Composite MAX phase/MXene/Ni electrodes with a porous 3D structure for hydrogen evolution and energy storage application.

MXenes, a family of two-dimensional (2D) transition metal carbides, have been discovered as exciting candidates for various energy storage and conversion applications, including green hydrogen production by water splitting. Today, these materials mostly remain interesting objects for in-depth fundamental studies and scientific curiosity due to issues related to their preparation and environmental stability, limiting potential industrial applications. This work proposes a simple and inexpensive concept of composite electrodes composed of molybdenum- and titanium-containing MAX phases and MXene as functional materials. The concept is based on the modification of the initial MAX phase by the addition of metallic Ni, tuning Al- and carbon content and synthesis conditions, followed by fluoride-free etching under alkaline conditions. The proposed methodology allows producing a composite electrode with a well-developed 3D porous MAX phase-based structure acting as a support for electrocatalytic species, including MXene, and possessing good mechanical integrity. Electrochemical tests have shown a high electrochemical activity of such electrodes towards the hydrogen evolution reaction (HER), combined with a relatively high areal capacitance (up to 10 F cm-2).

Phosphorus removal from urban wastewater through adsorption using biogenic calcium carbonate.

Phosphorus (P) removal from urban wastewater is increasingly relevant in the wastewater treatment sector. The present work aims to contribute to the study of the adsorption process as a P removal technology. Biogenic calcium carbonate from industrial eggshell waste prepared by milling and calcination was used as an adsorbent. Batch adsorption experiments were conducted using real wastewater with 40 mg P/L (orthophosphate), original pH 7.33, under stirring conditions (100 rpm). The adsorbent was characterized using SEM-EDS, XRD, and FTIR-ATR before and after adsorption. From an initial screening of calcination times (15, 30, 60, and 120 min) and considering a balance between P removal and energy saving, the adsorbent selected was eggshell calcined at 700 °C for 60 min. The Langmuir isotherms describe the experimental data with a maximum adsorption capacity of 4.57 mg P/g at 25 °C. The adsorption process reached equilibrium within 120 min for different dosages (5, 10, and 20 g/L at 25 °C). Batch experiments showed that SO42-, at a concentration of 2689 mg/L reduced the P adsorption selectivity for dosages ≤10 g/L at 25 °C. Characterization of the loaded adsorbent shows that P adsorption from real wastewater is mostly electrostatic attraction, with the contribution of ligand exchange and microprecipitation. The adsorption capacity and behavior of the selected adsorbent seem promising for P removal from urban wastewater compared with other low-cost adsorbents.

Prospects of Using Pseudobrookite as an Iron-Bearing Mineral for the Alkaline Electrolytic Production of Iron.

The alkaline electrolytic production of iron is gaining interest due to the absence of CO2 emissions and significantly lower electrical energy consumption when compared with traditional steelmaking. The possibility of using an iron-bearing pseudobrookite mineral, Fe2TiO5, is explored for the first time as an alternative feedstock for the electrochemical reduction process. To assess relevant impacts of the presence of titanium, similar electroreduction processes were also performed for Fe2TiO5·Fe2O3 and Fe2O3. The electroreduction was attempted using dense and porous ceramic cathodes. Potentiostatic studies at the cathodic potentials of -1.15--1.30 V vs. an Hg|HgO|NaOH reference electrode and a galvanostatic approach at 1 A/cm2 were used together with electroreduction from ceramic suspensions, obtained by grinding the porous ceramics. The complete electroreduction to Fe0 was only possible at high cathodic polarizations (-1.30 V), compromising the current efficiencies of the electrochemical process due to the hydrogen evolution reaction impact. Microstructural evolution and phase composition studies are discussed, providing trends on the role of titanium and corresponding electrochemical mechanisms. Although the obtained results suggest that pseudobrookite is not a feasible material to be used alone as feedstock for the electrolytic iron production, it can be considered with other iron oxide materials and/or ores to promote electroreduction.

Beneficial use of lime mud from kraft pulp industry for drying and microbiological decontamination of sewage sludge.

Sewage sludge (SS) is a global environmental, social, and economic problem that requires a sustainable management approach. Still, the production of other industrial wastes, such as lime mud (LM), has recently gained considerable attention to avoid landfilling. This work aims to present a new approach for converting SS and LM into value-added products within the circular economy perspective. In particular, the effect of LM and calcined lime mud (CLM) as drying adjuvants and SS sanitation agents are investigated. Two out of three SS samples show Escherichia coli contamination above the Portuguese limit established for soil application, while no Salmonella spp. was detected in the searched samples. The addition of CLM to SS in a ratio between 0.05 and 0.15 g CLM/gwb, lead to complete elimination of the microbiological contamination in almost all cases. Contrarily, the use of LM does not seem efficient to act as a sanitation agent. Both LM and CLM show a positive impact on the drying process when compared to the raw SS, increasing the drying rate, and reducing the drying time. The most favourable drying conditions to maximize the drying rate and minimize the drying time (until 30% of moisture) are 130 °C, 0.15 g adj/gwb, and 2.5 mm of plate thickness. The thermal treatment (100 and 130 °C) without adjuvants reduces the microbiological contamination below the legal limit. Overall, a beneficial effect is observed by adding CLM to SS, open the possibility of producing a safer organic soil improver.

Prospects for Electrical Performance Tuning in Ca3Co4O9 Materials by Metallic Fe and Ni Particles Additions.

This work further explores the possibilities for designing the high-temperature electrical performance of the thermoelectric Ca3Co4O9 phase, by a composite approach involving separate metallic iron and nickel particles additions, and by employing two different sintering schemes, capable to promote the controlled interactions between the components, encouraged by our recent promising results obtained for similar cobalt additions. Iron and nickel were chosen because of their similarities with cobalt. The maximum power factor value of around 200 µWm-1K-2 at 925 K was achieved for the composite with the nominal nickel content of 3% vol., processed via the two-step sintering cycle, which provides the highest densification from this work. The effectiveness of the proposed approach was shown to be strongly dependent on the processing conditions and added amounts of metallic particles. Although the conventional one-step approach results in Fe- and Ni-containing composites with the major content of the thermoelectric Ca3Co4O9 phase, their electrical performance was found to be significantly lower than for the Co-containing analogue, due to the presence of less-conducting phases and excessive porosity. In contrast, the relatively high performance of the composite with a nominal nickel content of 3% vol. processed via a two-step approach is related to the specific microstructural features from this sample, including minimal porosity and the presence of the Ca2Co2O5 phase, which partially compensate the complete decomposition of the Ca3Co4O9 matrix. The obtained results demonstrate different pathways to tailor the phase composition of Ca3Co4O9-based materials, with a corresponding impact on the thermoelectric performance, and highlight the necessity of more controllable approaches for the phase composition tuning, including lower amounts and different morphologies of the dispersed metallic phases.

Recovery of phosphate from aqueous solutions using calcined eggshell as an eco-friendly adsorbent.

Phosphorus scarcity has become a significant issue in the European Union (EU) during 21st Century, due to its relevance as an irreplaceable macronutrient for life, and because of the total dependency of EU regarding imports. This work aims to evaluate the phosphorus recovery by adsorption in batch and fixed-bed column, using a thermally modified eggshell as an adsorbent. The screening phase revealed that calcined eggshell at 700 °C (CES700) is the most suitable material compared with the other thermally modified eggshells tested. Thus, CES700 was characterized regarding the specific surface area, pore volume, zero-point charge pH, total dissolved solids and organic matter. The influence of pH and adsorbent dosage was investigated in batch conditions. Langmuir-Freundlich model described the equilibrium data and the maximum adsorption capacity was about 39 mg P-PO4/g. The kinetics follows a pseudo-first order model, with constants between 0.063 and 0.224 min-1. Fixed-bed studies indicated that increasing fluid superficial velocity and feed concentration led to an early saturation of the adsorbent. Yoon-Nelson, Thomas and Bohard-Adams empirical models properly adjusted the breakthrough curves with R2 ≥ 0.98. Germination tests using CES700 loaded with phosphate revealed a germination index of 120 and 124% to 48 and 72 h, respectively. CES700 is statically better than the other tested materials, which opens the possibility of its use as fertilizer. This study showed that the developed material, CES700, can be applied in batch or fixed-bed processes to recover phosphate ions from liquid effluents, and the loaded adsorbent has potential to be further used as fertilizer.

Phytotoxicity assessment of olive mill solid wastes and the influence of phenolic compounds.

The main objective of this work is to evaluate the phytotoxicity of olive mill solid wastes (OMW) produced in two different centrifugation technologies and also the toxicity associated with specific phenolic compounds. Two samples of waste were collected in two-phase (2P-OMW) and three-phase (3P-OMW) centrifugation olive oil production processes, and cress bioassays with Lepidium sativum L. were employed to evaluate phytotoxicity. Although both OMW have similar total phenolic content (TPh), results confirmed that 2P-OMW is more phytotoxic than 3P-OMW. When extracts from 2P-OMW at liquid to solid ratio of 10 L kg-1 were applied none of the seeds germinated, i.e. germination index (GI) was 0%, while for 3P-OMW GI was 94.3%. Growth tests in soil and mixtures with OMW also led to more favorable results for 3P-OMW, whereas worse results than those obtained in the control experiments were observed. In order to discriminate the individual influence of eleven phenolic compounds, gallic acid, protocatechuic acid, cinnamic acid, syringic acid, 3,4,5-trimethoxybenzoic acid, 4-hydroxybenzoic acid, vanillic acid, p-coumaric acid, caffeic acid, veratric acid and phenol were tested in the concentration range of 5-500 mg L-1. Results showed that cinnamic acid is the most phytotoxic, with EC50 of 60 mg L-1, which is related with its hydrophobicity. Moreover, increasing -OH and -OCH3 groups in these molecules seem to reduce phytotoxicity. Tests with a mixture of six phenolic compounds demonstrated there are neither synergistic nor additive effects. The phytotoxicity appears to be determined by the presence of the most lipophilic phenolic molecule.