Nickel-based catalysts for electrolytic decomposition of ammonia towards hydrogen production.

Nickel is an attractive metal for electrochemical applications because it is abundant, cheap, chemically resilient, and catalytically active towards many reactions. Nickel-based materials (metallic nickel, its alloys, oxides, hydroxides, and composites) have been also considered as promising electrocatalysts for ammonia oxidation. The electrolysis of ammonia aqueous solution results in evolution of gaseous hydrogen and nitrogen. Up to date studies showed that metallic Ni and Ni (hydro)oxides are not catalytically active unless they are electrochemically converted to NiOOH at ~1.3 V vs. RHE. Then, dehydrogenation of NH3 begins with electron coupled proton transfer to NiOOH resulting in a would-be reversible reduction of the latter to Ni(OH)2. Unlike the water electrolysis process, in which solely oxygen is obtained at the anode, during ammonia electrooxidation apart from release of N2, many undesired oxygenated nitrogen moieties may also turn up. These products appear after at least partial dehydrogenation of ammonia. Studies on NiOOH activity have been conducted for systems containing various modifiers, e.g., Cu, Co, S, P, however, their particular role in catalytic activity has not yet been elucidated. Nowadays research is being conducted in the direction of increasing the activity, selectivity, and stability of NiOOH. In this review, the electroactivity of Ni is analyzed and discussed in accordance with its oxidation states along with the ammonia oxidation mechanism. The main research problems to be solved and challenges for the future industrial use of ammonia are presented.

Graphene-Coated PVDF Membranes: Effects of Multi-Scale Rough Structure on Membrane Distillation Performance.

Graphene-coated membranes for membrane distillation have been fabricated by using a wet-filtration approach. Graphene nanoplatelets have been deposited onto PVDF membrane surfaces. Morphology and physicochemical properties have been explored to evaluate the changes in the surface topography and related effects on the membrane performance in water desalination. The membranes have been tested in membrane distillation plants by using mixtures of sodium chloride and humic acid. The multi-scale rough structure of the surface has been envisaged to amplify the wetting and fouling resistance of the graphene-coated membranes so that a better flux and full salt rejection have been achieved in comparison with pristine PVDF. Total salt rejection and an increase of 77% in flux have been observed for coated membrane with optimized graphene content when worked with NaCl 0.6 M (DCMD, ΔT ≈ 24 °C) over a test period of 6 h. The experimental findings suggest these novel graphene-coated membranes as promising materials to develop functional membranes for high-performing water desalination.

Microporous N-Doped Carbon Obtained from Salt Melt Pyrolysis of Chitosan toward Supercapacitor and Oxygen Reduction Catalysts.

The direct carbonization of low-cost and abundant chitosan biopolymer in the presence of salt eutectics leads to highly microporous, N-doped nanostructures. The microporous structure is easily manufactured using eutectic mixture (ZnCl2-KCl) and chitosan. Potassium ions here can act as an intercalating agent, leading to the formation of lamellar carbon sheets, whereas zinc chloride generates significant porosity. Here, we present an efficient synthetic way for microporous carbon nanostructures production with a total nitrogen content of 8.7%. Preliminary studies were performed to show the possibility of the use of such material as a catalyst for supercapacitor and ORR. The textural properties enhanced capacitance, which stem from improved accessibility of previously blocked or inactive pores in the carbon structure, leading to the conclusion that porogen salts and molten salt strategies produce materials with tailor-made morphologies. The synergistic effect of the eutectic salt is seen in controlled porous structures and pore size, and the micropores boosting adsorption ability.

Waste management in the mining industry of metals ores, coal, oil and natural gas - A review.

Waste generated due to mining activity poses a serious issue due to the large amounts generated, even up to 65 billion tons per year, and is often associated with the risk posed by its storage and environmental management. This work aims to review waste management in the mining industry of metals ores, coal, oil and natural gas. It includes an analysis and discussion on the possibilities for reuse of certain types of wastes generated from mining activity, and discusses the benefits, disadvantages and the impact of waste management on the environment. The article presents current methods of waste management arising during the extraction and processing of raw materials and the threats resulting from its application. Furthermore, the potential methods of mining waste management are discussed through an in-depth characterization of the properties and composition of various types of rocks. The presented work addresses not only the issues of more sustainable management of waste from the mining industry, but also responds to the current efforts to implement the assumptions of a circular economy, which is aimed at closing the loop. The methods of recycling by-products and treating waste as a resource more and more often not only meet environmental expectations, but also become a legal requirement. In this respect, the presented work can serve as a valuable support in decision-making about waste management.

Effect of Functionalization of Reduced Graphene Oxide Coatings with Nitrogen and Sulfur Groups on Their Anti-Corrosion Properties.

Electrophoretic production of anticorrosion carbonaceous coatings on copper could be successfully performed by anodic oxidation of negatively charged graphene platelets suspended in an aqueous solution. The various platelets were synthesized by Hummer's method followed by a hydrothermal reduction in the presence of NH4SCN which was expected to substitute some parts of graphene structure with nitrogen and sulfur groups. X-ray photoelectron spectroscopy analysis confirmed that the graphene precursors, as well as the coatings, contained typical nitrogen groups, such as pyridinic and pyrrolic, and sulfur groups, such as thiol, thiophene, or C-SO2. However, due to oxidation during deposition, the qualitative and quantitative composition of the graphene coatings changed relative to the composition of the precursors. In particular, the concentration of nitrogen and sulfur dropped and some thiophene groups were oxidized to C-SO2. Studies showed the functionalized coatings had a uniform, defect-free, hydrophobic, more adhesive surface than nonmodified films. The corrosion measurements demonstrated that these coatings had better protective properties than the ones without these heteroatoms. This behavior can be assigned to the catalytic activity of nitrogen towards oxidation of C-SO2 groups to C-SO3H with oxygen.

Electricity generation from rapeseed straw hydrolysates using microbial fuel cells.

Rapeseed straw is an attractive fuel material for microbial fuel cells (MFCs) due to its high content of carbohydrates (more than 60% carbohydrates). This study has demonstrated that reducing sugars can be efficiently extracted from raw rapeseed straw by combination of hydrothermal pretreatment and enzymatic hydrolysis followed by utilization as a fuel in two-chamber MFCs for electrical power generation. The most efficient method of saccharification of this lignocellulosic biomass (17%) turned out hydrothermal pretreatment followed by enzymatic hydrolysis. Electricity was produced using hydrolysate concentrations up to 150 mg/dm(3). The power density reached 54 mW/m(2), while CEs ranged from 60% to 10%, corresponding to the initial reducing sugar concentrations of 10-150 mg/dm(3). The COD degradation rates based on charge calculation increased from 0.445 g COD/m(2)/d for the hydrolysate obtained with the microwave treatment to 0.602 g COD/m(2)/d for the most efficient combination of hydrothermal treatment followed by enzymatic hydrolysis.