Efficient photoactivated hydrogen evolution promoted by CuxO-gCN-TiO2-Au (x = 1,2) nanoarchitectures.

In this work, we propose an original and potentially scalable synthetic route for the fabrication of CuxO-gCN-TiO2-Au (x = 1,2) nanoarchitectures, based on Cu foam anodization, graphitic carbon nitride liquid-phase deposition, and TiO2/Au sputtering. A thorough chemico-physical characterization by complementary analytical tools revealed the formation of nanoarchitectures featuring an intimate contact between the system components and a high dispersion of gold nanoparticles. Modulation of single component interplay yielded excellent functional performances in photoactivated hydrogen evolution, corresponding to a photocurrent of ≈-5.7 mA cm-2 at 0.0 V vs. the reversible hydrogen electrode (RHE). These features, along with the very good service life, represent a cornerstone for the conversion of natural resources, as water and largely available sunlight, into added-value solar fuels.

Charge Storage Mechanism in Electrospun Spinel-Structured High-Entropy (Mn0.2 Fe0.2 Co0.2 Ni0.2 Zn0.2 )3 O4 Oxide Nanofibers as Anode Material for Li-Ion Batteries.

High-entropy oxides (HEOs) have emerged as promising anode materials for next-generation lithium-ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen-deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li+ storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X-ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal-forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe3+ , Co3+ /Co2+ , and Ni2+ , undergo reduction to Fe0 , Co0 , and Ni0 to different extent (Fe < Co < Ni). Manganese undergoes partial reduction to Mn3+ /Mn2+ and, upon re-oxidation, does not revert to the pristine oxidation state (+4). Zn2+ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li-ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed.

Interplay between coordination sphere engineering and properties of nickel diketonate-diamine complexes as vapor phase precursors for the growth of NiO thin films.

NiO-based films and nanostructured materials have received increasing attention for a variety of technological applications. Among the possible strategies for their fabrication, atomic layer deposition (ALD) and chemical vapor deposition (CVD), featuring manifold advantages of technological interest, represent appealing molecule-to-material routes for which a rational precursor design is a critical step. In this context, the present study is focused on the coordination sphere engineering of three heteroleptic Ni(II) ß-diketonate-diamine adducts of general formula [NiL2TMEDA] [L = 1,1,1-trifluoro-2,4-pentanedionate (tfa), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate (fod) or 2,2,6,6-tetramethyl-3,5-heptanedionate (thd), and TMEDA = N,N,N',N'-tetramethylethylenediamine]. Controlled variations in the diketonate structure are pursued to investigate the influence of steric hindrance and fluorination degree on the chemico-physical characteristics of the compounds. A multi-technique investigation supported by density functional calculations highlights that all complexes are air-insensitive and monomeric and that their thermal properties and fragmentation patterns are directly dependent on functional groups in the diketonate ligands. Preliminary thermal CVD experiments demonstrate the precursors' suitability for the obtainment of NiO films endowed with flat and homogeneous surfaces, paving the way to future implementation for CVD end-uses.

Structure and magnetism of electrospun porous high-entropy (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4, (Cr1/5Mn1/5Fe1/5Co1/5Zn1/5)3O4 and (Cr1/5Mn1/5Fe1/5Ni1/5Zn1/5)3O4 spinel oxide nanofibers.

High-entropy oxide nanofibers, based on equimolar (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations, were prepared by electrospinning followed by calcination. The obtained hollow nanofibers exhibited a porous structure consisting of interconnected nearly strain-free (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4, (Cr1/5Mn1/5Fe1/5Co1/5Zn1/5)3O4 and (Cr1/5Mn1/5Fe1/5Ni1/5Zn1/5)3O4 single crystals with a pure Fd3̄m spinel structure. Oxidation state of the cations at the nanofiber surface was assessed by X-ray photoelectron spectroscopy and cation distributions were proposed satisfying electroneutrality and optimizing octahedral stabilization. The magnetic data are consistent with a distribution of cations that satisfies the energetic preferences for octahedral vs. tetrahedral sites and is random only within the octahedral and tetrahedral sublattices. The nanofibers are ferrimagnets with relatively low critical temperature more similar to cubic chromites and manganites than to ferrites. Replacing the magnetic cations Co or Ni with non-magnetic Zn lowers the critical temperature from 374 K (Cr,Mn,Fe,Co,Ni) to 233 and 105 K for (Cr,Mn,Fe,Ni,Zn) and (Cr,Mn,Fe,Co,Zn), respectively. The latter nanofibers additionally have a low temperature transition to a reentrant spin-glass-like state.

Quantum view of Li-ion high mobility at carbon-coated cathode interfaces.

Lithium-ion batteries (LIBs) are among the most promising power sources for electric vehicles, portable electronics and smart grids. In LIBs, the cathode is a major bottleneck, with a particular reference to its low electrical conductivity and Li-ion diffusivity. The coating with carbon layers is generally employed to enhance the electrical conductivity and to protect the active material from degradation during operation. Here, we demonstrate that this layer has a primary role in the lithium diffusivity into the cathode nanoparticles. Positron is a useful quantum probe at the electroactive materials/carbon interface to sense the mobility of Li-ion. Broadband electrical spectroscopy demonstrates that only a small number of Li-ions are moving, and that their diffusion strongly depends on the type of carbon additive. Positron annihilation and broadband electrical spectroscopies are crucial complementary tools to investigate the electronic effect of the carbon phase on the cathode performance and Li-ion dynamics in electroactive materials.

Effect of Relaxations on the Conductivity of La1/2+1/2x Li1/2-1/2x Ti1-x Al x O3 Fast Ion Conductors.

Perovskite-type solid-state electrolytes, Li3x La2/3-x TiO3 (LLTO), are considered among the most promising candidates for the development of all-solid-state batteries based on lithium metal. Their high bulk ionic conductivity can be modulated by substituting part of the atoms hosted in the A- or B-site of the LLTO structure. In this work, we investigate the crystal structure and the long-range charge migration processes characterizing a family of perovskites with the general formula La1/2+1/2x Li1/2-1/2x Ti1-x Al x O3 (0 ≤ x ≤ 0.6), in which the charge balance and the nominal A-site vacancies (n A = 0) are preserved. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations reveal the presence of a very complex nanostructure constituted by a mixture of two different ordered nanoregions of tetragonal P4/mmm and rhombohedral R3̅c symmetries. Broadband electrical spectroscopy studies confirm the presence of different crystalline domains and demonstrate that the structural fluctuations of the BO6 octahedra require to be intra- and intercell coupled, to enable the long-range diffusion of the lithium cation, in a similar way to the segmental mode that takes place in polymer-ion conductors. These hypotheses are corroborated by density functional theory (DFT) calculations and molecular dynamic simulations.

What is Next in Anion-Exchange Membrane Water Electrolyzers? Bottlenecks, Benefits, and Future.

As highlighted by the recent roadmaps from the European Union and the United States, water electrolysis is the most valuable high-intensity technology for producing green hydrogen. Currently, two commercial low-temperature water electrolyzer technologies exist: alkaline water electrolyzer (A-WE) and proton-exchange membrane water electrolyzer (PEM-WE). However, both have major drawbacks. A-WE shows low productivity and efficiency, while PEM-WE uses a significant amount of critical raw materials. Lately, the use of anion-exchange membrane water electrolyzers (AEM-WE) has been proposed to overcome the limitations of the current commercial systems. AEM-WE could become the cornerstone to achieve an intense, safe, and resilient green hydrogen production to fulfill the hydrogen targets to achieve the 2050 decarbonization goals. Here, the status of AEM-WE development is discussed, with a focus on the most critical aspects for research and highlighting the potential routes for overcoming the remaining issues. The Review closes with the future perspective on the AEM-WE research indicating the targets to be achieved.

Enhancement of Activity and Development of Low Pt Content Electrocatalysts for Oxygen Reduction Reaction in Acid Media.

Platinum is a main catalyst for the electroreduction of oxygen, a reaction of primary importance to the technology of low-temperature fuel cells. Due to the high cost of platinum, there is a need to significantly lower its loadings at interfaces. However, then O2-reduction often proceeds at a less positive potential, and produces higher amounts of undesirable H2O2-intermediate. Hybrid supports, which utilize metal oxides (e.g., CeO2, WO3, Ta2O5, Nb2O5, and ZrO2), stabilize Pt and carbon nanostructures and diminish their corrosion while exhibiting high activity toward the four-electron (most efficient) reduction in oxygen. Porosity of carbon supports facilitates dispersion and stability of Pt nanoparticles. Alternatively, the Pt-based bi- and multi-metallic catalysts, including PtM alloys or M-core/Pt-shell nanostructures, where M stands for certain transition metals (e.g., Au, Co, Cu, Ni, and Fe), can be considered. The catalytic efficiency depends on geometric (decrease in Pt-Pt bond distances) and electronic (increase in d-electron vacancy in Pt) factors, in addition to possible metal-support interactions and interfacial structural changes affecting adsorption and activation of O2-molecules. Despite the stabilization of carbons, doping with heteroatoms, such as sulfur, nitrogen, phosphorus, and boron results in the formation of catalytically active centers. Thus, the useful catalysts are likely to be multi-component and multi-functional.

Electric Response and Conductivity Mechanism of Blended Polyvinylidene Fluoride/Nafion Electrospun Nanofibers.

The electrical relaxation and polarization phenomena of electrospun PVDF (P)/Nafion (N) blended fiber mats ([P/N0.9]M and ß-[P]M) and membranes ([P/N0.9]MM) are compared with those of the solvent-cast membrane of identical composition ([N]C and [P/N0.9]C). The nature of the interactions between the two blended polymer components, that plays a pivotal role in the electrical nature of the resulting materials, is found to be governed by the fabrication method, with those materials obtained via electrospinning undergoing a "reciprocal templating" phenomenon that renders their electrical behavior (especially when in the dry state) significantly different from that of the blended membrane obtained via solvent casting. Broadband Electrical Spectroscopy (BES) demonstrates that the electric response of the blended materials is modulated by polarization phenomena and by α, ß, and γ dielectric relaxation events of Nafion domains supported on ß-PVDF. The coupling between the relaxations of ß-PVDF with those of Nafion matrix is directly correlated to the "reciprocal templating" effect, which modulates the interactions between Nafion and PVDF in electrospun membranes. Two types of conductivity mechanisms characterize the H+ migration within the polymer blends: (1) interdomain H+ migration events by "charge-exchange" phenomena along percolation pathways and (2) H+ exchange between delocalization bodies (DBs) at binding sites at the interface between domains with different ε, size, and morphology. The electrical response of the electrospun membranes also suggests that they do not comprise water clusters with a large size such as those typically observed in pristine Nafion. Rather, the adsorbed H2O molecules, under wet conditions, form thin solvation shells wrapping the polar side chains of the Nafion component. At T = 80 °C, the conductivity of the studied materials decreases in the order [N]C (0.043 S·cm-1) ≈ [P/N0.9]C (0.042 S·cm-1) > [P/N0.9]M (0.031 S·cm-1) > [P/N0.9]MM (0.011 S·cm-1).

Interplay Between Hydroxyl Density and Relaxations in Poly(vinylbenzyltrimethylammonium)-b-poly(methylbutylene) Membranes for Electrochemical Applications.

Anion-exchange membranes (AEMs) consisting of poly(vinyl benzyl trimethylammonium)-b-poly(methylbutylene) of three different ion exchange capacities (IECs), 1.14, 1.64, and 2.03 mequiv g-1, are studied by High-Resolution Thermogravimetry, Modulated Differential Scanning Calorimetry, Dynamic Mechanical Analysis, and Broadband Electrical Spectroscopy in their OH- form. The thermal stability and transitions are elucidated, showing a low temperature Tg and a higher temperature transition assigned to a disorder-order transition, Tδ, which depends on the IEC of the material. The electric response is analyzed in detail, allowing the identification of three polarizations (only two of which contribute significantly to the overall conductivity, σEP and σIP,1) and two dielectric relaxation events (ß1 and ß2), one associated with the tolyl side groups (ß1) and one with the cationic side chains (ß2). The obtained results are integrated in a coherent picture and a conductivity mechanism is proposed, involving two distinct conduction pathways, σEP and σIP,1. Importantly, we observed a reordering of the ion pair dipoles which is responsible for the Tδ at temperatures higher than 20 °C, which results in a dramatic decrease of the ionic conductivity. Clustering is highly implicated in the higher IEC membrane in the hydroxyl form, which reduces the efficiency of the anionic transport.

Molecular Engineering of MnII Diamine Diketonate Precursors for the Vapor Deposition of Manganese Oxide Nanostructures.

Molecular engineering of manganese(II) diamine diketonate precursors is a key issue for their use in the vapor deposition of manganese oxide materials. Herein, two closely related ß-diketonate diamine MnII adducts with different fluorine contents in the diketonate ligands are examined. The target compounds were synthesized by a simple procedure and, for the first time, thoroughly characterized by a joint experimental-theoretical approach, to understand the influence of the ligand on their structures, electronic properties, thermal behavior, and reactivity. The target compounds are monomeric and exhibit a pseudo-octahedral coordination of the MnII centers, with differences in their structure and fragmentation processes related to the ligand nature. Both complexes can be readily vaporized without premature side decompositions, a favorable feature for their use as precursors for chemical vapor deposition (CVD) or atomic layer deposition applications. Preliminary CVD experiments at moderate growth temperatures enabled the fabrication of high-purity, single-phase Mn3 O4 nanosystems with tailored morphology, which hold great promise for various technological applications.

A lipophilic ionic liquid based on formamidinium cations and TFSI: the electric response and the effect of CO2 on the conductivity mechanism.

This work describes the preparation of the new lipophilic ionic liquid tetraoctyl-formamidinium bis(trifluoromethanesulfonyl) imide (TOFATFSI), which is miscible with lower alkanes. In particular, this work focuses on the electric behaviour of TOFATFSI in the particularly challenging highly apolar environment of supercritical CO2. The conductivity and relaxation phenomena are revealed through the analysis of the broadband electric spectra with a particular emphasis on the effect of temperature and CO2 uptake on the IL conductivity. It is found that temperature boosts the conductivity via an increase in the charge carrier mobility. Also, CO2 absorption affects both the conductivity and the permittivity of the material due to the presence of CO2-IL interactions that modulate the nanostructure and the size of the TOFATFSI aggregates, which increases both the mobility and the density of the charge carriers.

Dielectric relaxations of polyether-based polyurethanes containing ionic liquids as antistatic agents.

Dielectric properties of polyurethanes containing poly(propylene oxide) (PO) and poly(ethylene oxide) (EO) units are discussed, along with the results of direct current (DC) measurements and broadband electrical spectroscopy (BES) studies. The dielectric properties of polyether-containing polyurethanes (PUs) are compared to those of PUs containing 1000 ppm of ionic liquids (ILs) as antistatic agents. The effects of the chemical environment of these ILs, including anion-fixed polymers (PU-AF), cation-fixed polymers (PU-CF), and a simple mixture of IL with the PUs (PU-IL), are compared and discussed on the basis of ion mobility. DC measurements suggest that the charge current is attributed not only to the electrode polarization but also to continuous dielectric relaxation. BES studies elucidate that both fast and slow relaxations are taking place in EO-rich domains in pristine PU and PU-AF. The activation energies of the slow relaxation and of the ionic conductivity are similar, suggesting that the ionic conductivity of these materials is attributed to the ion exchange reaction in EO/ion complexes. In contrast, only fast relaxations are observed in the domains mostly comprised of ion-depleted EO in the PUs containing "free" anions, i.e., PU-CF and PU-IL. This suggests that [Tf2N](-) ligands are weakly interacting with the EO chains and contribute effectively to the ion conduction. Thus, enhanced ionic conductivity is observed in PU-CF and PU-IL, yielding sufficient antistatic effects. Taking into account its long shelf life, arising from the lack of IL bleed-out, PU-CF is concluded to be the most promising candidate.

Interplay between solid state transitions, conductivity mechanisms, and electrical relaxations in a [PVBTMA] [Br]-b-PMB diblock copolymer membrane for electrochemical applications.

Understanding the structure-property relationships and the phenomena responsible for ion conduction is one of the keys in the design of novel ionomers with improved properties. In this report, the morphology and the mechanism of ion exchange in a model anion exchange membrane (AEM), poly(vinyl benzyl trimethyl ammonium bromide)-block-poly(methylbutylene) ([PVBTMA][Br]-b-PMB), is investigated with small angle X-ray scattering, high-resolution thermogravimetry, modulated differential scanning calorimetry, dynamic mechanical analysis, and broadband electrical spectroscopy. The hyper-morphology of the material consists of hydrophilic domains characterized by stacked sides of [PVBTMA][Br] which are sandwiched between "spaghetti-like" hydrophobic cylindrical parallel domains of the PMB block. The most important interactions in the hydrophilic domains occur between the dipoles of ammonium bromide ion pairs in the side chains of adjacent chains. A reordering of the ion pair dipoles is responsible for a disorder-order transition (Tδ) at high temperature, observed here for the first time in AEMs, which results in a dramatic decrease of the ionic conductivity. The overall mechanism of long range charge transfer, deduced from a congruent picture of all of the results, involves two distinct ion conduction pathways. In these pathways, hydration and the motion of the ionic side groups are crucial to the conductivity of the AEM. Unlike the typical perfluorinated sulfonated proton-conducting polymer, the segmental motion of the backbone is negligible.

A Key concept in Magnesium Secondary Battery Electrolytes.

A critical roadblock toward practical Mg-based energy storage technologies is the lack of reversible electrolytes that are safe and electrochemically stable. Here, we report on high-performance electrolytes based on 1-ethyl-3-methylimidazolium chloride (EMImCl) doped with AlCl3 and highly amorphous δ-MgCl2 . The phase diagram of the electrolytes reveals the presence of four thermal transitions that strongly depend on salt content. High-level density functional theory (DFT)-based electronic structure calculations substantiate the structural and vibrational assignment of the coordination complexes. A 3D chloride-concatenated dynamic network model accounts for the outstanding redox behaviour and the electric and magnetic properties, providing insight into the conduction mechanism of the electrolytes. Mg anode cells assembled using the electrolytes were cyclically discharged at a high rate (35 mA g(-1) ), exhibiting an initial capacity of 80 mA h g(-1) and a steady-state voltage of 2.3 V.

Nanocomposite membranes based on polybenzimidazole and ZrO2 for high-temperature proton exchange membrane fuel cells.

Owing to the numerous benefits obtained when operating proton exchange membrane fuel cells at elevated temperature (>100 °C), the development of thermally stable proton exchange membranes that demonstrate conductivity under anhydrous conditions remains a significant goal for fuel cell technology. This paper presents composite membranes consisting of poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI4N) impregnated with a ZrO2 nanofiller of varying content (ranging from 0 to 22 wt %). The structure-property relationships of the acid-doped and undoped composite membranes have been studied using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, wide-angle X-ray scattering, infrared spectroscopy, and broadband electrical spectroscopy. Results indicate that the level of nanofiller has a significant effect on the membrane properties. From 0 to 8 wt %, the acid uptake as well as the thermal and mechanical properties of the membrane increase. As the nanofiller level is increased from 8 to 22 wt % the opposite effect is observed. At 185 °C, the ionic conductivity of [PBI4N(ZrO2 )0.231 ](H3 PO4 )13 is found to be 1.04×10(-1)  S cm(-1) . This renders membranes of this type promising candidates for use in high-temperature proton exchange membrane fuel cells.

Interplay between water uptake, ion interactions, and conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) anion exchange membrane.

We demonstrate that the true hydroxide conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) [ETFE] anion exchange membrane (AEM) is as high as 132 mS cm(-1) at 80 °C and 95% RH, comparable to a proton exchange membrane, but with very much less water present in the film. To understand this behaviour we studied ion transport of hydroxide, carbonate, bicarbonate and chloride, as well as water uptake and distribution. Water uptake of the AEM in water vapor is an order of magnitude lower than when submerged in liquid water. In addition (19)F pulse field gradient spin echo NMR indicates that there is little tortuosity in the ionic pathways through the film. A complete analysis of the IR spectrum of the AEM and the analyses of water absorption using FT-IR led to conclusion that the fluorinated backbone chains do not interact with water and that two types of water domains exist within the membrane. The reduction in conductivity was measured during exposure of the OH(-) form of the AEM to air at 95% RH and was seen to be much slower than the reaction of CO2 with OH(-) as the amount of water in the film determines its ionic conductivity and at relative wet RHs its re-organization is slow.

Molecular relaxations in magnesium polymer electrolytes via GHz broadband electrical spectroscopy.

GHz broadband electrical spectroscopy (G-BES) is adopted to investigate the molecular relaxations and interactions occurring within the system in an oxygen- and water-free atmosphere in the 300 kHz-20 GHz and -40 to 250 °C frequency and temperature ranges, respectively. A new electrolyte for magnesium secondary batteries that can transfer magnesium ions efficiently is presented. This electrolyte is based on polyethylene glycol 400 and a polymeric form of δ-MgCl2 . The information obtained by G-BES is crucial for studying the conduction mechanism of these new electrolytes.

Dielectric relaxations and conduction mechanisms in polyether-clay composite polymer electrolytes under high carbon dioxide pressure.

The composite material P(EO/EM)-Sa consisting of synthetic saponite (Sa) dispersed in poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (P(EO/EM)) is studied by "in situ" measurements using broadband electrical spectroscopy (BES) under pressurized CO2 to characterize the dynamic behavior of conductivity and the dielectric relaxations of the ion host polymer matrix. It is revealed that there are three dielectric relaxation processes associated with: (I) the dipolar motions in the short oxyethylene side chains of P(EO/EM) (ß); and (II) the segmental motion of the main chains comprising the polyether components (αfast, αslow). αslow is attributed to the slow α-relaxation of P(EO/EM) macromolecules, which is hindered by the strong coordination interactions with the ions. Two conduction processes are observed, σDC and σID, which are attributed, respectively, to the bulk conductivity and the interdomain conductivity. The temperature dependence of conductivity and relaxation processes reveals that αfast and αslow are strongly correlated with σDC and σID. The "in situ" BES measurements under pressurized CO2 indicate a fast decrease in σDC at the initial CO2 treatment time resulting from the decrease in the concentration of polyether-M(n+) complexes, which is driven by the CO2 permeation. The relaxation frequency (fR) of αslow at the initial CO2 treatment time increases and shows a steep rise with time with the same behavior of the αfast mode. It is demonstrated that the interactions between polyether chains of P(EO/EM) and cations in the polymer electrolyte layers embedded in Sa are probably weakened by the low permittivity of CO2 (ε = 1.08). Thus, the formation of ion pairs in the polymer electrolyte domains of P(EO/EM)-Sa occurs, with a corresponding reduction in the concentration of ion carriers.