Hydrogen-Assisted Thermal Treatment of Electrode Materials for Electrochemical Double-Layer Capacitors.

The capacitance of electrode materials used in electrochemical double-layer capacitors (EDLCs) is currently limited by several factors, including inaccessible isolated micropores in high-surface area carbons, the finite density of states resulting in a quantum capacitance in series to Helmholtz double-layer capacitance, and the presence of surface impurities, such as functional groups and adsorbed species. To unlock the full potential of EDLC active materials and corresponding electrodes, several post-production treatments are commonly proposed to improve their capacitance and, thus, the energy density of the corresponding devices. In this work, we report a systematic study of the effect of a prototypical treatment, namely H2-assisted thermal treatment, on the chemical, structural, and thermal properties of activated carbon and corresponding electrodes. By combining multiple characterization techniques, we clarify the actual origins of the improvement of the performance (e.g., > +35% energy density for the investigated power densities in the 0.5-45 kW kg-1 range) of the EDLCs based on treated electrodes compared to the case based on the pristine electrodes. Contrary to previous works supporting a questionable graphitization of the activated carbon at temperatures <1000 °C, we found that a "surface graphitization" of the activated carbon, detected by spectroscopic analysis, is mainly associated with the desorption of surface contaminants. The elimination of surface impurities, including adsorbed species, improves the surface capacitance of the activated carbon (CsurfAC) by +37.1 and +36.3% at specific currents of 1 and 10 A g-1, respectively. Despite the presence of slight densification of the activated carbon upon the thermal treatment, the latter still improves the cell gravimetric capacitance normalized on the mass of the activated carbon only (CgAC), e.g., + 28% at 1 A g-1. Besides, our holistic approach identifies the change in the active material and binder contents as a concomitant cause of the increase of cell gravimetric capacitance (Cg), accounting for the mass of all of the electrode materials measured for treated electrodes compared to pristine ones. Overall, this study provides new insights into the relationship between the modifications of the electrode materials induced by H2-assisted thermal treatments and the performance of the resulting EDLCs.

Stable Sn-Based Hybrid Perovskite-Related Structures with Tunable Color Coordinates via Organic Cations in Low-Temperature Synthesis.

Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead common practice in Pb-based structures. Here, we present a set of Sn-Br layered perovskite-related structures that display different chromaticity coordinates and photoluminescence quantum yield (PLQY) up to 80%, depending on the choice of the organic monocation. We first develop a synthetic protocol that is performed under air and at 4 °C, requiring only a few steps. X-ray and 3D electron diffraction analyses show that the structures exhibit diverse octahedra connectivity (disconnected and face-sharing) and thus optical properties, while preserving the organic-inorganic layer intercalation. These results provide key insight into a previously underexplored strategy to tune the color coordinates of Pb-free layered perovskites through organic cations with complex molecular configurations.

Cell-Membrane-Coated and Cell-Penetrating Peptide-Conjugated Trimagnetic Nanoparticles for Targeted Magnetic Hyperthermia of Prostate Cancer Cells.

Prostate malignancy represents the second leading cause of cancer-specific death among the male population worldwide. Herein, enhanced intracellular magnetic fluid hyperthermia is applied in vitro to treat prostate cancer (PCa) cells with minimum invasiveness and toxicity and highly specific targeting. We designed and optimized novel shape-anisotropic magnetic core-shell-shell nanoparticles (i.e., trimagnetic nanoparticles - TMNPs) with significant magnetothermal conversion following an exchange coupling effect to an external alternating magnetic field (AMF). The functional properties of the best candidate in terms of heating efficiency (i.e., Fe3O4@Mn0.5Zn0.5Fe2O4@CoFe2O4) were exploited following surface decoration with PCa cell membranes (CM) and/or LN1 cell-penetrating peptide (CPP). We demonstrated that the combination of biomimetic dual CM-CPP targeting and AMF responsiveness significantly induces caspase 9-mediated apoptosis of PCa cells. Furthermore, a downregulation of the cell cycle progression markers and a decrease of the migration rate in surviving cells were observed in response to the TMNP-assisted magnetic hyperthermia, suggesting a reduction in cancer cell aggressiveness.

Mixed Organic Cations Promote Ambient Light-Induced Formation of Metallic Lead in Lead Halide Perovskite Crystals.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

Cerium Oxide Nanoparticle Administration to Skeletal Muscle Cells under Different Gravity and Radiation Conditions.

For their remarkable biomimetic properties implying strong modulation of the intracellular and extracellular redox state, cerium oxide nanoparticles (also termed "nanoceria") were hypothesized to exert a protective role against oxidative stress associated with the harsh environmental conditions of spaceflight, characterized by microgravity and highly energetic radiations. Nanoparticles were supplied to proliferating C2C12 mouse skeletal muscle cells under different gravity and radiation levels. Biological responses were thus investigated at a transcriptional level by RNA next-generation sequencing. Lists of differentially expressed genes (DEGs) were generated and intersected by taking into consideration relevant comparisons, which led to the observation of prevailing effects of the space environment over those induced by nanoceria. In space, upregulation of transcription was slightly preponderant over downregulation, implying involvement of intracellular compartments, with the majority of DEGs consistently over- or under-expressed whenever present. Cosmic radiations regulated a higher number of DEGs than microgravity and seemed to promote increased cellular catabolism. By taking into consideration space physical stressors alone, microgravity and cosmic radiations appeared to have opposite effects at transcriptional levels despite partial sharing of molecular pathways. Interestingly, gene ontology denoted some enrichment in terms related to vision, when only effects of radiations were assessed. The transcriptional regulation of mitochondrial uncoupling protein 2 in space-relevant samples suggests perturbation of the intracellular redox homeostasis, and leaves open opportunities for antioxidant treatment for oxidative stress reduction in harsh environments.

Two-Step Thermal Annealing: An Effective Route for 15 % Efficient Quasi-2D Perovskite Solar Cells.

Invited for this month's cover are collaborators from University of Pavia, École Polytechnique Fédérale de Lausanne, University of Messina and Istituto Italiano di Tecnologia. The cover picture shows the crystal structure of a Ruddlesden-Popper quasi-2D perovskite with chemical formula (PEA)2 MA39 Pb40 I121 (with PEA: phenylethylammonium and MA: methylammonium). The subscript 40 indicates the number of PbI6 octahedra separated by a double layer of PEA cations. Such quasi-2D perovskites exhibit efficient photovoltaic performances and higher stability with respect to the pure 3D counterpart (MAPbI3 ). This article is part of the Special Collection on "Perovskite Materials and Devices". Read the full text of the article at 10.1002/cplu.202000777.

Two-Step Thermal Annealing: An Effective Route for 15 % Efficient Quasi-2D Perovskite Solar Cells.

Low-dimensional perovskites (LDP) are nowadays recognized as promising materials for the realization of highly performing photovoltaic cells. However, issues related to film morphology, composition, crystal quality and material homogeneity limit the device performances and reproducibility. In this work, we implement a robust method for the deposition of a LDP mixing methylammonium (MA) and phenylethylammonium (PEA) cations to create the mixed system (PEA)2 MA39 Pb40 I121 by using a two-step thermal annealing treatment (at 60 and 100 °C). Our approach results in LDP films with high crystal quality and enhanced carrier lifetime, which double the power conversion efficiency of reference devices, reaching up to 15 %.

Multilayer Diffraction Reveals That Colloidal Superlattices Approach the Structural Perfection of Single Crystals.

Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called "atomically precise". That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, the constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of the nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr3 and PbS nanomaterials. The multilayer diffraction method requires only a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis. The average nanocrystal displacement of 0.33 to 1.43 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals.

Towards enhanced sodium storage of anatase TiO2via a dual-modification approach of Mo doping combined with AlF3 coating.

Recent studies on anatase TiO2 have demonstrated its capability of performing as an anode material for sodium-ion batteries (SIBs) even though, due to poor conductivity, realistic applications have not yet been foreseen. In order to try to address this issue, herein, we shall introduce a cost effective and facile route based on the co-precipitation method for the synthesis of Mo-doped anatase TiO2 nanoparticles with AlF3 surface coating. The electrochemical measurements demonstrate that the Mo-doped anatase TiO2 nanoparticles deliver an ∼40% enhanced reversible capacity compared to pristine TiO2 (139.8 vs. 100.7 mA h g-1 at 0.1 C after 50 cycles) due to an improved electronic/ionic conductivity. Furthermore, upon AlF3 coating, the overall system can deliver a much higher reversible capacity of 178.9 mA h g-1 (∼80% increase with respect to pristine TiO2) with good cycling stability and excellent rate capabilities of up to 10 C. The experimental results indicate that the AlF3 surface coating could indeed effectively reduce the solid electrolyte interfacial resistance, enhance the electrochemical reactivity at the surface/interface region, and lower the polarization during cycling. The improved performance achieved using a cost-effective fabrication approach makes the dually modified anatase TiO2 a promising anode material for high-performance SIBs.

Macroscopic Versus Microscopic Schottky Barrier Determination at (Au/Pt)/Ge(100): Interfacial Local Modulation.

Macroscopic current-voltage measurements and nanoscopic ballistic electron emission spectroscopy (BEES) have been used to probe the Schottky barrier height (SBH) at metal/Ge(100) junctions for two metal electrodes (Au and Pt) and different metallization methods, specifically, thermal-vapor and laser-vapor deposition. Analysis of macroscopic current-voltage characteristics indicates that a SBH of 0.61-0.63 eV controls rectification at room temperature. On the other hand, BEES measured at 80 K reveals the coexistence of two distinct barriers at the nanoscale, taking values in the ranges 0.61-0.64 and 0.70-0.74 eV for the cases studied. For each metal-semiconductor junction, the macroscopic measurement agrees well with the lower barrier found with BEES. Ab initio modeling of BEES spectra ascribes the two barriers to two different atomic registries between the metals and the Ge(100) surface, a significant relevant insight for next-generation highly miniaturized Ge-based devices.

Metastable CdTe@HgTe Core@Shell Nanostructures Obtained by Partial Cation Exchange Evolve into Sintered CdTe Films Upon Annealing.

Partial Hg2+ → Cd2+ cation exchange (CE) reactions were exploited to transform colloidal CdTe nanocrystals (NCs, 4-6 nm in size) into CdTe@HgTe core@shell nanostructures. This was achieved by working under a slow CE rate, which limited the exchange to the surface of the CdTe NCs. In such nanostructures, when annealed at mild temperatures (as low as 200 °C), the HgTe shell sublimated or melted and the NCs sintered together, with the concomitant desorption of their surface ligands. At the end of this process, the annealed samples consisted of ligand-free CdTe sintered films containing an amount of Hg2+ that was much lower than that of the starting CdTe@HgTe NCs. For example, the CdTe@HgTe NCs that initially contained 10% of Hg2+, after being annealed at 200 °C were transformed to CdTe sintered films containing only traces of Hg2+ (less than 1%). This procedure was then used to fabricate a proof-of-concept CdTe-based photodetector exhibiting a photoresponse of up to 0.5 A/W and a detectivity of ca. 9 × 104 Jones under blue light illumination. Our strategy suggests that CE protocols might be exploited to lower the overall costs of production of CdTe thin films employed in photovoltaic technology, which are currently fabricated at high temperatures (above 350 °C), using post-process ligand-stripping steps.

Cs3Cu4In2Cl13 Nanocrystals: A Perovskite-Related Structure with Inorganic Clusters at A Sites.

An effort to synthesize the Cu(I) variant of a lead-free double perovskite isostructural with Cs2AgInCl6 resulted in the formation of Cs3Cu4In2Cl13 nanocrystals with an unusual structure, as revealed by single-nanocrystal three-dimensional electron diffraction. These nanocrystals adopt a A2BX6 structure (K2PtCl6 type, termed vacancy ordered perovskite) with tetrahedrally coordinated Cu(I) ions. In the structure, 25% of the A sites are occupied by [Cu4Cl]3+ clusters (75% by Cs+), and the B sites are occupied by In3+. Such a Cs3Cu4In2Cl13 compound prepared at the nanoscale is not known in the bulk and is an example of a multinary metal halide with inorganic cluster cations residing in A sites. The stability of the compound was supported by density functional theory calculations that also revealed that its bandgap is direct but parity forbidden. The existence of the Cs3Cu4In2Cl13 structure demonstrates that small inorganic cluster cations can occupy A sites in multinary metal halides.

Green Composites of Poly(3-hydroxybutyrate) Containing Graphene Nanoplatelets with Desirable Electrical Conductivity and Oxygen Barrier Properties.

Poly(3-hydroxybutyrate), a green polymer originating from prokaryotic microbes, has been used to prepare composites with graphene nanoplatelets (GnP) at different concentrations. The films were fabricated by drop-casting and were hot-pressed at a temperature lower than their melting point to provide the molecular chains enough energy to reorientate while avoiding melting and degradation. It was found that hot-pressing increases crystallinity and improves mechanical properties. The Young's modulus increased from 1.2 to 1.6 GPa for the poly(3-hydroxybutyrate) (P(3HB)) films and from 0.5 to 2.2 GPa for the 15 wt % P(3HB)/GnP composites. Electrical resistivity decreases enormously with GnP concentration and hot-pressing, reaching 6 Ω sq-1 for the hot-pressed 30 wt % P(3HB)/GnP composite. Finally, the hot-pressed P(3HB) samples exhibit remarkable oxygen barrier properties, with oxygen permeability reaching 2800 mL µm m-2 day-1, which becomes 895 mL µm m-2 day-1 when 15% GnP is added to the biopolymer matrix, one of the lowest values known for biopolymers and biocomposites. We propose that these biocomposites are used for elastic packaging and electronics.

Sustainable Active Food Packaging from Poly(lactic acid) and Cocoa Bean Shells.

Sustainable biocomposites have been developed by solvent mixing of poly(lactic acid) (PLA) with a fine powder of cocoa bean shells (CBS) and subsequent solution casting, using different concentrations of CBS. The inclusion of CBS recovers the crystallinity of the initially amorphous PLA films and improves the physical properties of the composites. Young's modulus increases by 80% with 75 wt % CBS inclusion; however, the composites maintain plasticity. The barrier properties of the hydrophobic composites were characterized, and the water vapor permeability is found to be ca. 3.5 × 10-5 g·m-1·day-1·Pa-1 and independent of the CBS content. On the other hand, oxygen permeability is found to depend on the CBS content, with values as low as 10 000 mL·µm·m-2·day-1·atm-1 for 50 wt % CBS. Furthermore, CBS confer antioxidant activity to the composites and improve swelling properties rendering the composites biodegradable in aquatic environments, reaching 70% of the maximum biodegradability in just 30 days. The above, in conjunction with the low level of migration measured in food simulant, make the PLA/CBS composites a highly promising material for active food packaging.

Carbon Dots from Citric Acid and its Intermediates Formed by Thermal Decomposition.

Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluorescent C-dots from citric acid has been studied as a function of reaction time by coupling infrared analysis, X-ray photoelectron spectroscopy, liquid chromatography/mass spectroscopy (LC/MS) with the change of the optical properties, absorption and emission. The reaction intermediates, which have been identified at different stages, produce two main emissive species, in the green and blue, as also indicated by the decay time analysis. C-dots formed from the intermediates have also been synthesised by thermal decomposition, which gave an emission maximum around 450 nm. The citric acid C-dots in water show short temporal stability, but their functionalisation with 3-aminopropyltriethoxysilane reduces the quenching. The understanding of the citric acid thermal decomposition reaction is expected to improve the control and reproducibility of C-dots synthesis.

Transparent and Robust All-Cellulose Nanocomposite Packaging Materials Prepared in a Mixture of Trifluoroacetic Acid and Trifluoroacetic Anhydride.

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young's modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films.

Wide-Angle X-ray Diffraction Evidence of Structural Coherence in CsPbBr3 Nanocrystal Superlattices.

Films made of colloidal CsPbBr3 nanocrystals packed in isolated or densely-packed superlattices display a remarkably high degree of structural coherence. The structural coherence is revealed by the presence of satellite peaks accompanying Bragg reflections in wide-angle X-ray diffraction experiments in parallel-beam reflection geometry. The satellite peaks, also called "superlattice reflections", arise from the interference of X-rays diffracted by the atomic planes of the orthorhombic perovskite lattice. The interference is due to the precise spatial periodicity of the nanocrystals separated by organic ligands in the superlattice. The presence of satellite peaks is a fingerprint of the high crystallinity and long-range order of nanocrystals, comparable to those of multilayer superlattices prepared by physical methods. The angular separation between satellite peaks is highly sensitive to changes in the superlattice periodicity. These characteristics of the satellite peaks are exploited to track the superlattice compression under vacuum, as well as to observe the superlattice growth in situ from colloidal solutions by slow solvent evaporation.

Fe2+ Deficiencies, FeO Subdomains, and Structural Defects Favor Magnetic Hyperthermia Performance of Iron Oxide Nanocubes into Intracellular Environment.

Herein, by studying a stepwise phase transformation of 23 nm FeO-Fe3O4 core-shell nanocubes into Fe3O4, we identify a composition at which the magnetic heating performance of the nanocubes is not affected by the medium viscosity and aggregation. Structural and magnetic characterizations reveal the transformation of the FeO-Fe3O4 nanocubes from having stoichiometric phase compositions into Fe2+-deficient Fe3O4 phases. The resultant nanocubes contain tiny compressed and randomly distributed FeO subdomains as well as structural defects. This phase transformation causes a 10-fold increase in the magnetic losses of the nanocubes, which remain exceptionally insensitive to the medium viscosity as well as aggregation unlike similarly sized single-phase magnetite nanocubes. We observe that the dominant relaxation mechanism switches from Néel in fresh core-shell nanocubes to Brownian in partially oxidized nanocubes and once again to Néel in completely treated nanocubes. The Fe2+ deficiencies and structural defects appear to reduce the magnetic energy barrier and anisotropy field, thereby driving the overall relaxation into Néel process. The magnetic losses of these nanoparticles remain unchanged through a progressive internalization/association to ovarian cancer cells. Moreover, the particles induce a significant cell death after being exposed to hyperthermia treatment. Here, we present the largest heating performance that has been reported to date for 23 nm iron oxide nanoparticles under intracellular conditions. Our findings clearly demonstrate the positive impacts of the Fe2+ deficiencies and structural defects in the Fe3O4 structure on the heating performance into intracellular environment.

Understanding and tailoring ligand interactions in the self-assembly of branched colloidal nanocrystals into planar superlattices.

Colloidal nanocrystals can self-assemble into highly ordered superlattices. Recent studies have focused on changing their morphology by tuning the nanocrystal interactions via ligand-based surface modification for simple particle shapes. Here we demonstrate that this principle is transferable to and even enriched in the case of a class of branched nanocrystals made of a CdSe core and eight CdS pods, so-called octapods. Through careful experimental analysis, we show that the octapods have a heterogeneous ligand distribution, resembling a cone wrapping the individual pods. This induces location-specific interactions that, combined with variation of the pod aspect ratio and ligands, lead to a wide range of planar superlattices assembled at an air-liquid interface. We capture these findings using a simple simulation model, which reveals the necessity of including ligand-based interactions to achieve these superlattices. Our work evidences the sensitivity that ligands offer for the self-assembly of branched nanocrystals, thus opening new routes for metamaterial creation.

Nitrogen-Doped Single-Walled Carbon Nanohorns as a Cost-Effective Carbon Host toward High-Performance Lithium-Sulfur Batteries.

Nitrogen-doped single-walled carbon nanohorns (N-SWCNHs) are porous carbon material characterized by unique horn-shape structures with high surface areas and good conductivity. Moreover, they can be mass-produced (tons/year) using a novel proprietary process technology making them an attractive material for various industrial applications. One of the applications is the encapsulation of sulfur, which turns them as promising conductive host materials for lithium-sulfur batteries. Therefore, we explore for the first time the electrochemical performance of industrially produced N-SWCNHs as a sulfur-encapsulating conductive material. Fabrication of lithium-sulfur cells based on N-SWCNHs with sulfur composite could achieve a remarkable initial gravimetric capacity of 1650 mA h g-1, namely equal to 98.5% of the theoretical capacity (1675 mA h g-1), with an exceptional sulfur content as high as 80% in weight. Using cyclic chronopotentiometry and impedance spectroscopy, we also explored the dissolution mechanism of polysulfides inside the electrolyte.