Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Formation of low-temperature deformation-induced segregations of nickel in Fe–Ni-based austenitic alloys

ABSTRACT

The authors present the results of an investigation in Fe–Ni-Cr austenitic alloys of the low-temperature deformation-induced segregations of nickel that form in the micro regions being (i) located close to grain- and subgrain boundaries and (ii) characteristic of the concentration and magnetic inhomogeneities indicated by the appearance of a dark diffraction contrast at the electron diffraction patterns taken from these regions typical (at the same time) of an enhanced value of Curie temperature. The observed effects were connected with the micro distortions caused by the local change of lattice parameter because of an increase in nickel concentration, as well as in the result of a magnetostriction dilatation. Using methods of the X-ray energy dispersive spectroscopy (XEDS) and atomic-probe body-section radiography (tomography – APT) has made it possible to determine the borders of those regions of austenite that were characteristic of an enhanced concentration of nickel in the fields of the localisation of a deformation-induced segregation of nickel in the vicinity of grain (subgrain) boundaries of austenitic alloys of the types Fe–13Cr–30Ni and Fe–37Ni–3Ti.     

Recent advances on the use of active anodes in environmental electrochemistry

Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed.     

Recent Progress on Nickel-Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed.     

Studying the process of ionization of hydrogen in conditions of its forced delivery to a porous nickel oxide electrode

The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm^?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm^?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process.     

A Promising MoO_x-based Catalyst for n-Heptane Isomerization

The increasing demand for higher-octane gasoline and the regulations limiting the amount of aromatics in the fuel motivate the interest in catalytic isomerization of n-alkanes. In the last ten years, transition metal oxides or oxycarbides based on molybdenum or tungstate have attracted much attention due to their high activity and isomerization selectivity compared to the conventional bifunctional supported platinum catalyst and high resistance to sulphur and nitrogen catalyst poisons1-5. Ma…     

Crystallographic report: Bis{[diacetyl‐bis(2,6‐isopropylphenylimine)]nickel(I)(µ‐chloro)}

The first α‐diimine nickel(I) complex having a chloro bridge is reported. The centrosymmetric dinuclear structure of {[ArN?C(Me)C(Me)?NAr]NiCl}₂[Ar?2,6?C₆H₃(i‐Pr)₂] features two chelating α‐diimine ligands and two bridged chlorine atoms, so that a distorted tetrahedral N₂Cl₂ coordination geometry for nickel results. Copyright © 2004 John Wiley & Sons, Ltd.     

Nickel Chloride Promoted Glaser Coupling Reaction in Hot Water

A Glaser coupling reaction of terminal alkynes in the presence of nickel chloride withoutany organics and bases in hot water has been developed, which produces the correspondinghomo-coupling products in good yields.     

La5Al3Ni2 – an Intermetallic Phase Observed upon Crystallization of La50Al25Ni25 Metallic Glass

The yet unknown intermetallic phase La₅Al₃Ni₂ was obtained by partially crystallizing amorphous La₅₀Al₂₅Ni₂₅ at 550 K (further heating above 600 K leads to irreversible disappearance of this phase), and its crystal structure was determined from X‐ray powder diffraction data. The crystal structure of the La₅Al₃Ni₂ phase constitutes a new structure type (Cmcm, a = 14.231Å, b = 6.914Å, c = 10.460Å, oC40) and is built from [Al₃Ni₂] chains surrounded by La atoms. In the ternary system La‐Al‐Ni La₅Al₃Ni₂ is located on the section La₅₀Al_50−nNi_n (0 ≤ n ≤ 50) with the binary compounds LaAl and LaNi as end members. Strikingly, also the crystal structures of the end members can be conceived as chain structures with Al and Ni chains surrounded by La, respectively.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.