Composition effects of electrodeposited Cu-Ag nanostructured electrocatalysts for CO2 reduction.

The electrochemical carbon dioxide reduction (CO2RR) on Cu-based catalysts is a promising strategy to store renewable electricity and produce valuable C2+ chemicals. We investigate the CO2RR on Cu-Ag nanostructures that have been electrodeposited in a green choline chloride and urea deep eutectic solvent (DES). We determine the electrochemically active surface area (ECSA) using lead underpotential deposition (UPD) to investigate the CO2RR intrinsic activity and selectivity. We show that the addition of Ag on electrodeposited Cu primarily suppresses the production of hydrogen and methane. While the production of carbon monoxide slightly increases, the partial current of the total C2+ products does not considerably increase. Despite that the production rate of C2+ is similar on Cu and Cu-Ag, the addition of Ag enhances the formation of alcohols and oxygenates over ethylene. We highlight the potential of metal electrodeposition from DES as a sustainable strategy to develop bimetallic Cu-based nanocatalysts for CO2RR.

Direct evidence for eoarchean iron metabolism?

Metasedimentary rocks from Isua, West Greenland (> 3,700 million years old) contain carbonaceous compounds, compatible with a biogenic origin (Hassenkam, Andersson, Dalby, Mackenzie, & Rosing, 2017; Ohtomo, Kakegawa, Ishida, Nagase, & Rosing, 2014; Rosing, 1999). The metamorphic mineral assemblage with garnet and quartz intergrowths contains layers of carbonaceous inclusions contiguous with carbon-rich sedimentary beds in the host rock. Previous studies (Hassenkam et al., 2017; Ohtomo et al., 2014; Rosing, 1999) on Isua rocks focused on testing the biogenic origin of the carbonaceous material, but here we searched for evidence which could provide new insights into the nature of the life that generated this carbonaceous material. We studied material trapped in inclusions armoured within quartz grains inside garnet porphyroblasts by non-destructive ptychographic X-ray nanotomography (PXCT). The 3D electron density maps generated by PXCT were correlated with maps from X-ray fluorescence tomography and micro-Raman spectroscopy. We found that the material trapped inside inclusions in the quartz grains consist of disordered carbon material encasing domains of iron-rich carbonaceous material. These results corroborate earlier claims (Hassenkam et al., 2017; Ohtomo et al., 2014; Rosing, 1999) for biogenic origins and are compatible with relics of metamorphosed biological material originally containing high iron/carbon ratios, comparable to ratios found in most extant organisms. These iron-rich domains represent the oldest evidence for organic iron complexes in the geologic record and are consistent with Fe-isotopic evidence for metabolic iron fractionation in > 3,700 Ma Isua banded iron formation (Czaja et al., 2013; Whitehouse & Fedo, 2007).

Hydrotalcite stability during long-term exposure to natural environmental conditions.

Hydrotalcite-like compounds are a group of layered double hydroxides widely studied as sorbents to remove organic and inorganic contaminants under laboratory conditions. This study is a proof-of-concept of the long-term fate of hydrotalcite compounds under natural environmental conditions, to bridge the gap between laboratory studies and their field application as sorbents. Hydrotalcite (HT) with intercalated carbonate species (HT-CO3) and dodecyl sulphate (HT-DS) were synthesised and placed in two groundwater monitoring wells in Denmark, one contaminated with chlorinated hydrocarbons and another with uncontaminated groundwater. To assess the structural and surface compositional changes of hydrotalcite compounds upon prolonged exposure to groundwater, the material was analysed with powder X-ray diffraction (PXRD), Fourier-transformed infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results showed that the stability and dissolution behaviour of hydrotalcite compounds under groundwater conditions depended on the intercalated anion (CO32- > DS) and groundwater dynamics (static flow > dynamic flow), while the hydrotalcite aggregate size only had a minor effect. Groundwater geochemistry influenced the precipitation of insoluble species (CaCO3, and adsorbed sulphate) on the hydrotalcite surface. The instability of hydrotalcite compounds, especially in the case of HT-DS, may constitute a significant limiting factor on their future application as sorbents under dynamic flow conditions.

Sorption of chlorinated hydrocarbons from synthetic and natural groundwater by organo-hydrotalcites: Towards their applications as remediation nanoparticles.

Chlorinated hydrocarbons (CHCs) are recalcitrant compounds frequently found as contaminants in groundwater. Hydrotalcites (HT) have emerged as promising sorbents due to their tunable properties and anion exchange capacity. Here, two types of organo-HT were synthesized, via coprecipitation, by intercalation of two different anionic surfactants, sodium dodecyl sulfate and sodium 1-dodecane sulfonate. These compounds were first characterized by a suite of techniques to quantify surfactant intercalation and to evaluate their physico-chemical properties. Next, the sorption affinity of these organo-HT towards a suite of CHCs was tested under various conditions, including interlayer surfactant type, single and multiple CHCs systems, and different water chemistry (pH, ionic composition). Sorption coefficients (Kd) and organic-matter-normalized partition coefficient (Kom) derived from linear sorption isotherms for individual CHC were inversely correlated to their hydrophobicity in the order of: tetrachloroethylene > tetrachloromethane > trichloroethylene> 1,1,2-trichloroethane > trichloromethane. Kom values were further affected by the organo-HT drying process. In contrast, varying water chemistry and pH, and the co-existence of multiple CHCs had little effect on Kom values, indicating that competition between CHCs and ionic strength have a marginal effect on the sorption affinity. The inverse linear relationship between CHC hydrophobicity and Kom is shown to be a suitable tool to predict organo-HT's sorption efficiency in complex CHCs contaminated groundwaters. Overall, organo-HT's might be used as potential sorbents for ex situ treatment of CHCs in groundwater.