Isolation of pseudocapacitive surface processes at monolayer MXene flakes reveals delocalized charging mechanism.

Pseudocapacitive charge storage in Ti3C2Tx MXenes in acid electrolytes is typically described as involving proton intercalation/deintercalation accompanied by redox switching of the Ti centres and protonation/deprotonation of oxygen functional groups. Here we conduct nanoscale electrochemical measurements in a unique experimental configuration, restricting the electrochemical contact area to a small subregion (0.3 µm2) of a monolayer Ti3C2Tx flake. In this unique configuration, proton intercalation into interlayer spaces is not possible, and surface processes are isolated from the bulk processes, characteristic of macroscale electrodes. Analysis of the pseudocapacitive response of differently sized MXene flakes indicates that entire MXene flakes are charged through electrochemical contact of only a small basal plane subregion, corresponding to as little as 3% of the flake surface area. Our observation of pseudocapacitive charging outside the electrochemical contact area is suggestive of a fast transport of protons mechanism across the MXene surface.

Structure and Surface Relaxation of CeO2 Nanoparticles Unveiled by Combining Real and Reciprocal Space Total Scattering Analysis.

We present a combined real and reciprocal space structural and microstructural characterization of CeO2 nanoparticles (NPs) exhibiting different crystallite sizes; ~3 nm CeO2 NPs were produced by an inverse micellae wet synthetic path and then annealed at different temperatures. X-ray total scattering data were analyzed by combining real-space-based Pair Distribution Function analysis and the reciprocal-space-based Debye Scattering Equation method with atomistic models. Subtle atomic-scale relaxations occur at the nanocrystal surface. The structural analysis was corroborated by ab initio DFT and force field calculations; micro-Raman and electron spin resonance added important insights to the NPs' defective structure. The combination of the above techniques suggests a core-shell like structure of ultrasmall NPs. These exhibit an expanded outer shell having a defective fluorite structure, while the inner shell is similar to the bulk structure. The presence of partially reduced O2-δ species testifies to the high surface activity of the NPs. On increasing the annealing temperature, the particle dimensions increase, limiting disorder as a consequence of the progressive surface-to-volume ratio reduction.

Nanoscaffold effects on the performance of air-cathodes for microbial fuel cells: Sustainable Fe/N-carbon electrocatalysts for the oxygen reduction reaction under neutral pH conditions.

Nanostructured electrocatalysts for microbial fuel cell air-cathodes were obtained via use of conductive carbon blacks for the synthesis of high performing 3D conductive networks. We used two commercially available nanocarbons, Black Pearls 2000 and multiwalled carbon nanotubes, as conductive scaffolds for the synthesis of nanocomposite electrodes by combining: a hydrothermally carbonized resin, a sacrificial polymeric template, a nitrogenated organic precursor and iron centers. The resulting materials are micro-mesoporous, possess high specific surface area and display N-sites (N/C of 3-5 at%) and Fe-centers (Fe/C < 1.5at.%) at the carbon surface as evidenced from characterization methods. Voltammetry studies of oxygen reduction reaction activity were carried out at neutral pH, which is relevant to microbial fuel cell applications, and activity trends are discussed in light of catalyst morphology and composition. Tests of the electrocatalyst using microbial fuel cell devices indicate that optimization of the nanocarbon scaffold for the Pt-free carbon-based electrocatalysts results in maximum power densities that are 25% better than those of Pt/C cathodes, at a fraction of the materials costs. Therefore, the proposed Fe/N-carbon catalysts are promising and sustainable high-performance cathodic materials for microbial fuel cells.

LC-MS analysis of nitroguanidine compounds by catalytic reduction using palladium modified graphitic carbon nitride catalyst.

The analysis of compounds of the nitroguanidine family at trace level poses an analytical challenge. Nitroguanidine, 1-methyl-3-nitroguanidine, and 1-methyl-3-nitro-1-nitrosoguanidine, which are addressed in this article, have low lipophilicity, with log(Kow) equal to -0.89, - 0.84, and 0.68, respectively, and as such are not amenable for preconcentration from water. Liquid-liquid extraction and SPE fail to concentrate them from water and it is also not possible to extract them by ion exchange resin even after a pH change. Nitroguanidine and 1-methyl-3-nitroguanidine nitramines are explosives of growing use and thereby growing environmental concern due to lower detonation sensitivity compared to RDX. A sensitive method for the determination of nitroguanidine, 1-methyl-3-nitroguanidine, and 1-methyl-3-nitroso-1-nitroguanidine by reduction to the respective amines and subsequent hydrophobization by derivatization with 4-nitrobenzaldehyde followed by LC-ESI-MS analysis is described. Reduction by sodium borohydride using palladium modified graphitic carbon nitride (Pd/g-C3N4) provided improved sensitivity compared to the traditional palladium modified activated carbon due to the lower adsorption of the reduction products on the carbon nitride substrate. The limit of detection of the method was 10 ng L-1 for nitroguanidine, and repeated analyses of spiked effluents and contaminated spring water gave relative standard deviations of 8.8% and 6.5%, respectively. The findings illuminate the great promise of Pd/g-C3N4 as a reduction catalyst for the determination of challenging hydrophilic organic contaminants.

ORR in Non-Aqueous Solvent for Li-Air Batteries: The Influence of Doped MnO2-Nanoelectrocatalyst.

One of the major drawbacks in Lithium-air batteries is the sluggish kinetics of the oxygen reduction reaction (ORR). In this context, better performances can be achieved by adopting a suitable electrocatalyst, such as MnO2. Herein, we tried to design nano-MnO2 tuning the final ORR electroactivity by tailoring the doping agent (Co or Fe) and its content (2% or 5% molar ratios). Staircase-linear sweep voltammetries (S-LSV) were performed to investigate the nanopowders electrocatalytic behavior in organic solvent (propylene carbonate, PC and 0.15 M LiNO3 as electrolyte). Two percent Co-doped MnO2 revealed to be the best-performing sample in terms of ORR onset shift (of ~130 mV with respect to bare glassy carbon electrode), due to its great lattice defectivity and presence of the highly electroactive γ polymorph (by X-ray diffraction analyses, XRPD and infrared spectroscopy, FTIR). 5% Co together with 2% Fe could also be promising, since they exhibited fewer diffusive limitations, mainly due to their peculiar pore distribution (by Brunauer-Emmett-Teller, BET) that disfavored the cathode clogging. Particularly, a too-high Fe content led to iron segregation (by energy dispersive X-ray spectroscopy, EDX, X-ray photoelectron spectroscopy, XPS and FTIR) provoking a decrease of the electroactive sites, with negative consequences for the ORR.

Exploring SnxTi1-xO2 Solid Solutions Grown onto Graphene Oxide (GO) as Selective Toluene Gas Sensors.

The major drawback of oxide-based sensors is the lack of selectivity. In this context, SnxTi1-xO2/graphene oxide (GO)-based materials were synthesized via a simple hydrothermal route, varying the titanium content in the tin dioxide matrix. Then, toluene and acetone gas sensing performances of the as-prepared sensors were systematically investigated. Specifically, by using 32:1 SnO2/GO and 32:1 TiO2/GO, a greater selectivity towards acetone analyte, also at room temperature, was obtained even at ppb level. However, solid solutions possessing a higher content of tin relative to titanium (as 32:1 Sn0.55Ti0.45O2/GO) exhibited higher selectivity towards bigger and non-polar molecules (such as toluene) at 350 °C, rather than acetone. A deep experimental investigation of structural (XRPD and Raman), morphological (SEM, TEM, BET surface area and pores volume) and surface (XPS analyses) properties allowed us to give a feasible explanation of the different selectivity. Moreover, by exploiting the UV light, the lowest operating temperature to obtain a significant and reliable signal was 250 °C, keeping the greater selectivity to the toluene analyte. Hence, the feasibility of tuning the chemical selectivity by engineering the relative amount of SnO2 and TiO2 is a promising feature that may guide the future development of miniaturized chemoresistors.

Rare Earth Doped Ceria: The Complex Connection Between Structure and Properties.

The need for high efficiency energy production, conversion, storage and transport is serving as a robust guide for the development of new materials. Materials with physical-chemical properties matching specific functions in devices are produced by suitably tuning the crystallographic- defect- and micro-structure of the involved phases. In this review, we discuss the case of Rare Earth doped Ceria. Due to their high oxygen diffusion coefficient at temperatures higher than ~500°C, they are very promising materials for several applications such as electrolytes for Solid Oxide Fuel and Electrolytic Cells (SOFC and SOEC, respectively). Defects are integral part of the conduction process, hence of the final application. As the fluorite structure of ceria is capable of accommodating a high concentration of lattice defects, the characterization and comprehension of such complex and highly defective materials involve expertise spanning from computational chemistry, physical chemistry, catalysis, electrochemistry, microscopy, spectroscopy, and crystallography. Results coming from different experimental and computational techniques will be reviewed, showing that structure determination (at different scale length) plays a pivotal role bridging theoretical calculation and physical properties of these complex materials.

Synergistic Effects of Active Sites' Nature and Hydrophilicity on the Oxygen Reduction Reaction Activity of Pt-Free Catalysts.

This work highlights the importance of the hydrophilicity of a catalyst's active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu.

Comparison of Branched and Linear Perfluoropolyether Chains Functionalization on Hydrophobic, Morphological and Conductive Properties of Multi-Walled Carbon Nanotubes.

The functionalization of multi-walled carbon nanotubes (MW-CNTs) was obtained by generating reactive perfluoropolyether (PFPE) radicals that can covalently bond to MW-CNTs' surface. Branched and linear PFPE peroxides with equivalent molecular weights of 1275 and 1200 amu, respectively, have been thermally decomposed for the production of PFPE radicals. The functionalization with PFPE chains has changed the wettability of MW-CNTs, which switched their behavior from hydrophilic to super-hydrophobic. The low surface energy properties of PFPEs have been transferred to MW-CNTs surface and branched units with trifluoromethyl groups, CF3, have conferred higher hydrophobicity than linear units. Porosimetry discriminated the effects of PFPE functionalization on meso-porosity and macro-porosity. It has been observed that reactive sites located in MW-CNTs mesopores have been intensively functionalized by branched PFPE peroxide due to its low average molecular weight. Conductivity measurements at different applied pressures have showed that the covalent linkage of PFPE chains, branched as well as linear, weakly modified the electrical conductivity of MW-CNTs. The decomposed portions of PFPE residues, the PFPE chains bonded on carbon nanotubes, and the PFPE fluids obtained by homo-coupling side-reactions were evaluated by mass balances. PFPE-modified MW-CNTs have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), static contact angle (SCA), surface area, and porosity measurements.

Comparative toxicity of three differently shaped carbon nanomaterials on Daphnia magna: does a shape effect exist?

The acute toxicity of three differently shaped carbon nanomaterials (CNMs) was studied on Daphnia magna, comparing the induced effects and looking for the toxic mechanisms. We used carbon nano-powder (CNP), with almost spherical primary particle morphology, multi-walled carbon nanotubes (CNTs), tubes of multi-graphitic sheets, and cubic-shaped carbon nanoparticles (CNCs), for which no ecotoxicological data are available so far. Daphnids were exposed to six suspensions (1, 2, 5, 10, 20 and 50 mg L-1) of each CNM, and then microscopically analyzed. Ultrastructural analyses evidenced cellular uptake of nanoparticle in CNP and CNT exposed groups, but not in samples exposed to CNCs. Despite this difference, very similar effects were observed in tissues exposed to the three used CNMs: empty spaces between cells, cell detachment from the basal lamina, many lamellar bodies and autophagy vacuoles. These pathological figures were qualitatively similar among the three groups, but they differed in frequency and severity. CNCs caused the most severe effects, such as partial or complete dissolution of the brush border and thinning of the digestive epithelium. Being the cubic shape not allowed to be internalized into cells, but more effective than others in determining physical damages, we can conclude that shape is an important factor for driving nanoparticle uptake by cells and for determining the acute toxicological endpoints. Shape also plays a key role in determining the kind and the severity of pathologies, which are linked to the physical interactions of CNMs with the exposed tissues.

Fe-based heterogeneous catalysts for the Fischer-Tropsch reaction: Sonochemical synthesis and bench-scale experimental tests.

The sonochemical synthesis of nanostructured materials owes its origins to the extreme conditions created during acoustic cavitation, i.e., the formation of localized hot spots in the core of collapsing bubbles in a liquid irradiated with high intensity ultrasound (US). In particular, in the present work a sonochemical synthesis has been investigated for the production of three different iron-based samples supported on SiO2 and loaded with different metals and promoters (10 %wt of Fe; 30 %wt of Fe; 30 %wt of Fe, 2 %wt of K and 3.75 %wt of Cu) active in the Fischer-Tropsch (FT) process. Sonochemically synthesized heterogeneous catalysts were characterized by BET, XRPD, TPR, ICP, CHN, TEM, SEM and then tested in a fixed bed FT-bench-scale rig fed with a mixture of H2 and CO at a H2/CO molar ratio equal to 2, at activation temperatures of 350-400°C and reaction temperatures of 250-260°C. The experimental results showed that the ultrasonic samples are effective catalysts for the FT process. Notably, increasing the activation temperature increased CO conversion, while product selectivity did not diminish. All the sonochemically prepared samples presented in this work provided better catalytic results compared to the corresponding traditional FT impregnated catalysts.

Tailored N-Containing Carbons as Catalyst Supports in Alcohol Oxidation.

The introduction of N-containing functionalities in carbon-based materials is brought to stable and highly active metal-supported catalysts. However, up to now, the role of the amount and the nature of N-groups have not been completely clear. This study aims to clarify these aspects by preparing tailored N-containing carbons where different N-groups are introduced during the synthesis of the carbon material. These materials were used as the support for Pd nanoparticles. Testing these catalysts in alcohol oxidations and comparing the results with those obtained using Pd nanoparticles supported on different N-containing supports allowed us to obtain insight into the role of the different N-containing groups. In the cinnamyl alcohol oxidation, pyridine-like groups seem to favor both activity and selectivity toward cinnamaldehyde.

Conformational polymorphism in a Schiff-base macrocyclic organic ligand: an experimental and theoretical study.

Polymorphism in the highly flexible organic Schiff-base macrocycle ligand 3,6,9,17,20,23-hexa-azapentacyclo(23.3.1.1(11,15).0(2,6).0(16,20))triaconta-1(29),9,11,13,15(30),23,25,27-octaene (DIEN, C(24)H(30)N(6)) has been studied by single-crystal X-ray diffraction and both solid-state and gas-phase density functional theory (DFT) calculations. In the literature, only solvated structures of the title compound are known. Two new polymorphs and a new solvated form of DIEN, all obtained from the same solvent with different crystallization conditions, are presented for the first time. They all have P\bar 1 symmetry, with the macrocycle positioned on inversion centres. The two unsolvated polymorphic forms differ in the number of molecules in the asymmetric unit Z', density and cohesive energy. Theoretical results confirm that the most stable form is (II°), with Z' = 1.5. Two distinct molecular conformations have been found, named `endo' or `exo' according to the orientation of the imine N atoms, which can be directed towards the interior or the exterior of the macrocycle. The endo arrangement is ubiquitous in the solid state and is shared by two independent molecules which constitute an invariant supramolecular synthon in all the known crystal forms of DIEN. It is also the most stable arrangement in the gas phase. The exo form, on the other hand, appears only in phase (II°), which contains both the conformers. Similarities and differences among the occurring packing motifs, as well as solvent effects, are discussed with the aid of Hirshfeld surface fingerprint plots and correlated to the results of the energy analysis. A possible interconversion path in the gas phase between the endo and the exo conformers has been found by DFT calculations; it consists of a two-step mechanism with activation energies of the order of 30-40 kJ mol(-1). These findings have been related to the empirical evidence that the most stable phase (II°) is also the last appearing one, in accordance with Ostwald's rule.