Sustainable Production of Biofuels and Biochemicals via Electro-Fermentation Technology.

The energy crisis and climate change are two of the most concerning issues for human beings nowadays. For that reason, the scientific community is focused on the search for alternative biofuels to conventional fossil fuels as well as the development of sustainable processes to develop a circular economy. Bioelectrochemical processes have been demonstrated to be useful for producing bioenergy and value-added products from several types of waste. Electro-fermentation has gained great attention in the last few years due to its potential contribution to biofuel and biochemical production, e.g., hydrogen, methane, biopolymers, etc. Conventional fermentation processes pose several limitations in terms of their practical and economic feasibility. The introduction of two electrodes in a bioreactor allows the regulation of redox instabilities that occur in conventional fermentation, boosting the overall process towards a high biomass yield and enhanced product formation. In this regard, key parameters such as the type of culture, the nature of the electrodes as well as the operating conditions are crucial in order to maximize the production of biofuels and biochemicals via electro-fermentation technology. This article comprises a critical overview of the benefits and limitations of this emerging bio-electrochemical technology and its contribution to the circular economy.

A comparison of methods for the estimation of the enthalpy of formation of rare earth compounds.

Rare earth elements are helping drive the global transition towards a greener economy. However, the way in which they are produced is far from being considered green. One of the major obstacles to developing greener production methods and the design of novel processes and materials involving rare earth elements is the limited thermodynamic data available. In the present work, we apply a suite of methods to estimate the enthalpy of formation of several rare earth compounds, including a new method based on a linear relationship, established by the authors. Experimental values of the enthalpy of formation of LnCl3, LnOCl, LnPO4, Ln2O2S, Ln2O2CO3 and NaLnO2 were collated and used to assess the accuracy of the different methods, which were then used to predict values for compounds for which no data exists. It is shown that Mostafa et al.'s group contribution method and the linear relationship proposed by the authors give the lowest mean absolute error (<9%). The volume based thermodynamics (VBT) method yields estimates with absolute mean errors below 16.0% for LnPO4 and Ln2O2S, but above 26.0% for other compounds. Correction of the VBT method using an improved estimate of the Madelung energy for the calculation of the lattice enthalpy decreases the absolute mean error below 12.0% for all compounds except LnPO4. These complementary methods provide options for calculating the enthalpy of formation of rare earth compounds, depending on the experimental data available and desired accuracy.

A novel reductive alkali roasting of chromite ores for carcinogen-free Cr6+-ion extraction of chromium oxide (Cr2O3) - A clean route to chromium product manufacturing!

A novel reduction reaction for extracting Cr2O3 from chromite ores is demonstrated by excluding the formation of carcinogenic chromate (Cr6+) intermediates. We have investigated in detail the underpinning high-temperature reduction reaction: FeCr2O4+Na2CO3+2[C]=[Fe]+Na2Cr2O4+3CO(g), which defines the process chemistry for the formation of sodium chromite (Na2CrO2) as an intermediate product for Cr2O3 extraction. After high-temperature reduction, the magnetic separation, aqueous and acid leaching of reaction products yielded 81 wt% and 70 wt% pure Cr2O3 from low (∼4 wt%) and high (>8 wt%) silica-containing chromite ores, respectively. The process diagram explains the extraction of Cr2O3, Fe-Cr alloy, Al2O3, and MgO-Al2O3-silicate, reuse of CO2 for Na2CO3 recovery, and energy generation from CO combustion for demonstrating Cr6+-free extraction of metallic and mineral values from chromite ores. The process chemistry demonstrates the extraction of 75-80 % pure Cr2O3 from NaCrO2 by leaching with 0.05-0.5 M dilute H2SO4 in controlled pH conditions. The detailed chemical analysis of leachates after Cr2O3 extraction shows that the acid leachates with residual concentrations of ∼150 ppm Cr3+-ions can be recycled in situ for reusing water, for eliminating the risk of Cr6+-ion formation from atmospheric oxidation. The novel extraction route may be able to displace the current oxidative process for chromite ore processing by retrofitting.

Nanoparticle corona artefacts derived from specimen preparation of particle suspensions.

Progress in the implementation of nanoparticles for therapeutic applications will accelerate with an improved understanding of the interface between nanoparticle surfaces and the media they are dispersed in. We examine this interface by analytical scanning transmission electron microscopy and show that incorrect specimen preparation or analysis can induce an artefactual, nanoscale, calcium phosphate-rich, amorphous coating on nanoparticles dispersed in cell culture media. We report that this ionic coating can be induced on five different types of nanoparticles (Au, BaTiO3, ZnO, TiO2 and Fe2O3) when specimen preparation causes a significant rise in pH above physiological levels. Such a pH change reduces ionic solubility in the suspending media to permit precipitation of calcium phosphate. Finally, we demonstrate that there is no indication of a calcium-phosphorus-rich coating on BaTiO3 nanoparticles suspended in culture media when prepared without alteration of the pH of the suspending media and imaged by cryo-STEM. Therefore we recommend that future reports utilising nanoparticles dispersed in cell culture media monitor and report the pH of suspensions during sample preparation.

Towards sustainable processing of columbite group minerals: elucidating the relation between dielectric properties and physico-chemical transformations in the mineral phase.

Current methodologies for the extraction of tantalum and niobium pose a serious threat to human beings and the environment due to the use of hydrofluoric acid (HF). Niobium and tantalum metal powders and pentoxides are widely used for energy efficient devices and components. However, the current processing methods for niobium and tantalum metals and oxides are energy inefficient. This dichotomy between materials use for energy applications and their inefficient processing is the main motivation for exploring a new methodology for the extraction of these two oxides, investigating the microwave absorption properties of the reaction products formed during the alkali roasting of niobium-tantalum bearing minerals with sodium bicarbonate. The experimental findings from dielectric measurement at elevated temperatures demonstrate an exponential increase in the values of the dielectric properties as a result of the formation of NaNbO3-NaTaO3 solid solutions at temperatures above 700 °C. The investigation of the evolution of the dielectric properties during the roasting reaction is a key feature in underpinning the mechanism for designing a new microwave assisted high-temperature process for the selective separation of niobium and tantalum oxides from the remainder mineral crystalline lattice.