Ultrasound-Assisted Synthesis of Humic-Silica Composites by the Isolation of Humic Substances from Peat and Lignite.

The aim of the presented study was to evaluate an integrated, direct procedure for the synthesis of humic-silica composites (HSiC) by the isolation of humic substances (HS) from peat and lignite by the use of sodium silicate solution as an extractant. The obtained materials, because of the presence of humic functional groups, may potentially be used for removing contaminants from aqueous solutions. The quantitative assessment was based on experiments designed according to the Box-Behnken plan. The statistical analysis of the results allowed to determine the optimal conditions of the process tested, for which the isolation efficiency of humic substances (HS) was greater than 50 % for both raw materials. This made it possible to synthesize humic silica composites with a high content of HS, which have been qualitatively evaluated. This step was focused on the analysis of the humic structure using elemental analysis, spectroscopic methods, and differential thermal analysis coupled with thermogravimetry. On the basis of them, the presence of structures characteristic for HS in the HSiC tested was observed. Moreover, the results of the thermal analysis pointed to the higher thermal stability of the synthesized compounds, compared to the HS isolated with the use of a traditional extractant.

Thermal Characteristics of Selected Phosphate Ores and the Effect of Inorganic Salts on Their Calcination.

Calcination of phosphate ore is one of the methods of ore processing, i.e., increasing the phosphorus content (P2O5) in the ore. However, this process is very energy-intensive and not economically justified in most cases. It can be improved by using additives to lower the required calcination temperature. In this work, several samples of phosphate ores were subjected to thermal analysis using thermogravimetry coupled with mass spectrometry (TG-MS) to study their behavior during the calcination process. Then, selected phosphate ore from the Tunisian deposit was mixed with NaCl, KNO3, or Na2CO3 and calcined in various regimes (temperature and time). Uncalcined samples, together with obtained calcinates, were also subjected to thermal analysis by TG-MS. Temperature ranges in which the mass loss occurred were defined and discussed. Appropriate models of sample weight loss were derived and visualized by using the response surface methodology. Explanations of possible processes observed during the heating of phosphate ore samples with inorganic salt addition were proposed.

Ultrasound-Assisted Extraction of Humic Substances from Peat: Assessment of Process Efficiency and Products' Quality.

Results of efficiency of obtaining humic substances (HSs) from peat in traditional alkaline extraction (TAE) and ultrasound-assisted alkaline extraction (UAAE) are presented. The influence of the duration of the process and ultrasound intensity on the efficiency of extraction of humic acids (HAs) and fulvic acids (FAs) extraction was determined. The composition of the fulvic acid fraction was examined depending on the type of eluent used. Fulvic acids were divided into fractions using columns packed with DAX-8 resin. For this process, 0.1 M NaOH and 0.5 M NH3∙H2O were used as eluents. For the quality assessment of specific fulvic acids fractions, spectroscopic methods (UV-Vis and FTIR) were used. Ultrasound had a positive effect on HS extraction efficiency, especially in increasing the amount of a desired hydrophobic fraction of fulvic acids (HPO). However, a negative effect of the excessive prolongation and ultrasound intensity (approximately 400 mW∙cm-2) on the extraction efficiency of HPO eluted with 0.1 M NaOH solution was observed. Using peat as a raw carbon material for the HS extraction process can be used as an alternative industrial application of peat. UAAE may be considered as an alternative method to TAE, which provides a higher efficiency in HS isolation from peat.

Spinel of Nickel-Cobalt Oxide with Rod-Like Architecture as Electrocatalyst for Oxygen Evolution Reaction.

The renewable energy technologies require electrocatalysts for reactions, such as the oxygen and/or hydrogen evolution reaction (OER/HER). They are complex electrochemical reactions that take place through the direct transfer of electrons. However, mostly they have high over-potentials and slow kinetics, that is why they require electrocatalysts to lower the over-potential of the reactions and enhance the reaction rate. The commercially used catalysts (e.g., ruthenium nanoparticles-Ru, iridium nanoparticles-Ir, and their oxides: RuO2, IrO2, platinum-Pt) contain metals that have poor stability, and are not economically worthwhile for widespread application. Here, we propose the spinel structure of nickel-cobalt oxide (NiCo2O4) fabricated to serve as electrocatalyst for OER. These structures were obtained by a facile two-step method: (1) One-pot solvothermal reaction and subsequently (2) pyrolysis or carbonization, respectively. This material exhibits novel rod-like morphology formed by tiny spheres. The presence of transition metal particles such as Co and Ni due to their conductivity and electron configurations provides a great number of active sites, which brings superior electrochemical performance in oxygen evolution and good stability in long-term tests. Therefore, it is believed that we propose interesting low-cost material that can act as a super stable catalyst in OER.

Study of the Active Carbon from Used Coffee Grounds as the Active Material for a High-Temperature Stable Supercapacitor with Ionic-Liquid Electrolyte.

This study reveals a simple approach to recycle wasted coffee grounds into highly valuable carbon material with superior electrochemical performance. Activated carbon prepared from wasted coffee grounds has been formed via hydrothermal acidic hydrolysis followed by a KOH chemical activation at 800 ∘C. To understand the electrochemical properties of the sample, a set of characterization tools has been utilized: N2 and CO2 adsorption-desorption isotherms, thermal gravimetric analysis, Fourier transform infrared spectroscopy, Raman spectroscopy and scanning electron microscopy. The specific surface area obtained from a Brunner-Emmett-Teller (BET) analysis reached 2906±19m2g-1. Prepared sample (designated as ACG-800KOH) was tested as electrode material in an electric double layer capacitor (EDLC) device with ionic liquid PYR13-TFSI as an electrolyte. The EDLC test was conducted at temperatures ranging from 20 to 120 ∘C. The specific material capacitance reached 178 Fg-1 measured at 20 ∘C and 50 A g-1 and was in the range 182 to 285 Fg-1 at the 20 to 120 ∘C temperature range.

Self-discharge of electrochemical double layer capacitors.

Spontaneous voltage drop between EDLC electrodes, when it is kept under the open-circuit condition, is commonly called 'self-discharge' and is interpreted as a result of energy loss by the device. Three mechanisms of self-discharge were proposed: due to a leakage-current, faradaic reactions and charge redistribution. According to the law of energy preservation, if the voltage drop is associated with the energy loss, the energy would more likely be exchanged with the environment. While heat generation was measured during EDLC charging and discharging, the corresponding effect during storage under open-circuit conditions has not been reported. This may support the conclusion that voltage changes during 'self-discharge' are not related to a considerable energy loss. Moreover, it has been shown that a two-stage charging process, i.e. first galvanostatic charging followed by a potentiostatic charge redistribution, resulted in considerably slower potential changes when the device was switched to the open circuit. All discussed models were based on the assumption that the energy accumulated by EDLCs is proportional to the voltage in the second power, with capacitance (C/2) as the proportionality constant. However, it has been shown that during EDLC charging or discharging through a resistance R, equations valid for 'dielectric' and electrolytic capacitors, do not hold in the case of EDLCs. Consequently, the assumption that the energetic state of the EDLC is proportional at any time to the voltage in the second power may not be valid due to considerable variability of the 'constant' C. Therefore, voltage changes may not reflect the energetic state of the device.