decades, colloidal inorganic nanocrystals and, more specifically, semiconductor quantum dots have emerged as crucial materials for the development of nanoscience and nanotechnology, with applications in very diverse areas such as optoelectronics and biotechnology. Films made of inorganic NCs deposited on a substrate can be patterned by e-beam lithography, altering the structure of their capping ligands and thus allowing exposed areas to remain on the substrate while non-exposed areas are redispersed in a solvent, as in a standard lift-off process. This methodology can be described as a direct lithography process, since the exposure is performed directly on the material of interest, in contrast with conventional lithography which uses a polymeric resist as a mask for subsequent material deposition or etching. A few reports from the late 1990 and early 2000 used such direct lithography to fabricate electrical wires from metallic NCs. However, the poor conductivity obtained through this process hindered the widespread use of the technique. In the early 2010, the same method was used to define fluorescent patterns on QD films, allowing for further applications in biosensing. For the past 2 ,3 years, direct lithography on NC films with e-beams and X rays has gone through an important development as it has been demonstrated that it can tune further transformations on the NCs, leading to more complex patternings and opening a whole new set of possible applications., Comment: 21 pages, 8 figures

We report the colloidal synthesis of strongly fluorescent CsPbBr3 perovskite nanowires (NWs) with rectangular section and with tuneable width, from 20 nm (exhibiting no quantum confinement, hence emitting in the green) down to around 3 nm (in the strong quan-tum-confinement regime, emitting in the blue), by introducing in the synthesis a short acid (octanoic acid or hexanoic acid) together with alkyl amines (octylamine and oleylamine). Temperatures below 70 {\deg}C promoted the formation of monodisperse, few unit cell thick NWs that were free from byproducts. The photoluminescence quantum yield of the NW samples went from 12% for non-confined NWs emitting at 524 nm to a maximum of 77% for the 5 nm diameter NWs emitting at 497 nm, down to 30% for the thinnest NWs (diameter ~ 3nm), in the latter sample most likely due to aggregation occurring in solution., Comment: 5 pages, 4 figures