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.

Analysis of the Ordering Effects in Anthraquinone Thin Films and Its Potential Application for Sodium Ion Batteries.

The ordering effects in anthraquinone (AQ) stacking forced by thin-film application and its influence on dimer solubility and current collector adhesion are investigated. The structural characteristics of AQ and its chemical environment are found to have a substantial influence on its electrochemical performance. Computational investigation for different charged states of AQ on a carbon substrate obtained via basin hopping global minimization provides important insights into the physicochemical thin-film properties. The results reveal the ideal stacking configurations of the individual AQ-carrier systems and show ordering effects in a periodic supercell environment. The latter reveals the transition from intermolecular hydrogen bonding toward the formation of salt bridges between the reduced AQ units and a stabilizing effect upon the dimerlike rearrangement, while the strong surface-molecular interactions in the thin-film geometries are found to be crucial for the formed dimers to remain electronically active. Both characteristics, the improved current collector adhesion and the stabilization due to dimerization, are mutual benefits of thin-film electrodes over powder-based systems. This hypothesis has been further investigated for its potential application in sodium ion batteries. Our results show that AQ thin-film electrodes exhibit significantly better specific capacities (233 vs 87 mAh g-1 in the first cycle), Coulombic efficiencies, and long-term cycling performance (80 vs 4 mAh g-1 after 100 cycles) over the AQ powder electrodes. By augmenting the experimental findings via computational investigations, we are able to suggest design strategies that may foster the performance of industrially desirable powder-based electrode materials.

Tailored energy level alignment at MoOX/GaP interface for solar-driven redox flow battery application.

MoOX is commonly considered to be a high work-function semiconductor. From x-ray photoelectron spectroscopy and photo-electrochemical analysis, it is shown that MoOX can be considered as an effective hole transfer layer for the GaP-based device. Specifically, in the absence of carbon contamination using an ion beam cleaning step, the oxygen vacancy derived defect band located inside the bandgap becomes the main charge transfer mechanism. We demonstrate, for the first time, a device with a MoOX/GaP junction that functions as an unbiased photo-charging cell for the redox flow battery system with AQS/AQSH2∥I-/I3 - redox couples. This work has important implications toward enabling MoOX applications beyond the conventional solar cells, including electrochemical energy storage and chemical conversion systems.

Are There Any Overlooked Catalysts for Electrochemical NH3 Synthesis-New Insights from Analysis of Thermochemical Data.

We report relations between nitrogen-binding-energy descriptors obtained from experimental thermochemical data and limiting potentials from density functional theory data. We use the relations to build the largest volcano plot for nitrogen reduction reaction (NRR). We found that (1) Mn, Ga, and In are overlooked catalysts and (2) there are unidentified materials on the top of the volcano. Using experimental exchange current densities of hydrogen evolution reaction (HER) and Pourbaix diagrams we have identified conditions at which Mn, Ga, and In remain stable in water and selectively catalyze NRR over HER. We found that Fe, Au, Cu, Bi, and Pd, on contrary to what was reported earlier, need smaller applied potentials to start the onset of HER than NRR in water. We make a critical discussion about them and other candidates and we believe our results can be used to identify false positive measurements in the research field.

Unbiased, complete solar charging of a neutral flow battery by a single Si photocathode.

Solar redox flow batteries have attracted attention as a possible integrated technology for simultaneous conversion and storage of solar energy. In this work, we review current efforts to design aqueous solar flow batteries in terms of battery electrolyte capacity, solar conversion efficiency and depth of solar charge. From a materials cost and design perspective, a simple, cost-efficient, aqueous solar redox flow battery will most likely incorporate only one semiconductor, and we demonstrate here a system where a single photocathode is accurately matched to the redox couples to allow for a complete solar charge. The single TiO2 protected Si photocathode with a catalytic Pt layer can fully solar charge a neutral TEMPO-sulfate/ferricyanide battery with a cell voltage of 0.35 V. An unbiased solar conversion efficiency of 1.6% is obtained and this system represents a new strategy in solar RFBs where a single silicon photocathode is paired with energetically suitable redox couples to build an integrated solar energy conversion and storage device with full realization of the energy storage capacity.

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.

Interactions of Organics within Hydrated Selective Layer of Reverse Osmosis Desalination Membrane: A Combined Experimental and Computational Study.

In this work we have examined a computational approach in predicting the interactions between uncharged organic solutes and polyamide membranes. We used three model organic molecules with identical molecular weights (100.1 g/mol), 4-aminopiperidine, 3,3-dimethyl-2-butanone (pinacolone) and methylisobutyl ketone for which we obtained experimental data on partitioning, diffusion and separation on a typical seawater reverse osmosis (RO) membrane. The interaction energy between the solutes and the membrane phase (fully aromatic polyamide) was computed from molecular dynamics (MD) simulations and the resulting sequence was found to correlate well with the experimental rejections and sorption data. Sorption of the different organic solutes within the membrane skin layer determined from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) nicely agreed with interaction energies computed from molecular simulations. Qualitative information about solute diffusivity inside the membrane was also extracted from MD simulations while ATR-FTIR experiments indicated strongly hindered diffusion with diffusion coefficients in the membrane about 10-15 m2/s. The computational approach presented here could be a first step toward predicting rejections trends of, for example, hormones and pharmaceuticals by RO dense membranes.

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility.

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

Does hindered transport theory apply to desalination membranes?

As reverse osmosis (RO) and nanofiltration polyamide membranes become increasingly used for water purification, prediction of pollutant transport is required for membrane development and process engineering. Many popular models use hindered transport theory (HTT), which considers a spherical solute moving through an array of fluid-filled rigid cylindrical pores. Experiments and molecular dynamic simulations, however, reveal that polyamide membranes have a distinctly different structure of a "molecular sponge", a network of randomly connected voids widely distributed in size. In view of this disagreement, this study critically examined the validity of HTT by directly measuring diffusivities of several alcohols within a polyamide film of commercial RO membrane using attenuated total reflection-FTIR. It is found that measured diffusivities deviate from HTT predictions by as much as 2-3 orders of magnitude. This result indicates that HTT does not adequately describe solute transport in desalination membranes. As a more adequate alternative, the concept of random resistor networks is suggested, with resistances described by models of activated transport in "soft" polymers without a sharp size cutoff and with a proper address of solute partitioning.

Permeability and selectivity of reverse osmosis membranes: correlation to swelling revisited.

Membrane swelling governs both rejection of solutes and permeability of polymeric membranes, however very few data have been available on swelling in water of salt-rejecting reverse osmosis (RO) membranes. This study assesses swelling, thickness and their relation to water permeability for four commercial polyamide (PA) RO membranes (SWC4+, ESPA1, XLE and BW30) using atomic force microscopy (AFM) and attenuated total reflection Fourier transform IR spectroscopy (ATR-FTIR). ATR-FTIR offered a significantly improved estimate of the actual barrier thickness of PA, given AFM is biased by porosity ("fluffy parts") or wiggling of the active layer or presence of a coating layer. Thus obtained intrinsic permeability (permeability times thickness) and selectivity of aromatic polyamides plotted versus swelling falls well on a general trend, along with previously reported data on several common materials showing RO and NF selectivity. The observed general trend may be rationalized by viewing the polymers as a random composite medium containing molecularly small pores. The results suggest that the combination of a rigid low dielectric matrix, limiting the pore size, with multiple hydrophilic H-bonding sites may be a common feature of RO/NF membranes, allowing both high permeability and selectivity.

Wastewater from wood and pulp industry treated by combination of coagulation, adsorption on modified clinoptilolite tuff and membrane processes.

Wastewater from the wood and pulp industry is of environmental concern. It contains high concentrations of organic and inorganic matter. In this work a combined method of coagulation, adsorption and nanofiltration/reverse osmosis (NF/RO) was investigated in the purification of biologically treated wastewater from wood processing. Coagulation with 0.8 g dm(-3) AlCl3 x 6H2O and adsorption on 2.5 g m(-3) modified clinoptilolite tuff resulted in removal efficiencies of total carbon (TC), total organic carbon (TOC) and inorganic carbon (IC) up to 67.1%, 77.4% and 49.5%, respectively. Almost complete removal of solutes was achieved after NF/RO treatment. The TOC removal efficiency with RO membrane (CPA-3, LFC-1, XLE) and tight NF membrane (NF90) was 98% and with highly porous NF membrane (DK), 88%. After the proposed treatment the purified water stream can be recycled into the process or safely disposed to the river.

Enhanced partitioning and transport of phenolic micropollutants within polyamide composite membranes.

Aromatic phenols represent an important class of endocrine-disrupting and toxic pollutants, many of which (e.g., bisphenol A and substituted phenols) are known to be insufficiently removed by reverse osmosis (RO) and nanofiltration polyamide membranes that are widely used for water purification. In this study, the mechanism of phenol transport across the polyamide layer of RO membranes is studied using model phenolic compounds hydroquinone (HQ) and its oxidized counterpart benzoquinone (BQ). The study employs filtration experiments and two electrochemical techniques, impedance spectroscopy (EIS) and chronoamperometry (CA), to evaluate the permeability of an RO membrane SWC1 to these solutes in the concentration range 0.1-10 mM. In addition, combination of the permeability data with EIS results allows separately estimating the average diffusivity and partitioning of BQ and HQ. All methods produced permeability of the order 10(-7) to 10(-6) m s(-1) that decreased with solute concentration, even though the permeability obtained from filtration was consistently lower. The decrease of permeability with concentration could be related to the nonlinear convex partitioning isotherm, in agreement with earlier measurements by FTIR. The diffusivity of HQ and BQ was estimated to be of the order 10(-15) m(2) s(-1) and partitioning coefficient of the order 10. The high affinity of phenols toward polyamide and their high uptake may change membrane characteristics at high concentration of the solute. EIS results and hydraulic permeability indeed showed that permeability to ions and water significantly decreases with increasing concentration of organic solute.