Fucose modifies short chain fatty acid and H2S formation through alterations of microbial cross-feeding activities.

Algae are a rich but unexplored source of fibers with the potential to contribute to the next generation of prebiotics. The sulfated brown algae polysaccharide, fucoidan, is mainly composed of the deoxy-hexose L-fucose, which can be metabolized to 1,2-propanediol (1,2-PD) or lactate by gut microbes as precursors of propionate and butyrate. It was the aim of this study to investigate the impact of fucoidan on the fermentation capacity of the fecal microbiota and to compare to fucose. In batch fermentations of fecal microbiota collected from 17 donor samples, fucose promoted the production of propionate while no consistent effect was observed for commercial fucoidan and Fucus vesiculosus extract prepared in this study containing laminarin and fucoidan. H2S production was detected under all tested conditions, and levels were significantly lower in the presence of fucose in a dose-dependent manner. The addition of high fucose levels led to higher relative abundance of microbial 1,2-PD and lactate cross-feeders. Our results highlight that fucose and not fucoidan addition impacted fermentation capacity and increased the proportions of propionate and butyrate, which allows for precise modulation of intestinal microbiota activity.

Electrochemical nitrogen reduction reaction over gallium - a computational and experimental study.

Ga was identified earlier as one of the "overlooked" metals for catalyzing the electrochemical nitrogen reduction reaction (ENRR). We investigate here the electrocatalytic activity of Ga towards the nitrogen reduction reaction. We used a combination of molecular modelling and simulations using periodic density functional theory calculations (DFT), and experimental ENRR measurements. The ENRR was found to proceed via an associative mechanism where the first PCET to dinitrogen forming the surface adsorbed N2H* species is the overpotential limiting step. The bare Ga cathode has a high overpotential (>2 V (SHE)) for the ENRR. We also investigated the effect of a water-in-salt electrolyte (WISE) on the rate of ammonia formation. The addition of an Li salt lowers the overpotential to 1.88 V (SHE). DFT calculations revealed that the H-adatom was more favorably bound than the N-adatom, and the hydrogen evolution reaction (HER) is expected to dominate at high cathodic potentials. Experimental ENRR tests corroborate our results wherein no significant NH3 formation was detected. The low electrochemical activity of Ga is attributed to poor binding and activation of N2 which originates from an electropositive surface charge distribution.

Low-Valence Znδ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO2 Reduction.

A nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Znδ+ -NC) is reported. It contains saturated four-coordinate (Zn-N4 ) and unsaturated three-coordinate (Zn-N3 ) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory. Znδ+ -NC catalyzes electrochemical reduction of CO2 to CO with near-unity selectivity in water at an overpotential as low as 310 mV. A current density up to 1 A cm-2 can be achieved together with high CO selectivity of >95 % using Znδ+ -NC in a flow cell. Calculations suggest that the unsaturated Zn-N3 could dramatically reduce the energy barrier by stabilizing the COOH* intermediate owing to the electron-rich environment of Zn. This work sheds light on the relationship among coordination number, valence state, and catalytic performance and achieves high current densities relevant for industrial applications.

Direct Measurements of Electroviscous Phenomena in Nafion Membranes.

Investigation of electroviscous effects is of interest to technologies that exploit transport of ions through ion exchange membranes, charged capillaries, and porous media. When ions move through such media due to a hydrostatic pressure difference, they interact with the fixed charges, leading to an increased hydraulic resistance. Experimentally this is observed as an apparent increase in the viscosity of the solution. Electroviscous effects are present in all electrochemical membrane-based processes ranging from nanofiltration to fuel-cells and redox flow batteries. Direct measurements of electroviscous effects varying the applied ionic current through Nafion membranes have, to the best of the authors' knowledge, not yet been reported in literature. In the current study, electroviscous phenomena in different Nafion ion exchange membranes are measured directly with a method where the volume permeation is measured under constant trans-membrane pressure difference while varying the ion current density in the membrane. The direct measurement of the electroviscous effect is compared to the one calculated from the phenomenological transport equations and measured transport coefficients. Within the experimental uncertainty, there is a good agreement between the two values for all membranes tested. We report here an electroviscous effect for all Nafion membranes tested to be κH?κH-1=1.15-0.052+0.035.

Steady State and Dynamic Response of Voltage-Operated Membrane Gates.

An electrochemical flow cell with Nafion 212, aqueous LiI/I 2 redox solution, and carbon paper electrode was operated as an electro-osmotic gate based on the Electrokinetic Energy Conversion (EKEC) principle. The gate was operated in different modes. (i) In normal DC pump operation it is shown to follow the predictions from the phenomenological transport equations. (ii) Furthermore, it was also demonstrated to operate as a normally open, voltage-gated valve for microfluidic purposes. For both pump and valve operations low energy requirements (mW range) were estimated for precise control of small flows ( µ L range). (iii) Finally, the dynamic response of the pump was investigated by using alternating currents at a range of different frequencies.

Data on flow cell optimization for membrane-based electrokinetic energy conversion.

This article elaborates on the design and optimization of a specialized flow cell for the measurement of direct conversion of pressure into electrical energy (Electrokinetic Energy Conversion, EKEC) which has been presented in Østedgaard-Munck et al. (2017) [1]. Two main flow cell parameters have been monitored and optimized: A) the hydraulic pressure profile on each side of the membrane introduced by pumps recirculating the electrolyte solution through the flow fields and B) the electrical resistance between the current collectors across the combined flow cell. The latter parameter has been measured using four-point Electrochemical Impedance spectroscopy (EIS) for different flow rates and concentrations. The total cell resistance consists of contributions from different components: the membrane [Formula: see text], anode charge transfer [Formula: see text], cathode charge transfer [Formula: see text], and ion diffusion in the porous electrodes [Formula: see text]. The intrinsic membrane properties of Nafion 117 has been investigated experimentally in LiI/I2 solutions with concentrations ranging between 0.06 and 0.96 M and used to identify the preferred LiI/I2 solution concentration. This was achieved by measuring the solution uptake, internal solution concentration and ion exchange capacity. The membrane properties were further used to calculate the transport coefficients and electrokinetic Figure of merit in terms of the Uniform potential and Space charge models. Special attention has been put on the streaming potential coefficient which is an intrinsic property.

Counter-ion transport number and membrane potential in working membrane systems.

In this work we use the general space-charge (SC) theory for a combined transport model of fluid and ion through cylindrical nanopores to derive equations for the membrane potential and counter-ion transport numbers. We discuss this approach for ion exchange membranes assuming aqueous domains as interconnected network of cylindrical pores. The transport number calculations from the SC theory are compared with the corresponding ones from the uniform potential (UP) and Teorell-Meyer-Sievers (TMS) models in the case of both zero and non-zero concentration gradient across the membrane and with an applied current density. By using this approach we suggest the optimal conditions for performing membrane potential experiments (i.e. choice of electrolyte and concentration difference) depending on an easily accessible membrane property, namely the volumetric charge density. We also theoretically describe a novel dynamic method to determine in a single experiment the membrane potential and membrane conductivity. To exemplify the use of the dynamic method we report the calculations based on typical operating conditions of the reverse electrodialysis process. The numerical results are presented in terms of the electrical potential difference versus the average pore radius and charge density. The resulting map is a useful tool for a rational design of an effective membrane morphology for a specific electrochemical application.

Permeability of uncharged organic molecules in reverse osmosis desalination membranes.

Reverse osmosis (RO) membranes are primarily designed for removal of salts i.e. for desalination of brackish and seawater, but they have also found applications in removal of organic molecules. While it is clear that steric exclusion is the dominant removal mechanism, the fundamental explanation for how and why the separation occurs remains elusive. Until recently there was no strong microscopic evidences elucidating the structure of the active polyamide layers of RO membranes, and thus they have been conceived as "black boxes"; or as an array of straight capillaries with a distribution of radii; or as polymers with a small amount of polymer free domains. The knowledge of diffusion and sorption coefficients is a prerequisite for understanding the intrinsic permeability of any organic solute in any polymer. At the same time, it is technically challenging to accurately measure these two fundamental parameters in very thin (20-300 nm) water-swollen active layers. In this work we have measured partition and diffusion coefficients and RO permeabilities of ten organic solutes in water-swollen active layers of two types of RO membranes, low (SWC4+) and high flux (XLE). We deduced from our results and recent microscopic studies that the solute flux of organic molecules in polyamide layer of RO membranes occurs in two domains, dense polymer (the key barrier layer) and the water filled domains.

Tailoring Membrane Nanostructure and Charge Density for High Electrokinetic Energy Conversion Efficiency.

The electrokinetic energy conversion (EKEC) of hydraulic work directly into electrical energy has been investigated in charged polymeric membranes with different pore charge densities and characteristic diameters of the nanoporous network. The membranes were synthesized from blends of nitrocellulose and sulfonated polystyrene (SPS) and were comprehensively characterized with respect to structure, composition, and transport properties. It is shown that the SPS can be used as a sacrificial pore generation medium to tune the pore size and membrane porosity, which in turn highly affects the transport properties of the membranes. Furthermore, it is shown that very high EKEC efficiencies (>35%) are encountered in a rather narrow window of the properties of the nanoporous membrane network, that is, with pore diameters of ca. 10 nm and pore charge densities of 4.6 × 10(2) to 1.5 × 10(3) mol SO3(-) m(-3) for dilute solutions (0.03 M LiCl). The high absolute value of the efficiency combined with the determination of the optimal membrane morphology makes membrane-based EKEC devices a step closer to practical applications and high-performance membrane design less empirical.

High electrokinetic energy conversion efficiency in charged nanoporous nitrocellulose/sulfonated polystyrene membranes.

The synthesis, characterization, and electrokinetic energy conversion performance have been investigated experimentally in a charged polymeric membrane based on a blend of nitrocellulose and sulfonated polystyrene. The membrane is characterized by a moderate ion exchange capacity and a relatively porous structure with average pore diameter of 11 nm. With electrokinetic energy conversion, pressure can be converted directly into electric energy and vice versa. From the electrokinetic transport properties, a remarkably large intrinsic maximum efficiency of 46% is found. It is anticipated that the results are an experimental verification of theoretical models that predict high electrokinetic energy conversion efficiency in pores with high permselectivity and hydrodynamic slip flow. Furthermore, the result is a promising step for obtaining efficient low-cost electrokinetic generators and pumps for small or microscale applications.