Probing the Effects of Electrode Composition and Morphology on the Effectiveness of Silicon Oxide Overlayers to Enhance Selective Oxygen Evolution in the Presence of Chloride Ions.

Seawater electrolysis offers significant logistical advantages over freshwater electrolysis but suffers from a fundamental selectivity problem at the anode. To prevent the evolution of toxic chlorine alongside the evolution of oxygen, a promising approach is the use of electrochemically inert overlayers. Such thin films can exert a perm-selective effect, allowing the transport of water and oxygen between the bulk electrolyte and the electrocatalytic buried interface while suppressing the transport of chloride ions. In this work, we investigate thin (5-20 nm) overlayer films composed of amorphous silicon oxide (SiO x ) and their application to suppressing the chlorine evolution reaction (CER) in favor of the oxygen evolution reaction (OER) during acidic saltwater electrolysis on three different types of electrodes. While SiO x overlayers are seen to be an effective barrier against the CER on well-defined, smooth Pt thin films, decreasing the CER activity roughly 20-fold, this ability has not been previously explored on Ir-based catalysts with a higher surface area relevant to industrial applications. On amorphous iridium oxide electrodes, the selectivity toward the CER versus the OER was marginally reduced from ∼98 to ∼94%, which was attributed to the higher abundance of defects in overlayers deposited on the rougher electrode. On the other hand, Ir-based anodes consisting of thick mixed metal oxide films supported on Ti showed a significant decrease in CER selectivity, from ∼100 to ∼50%, although this came at the cost of reduced activity toward the OER. These results show that the morphology and composition of the underlying electrode play important roles in the effectiveness of the selective overlayers and provide guidance for further development of high-surface-area OER-selective anodes.

Effect of electrolyte composition on electrochemical oxidation: Active sulfate formation, benzotriazole degradation, and chlorinated by-products distribution.

Electrochemical oxidation is an effective technique for treating persistent organic pollutants, which are hardly removed in conventional wastewater treatment plants. Sulfate and chloride salts commonly used and present in natural wastewater influence the electrochemical degradation process. In this study, the effect of electrolyte composition on the active sulfate species (SO4●⁻ and S2O82⁻) formation, benzotriazole degradation-a model organic compound, and chlorinated by-products distribution have been investigated while using a boron-doped diamond (BDD) anode. Different Na2SO4:NaNO3 and Na2SO4:NaCl ratios with constant conductivity of 10 mS/cm were used in the experiments and applied anode potential was kept constant at 4.3 V vs. Ag/AgCl. The electrogenerated SO4●⁻ and S2O82⁻ formation were faster in 10:1 and 2:1 Na2SO4:NaNO3 ratios than in the 1:0 ratio. The ●OH-mediated SO4●⁻ production has prevailed in 10:1 and 2:1 ratios. However, ●OH-mediated SO4●⁻ production has hindered the 1:0 ratio due to excess chemisorption of SO42⁻ on the BDD anode. Similarly, the faster benzotriazole degradation, mineralization, and lowest energy consumption were achieved in the 10:1 Na2SO4:NaNO3 and Na2SO4:NaCl ratio. Besides, chlorinated organic by-product concentration (AOX) was lower in the 10:1 Na2SO4:NaCl ratio but increased with the increasing chloride ratio in the electrolyte. LC-MS analysis shows that several chlorinated organic transformation products were produced in 0:1 to 2:1 ratio, which was not found in the 10:1 Na2SO4:NaCl ratio. A comparatively higher amount of ClO4⁻ was formed in the 10:1 ratio than in 2:1 to 0:1 ratio. This ClO4⁻ formation train evidence the effective ●OH generation in a sulfate-enriched condition because the ClO4⁻ formation is positively correlated to ●OH concentration. Overall results show that sulfate-enriched electrolyte compositions are beneficial for electrochemical oxidation of biorecalcitrant organic pollutants.

Comparative Analysis of Photocatalytic and Electrochemical Degradation of 4-Ethylphenol in Saline Conditions.

We evaluated electrochemical degradation (ECD) and photocatalytic degradation (PCD) technologies for saline water purification, with a focus on rate comparison and formation and degradation of chlorinated aromatic intermediates using the same non-chlorinated parent compound, 4-ethylphenol (4EP). At 15 mA·cm-2, and in the absence of chloride (0.6 mol·L-1 NaNO3 was used as supporting electrolyte), ECD resulted in an apparent zero-order rate of 30 µmol L-1·h-1, whereas rates of ∼300 µmol L-1·h-1 and ∼3750 µmol L-1·h-1 were computed for low (0.03 mol·L-1) and high (0.6 mol·L-1) NaCl concentration, respectively. For PCD, initial rates of ∼330 µmol L-1·h-1 and 205 µmol L-1·h-1 were found for low and high NaCl concentrations, at a photocatalyst (TiO2) concentration of 0.5 g·L-1, and illumination at λmax ≈ 375 nm, with an intensity ∼0.32 mW·cm-2. In the chlorine mediated ECD approach, significant quantities of free chlorine (hypochlorite, Cl2) and chlorinated hydrocarbons were formed in solution, while photocatalytic degradation did not show the formation of free chlorine, nor chlorine-containing intermediates, and resulted in better removal of non-purgeable hydrocarbons than ECD. The origin of the minimal formation of free chlorine and chlorinated compounds in photocatalytic degradation is discussed based on photoelectrochemical results and existing literature, and explained by a chloride-mediated surface-charge recombination mechanism.

Anode materials for sulfide oxidation in alkaline wastewater: An activity and stability performance comparison.

Electrochemical sulfide removal can be attractive as a zero-chemical-input approach for treatment of waste streams such as spent caustics coupled to caustic recovery. A key concern is possible decline in catalytic activity, due to passivation from deposited elemental sulfur (S0) on the anode surface and stability limitation, due to sulfide oxidation under highly alkaline conditions. In this study, six commercially available electrode materials (Ir Mixed Metal Oxide (MMO), Ru MMO, Pt/IrOx, Pt, PbOx and TiO2/IrTaO2 coated titanium-based electrodes) were tested to investigate the impact of the electrocatalyst on the process efficiency in terms of sulfide removal and final product of sulfide oxidation, as well as to determine the stability of the electrocatalyst under high sulfide concentrations (50 mM Na2S) and high alkalinity (pH > 12). Short-term experiments showed that the catalyst type impacts the anode potential and the sulfide oxidation reaction products. Longer-term experiments under current densities up to 200 A m-2 showed a high differentiation in stability performance among the catalysts. Ru MMO was the most active towards sulfide oxidation with a coulombic efficiency of 63.2 ±â€¯0.5% at an average anode potential of 0.92 ±â€¯0.17 V vs SHE. Ir MMO was the most stable, preserving 100% of its original catalyst loading during the tests. The results demonstrated that Ru MMO and Ir MMO were the most suitable electrode materials for sulfide oxidation under highly alkaline conditions, while the need for establishing a good trade-off between activity, stability and cost still persists.

MnOx/IrOx as Selective Oxygen Evolution Electrocatalyst in Acidic Chloride Solution.

The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnOx), a known OER catalyst. Thin films (∼5-20 nm) of MnOx were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrOx/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring-disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnOx onto IrO x decreases the CER selectivity of the system in the presence of 30 mM Cl- from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnOx film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.

Direct anodic hydrochloric acid and cathodic caustic production during water electrolysis.

Hydrochloric acid (HCl) and caustic (NaOH) are among the most widely used chemicals by the water industry. Direct anodic electrochemical HCl production by water electrolysis has not been successful as current commercially available electrodes are prone to chlorine formation. This study presents an innovative technology simultaneously generating HCl and NaOH from NaCl using a Mn0.84Mo0.16O2.23 oxygen evolution electrode during water electrolysis. The results showed that protons could be anodically generated at a high Coulombic efficiency (i.e. ≥ 95%) with chlorine formation accounting for 3 ~ 5% of the charge supplied. HCl was anodically produced at moderate strengths at a CE of 65 ± 4% together with a CE of 89 ± 1% for cathodic caustic production. The reduction in CE for HCl generation was caused by proton cross-over from the anode to the middle compartment. Overall, this study showed the potential of simultaneous HCl and NaOH generation from NaCl and represents a major step forward for the water industry towards on-site production of HCl and NaOH. In this study, artificial brine was used as a source of sodium and chloride ions. In theory, artificial brine could be replaced by saline waste streams such as Reverse Osmosis Concentrate (ROC), turning ROC into a valuable resource.

Influence of setup and carbon source on the bacterial community of biocathodes in microbial electrolysis cells.

The microbial electrolysis cell (MEC) biocathode has shown great potential as alternative for expensive metals as catalyst for H2 synthesis. Here, the bacterial communities at the biocathode of five hydrogen producing MECs using molecular techniques were characterized. The setups differed in design (large versus small) including electrode material and flow path and in carbon source provided at the cathode (bicarbonate or acetate). A hydrogenase gene-based DNA microarray (Hydrogenase Chip) was used to analyze hydrogenase genes present in the three large setups. The small setups showed dominant groups of Firmicutes and two of the large setups showed dominant groups of Proteobacteria and Bacteroidetes. The third large setup received acetate but no sulfate (no sulfur source). In this setup an almost pure culture of a Promicromonospora sp. developed. Most of the hydrogenase genes detected were coding for bidirectional Hox-type hydrogenases, which have shown to be involved in cytoplasmatic H2 production.

Electrochemical conversion of micropollutants in gray water.

Electrochemical conversion of micropollutants in real gray water effluent was studied for the first time. Six compounds that are frequently found in personal care and household products, namely methylparaben, propylparaben, bisphenol A, triclosan, galaxolide, and 4- methylbenzilidene camphor (4-MBC), were analyzed in the effluent of the aerobic gray water treatment system in full operation. The effluent was used for lab-scale experiments with an electrochemical cell operated in batch mode. Three different anodes and five different cathodes have been tested. Among the anodes, Ru/Ir mixed metal oxide showed the best performance. Ag and Pt cathodes worked slightly better than Ti and mixed metal oxide cathodes. The compounds that contain a phenolic ring (parabens, bisphenol A, and triclosan) were completely transformed on this anode at a specific electric charge Q = 0.03 Ah/L. The compounds, which contain a benzene ring and multiple side methyl methyl groups (galaxolide, 4-MBC) required high energy input (Q ≤ 0.6 Ah/L) for transformation. Concentrations of adsorbable organohalogens (AOX) in the gray water effluent increased significantly upon treatment for all electrode combinations tested. Oxidation of gray water on mixed metal oxide anodes could not be recommended as a post-treatment step for gray water treatment according to the results of this study. Possible solutions to overcome disadvantages revealed within this study are proposed.

Acetate enhances startup of a H2-producing microbial biocathode.

H(2) can be produced from organic matter with a microbial electrolysis cell (MEC). To decrease MEC capital costs, a cathode is needed that is made of low-cost material and produces H(2) at high rate. A microbial biocathode is a low-cost candidate, but suffers from a long startup and a low H(2) production rate. In this study, the effects of cathode potential and carbon source on microbial biocathode startup were investigated. Application of a more negative cathode potential did not decrease the startup time of the biocathode. If acetate instead of bicarbonate was used as carbon source, the biocathode started up more than two times faster. The faster startup was likely caused by a higher biomass yield for acetate than for bicarbonate, which was supported by thermodynamic calculations. To increase the H(2) production rate, a flow through biocathode fed with acetate was investigated. This biocathode produced 2.2 m(3) H(2) m(-3) reactor day(-1) at a cathode potential of -0.7 V versus NHE, which was seven times that of a parallel flow biocathode of a previous study.

Monitoring the development of a microbial electrolysis cell bioanode using an electrochemical quartz crystal microbalance.

In this paper we explored the use of an electrochemical quartz crystal microbalance (QCM) to follow the development of electrochemically active biofilms on electrodes. With this technique it should be possible to monitor simultaneously the increase in biomass and the current generated by the electrogenic bacteria in the biofilm. We monitored the adsorption and the subsequent growth of bacteria that are used in microbial electrolysis cells, on a gold electrode (anode). After attachment it took about 3h for the bacteria to start to grow and develop a biofilm. Although the current was still relatively low, there is a clear correlation with the increase in biomass. The method is promising for the further investigation of the development of biofilms on electrodes (bioelectrodes).

Microbial electrolysis cell with a microbial biocathode.

This study demonstrates, for the first time, the proof-of-principle of an MEC in which both the anodic and cathodic reaction are catalyzed by microorganisms. No expensive chemical catalysts, such as platinum, are needed. Two of these MECs were simultaneously operated and reached a maximum of 1.4 A/m(2) at an applied cell voltage of 0.5 V. At a cathode potential of -0.7 V, the biocathode in the MECs had a higher current density (MEC 1: 1.9 A/m(2), MEC 2: 3.3 A/m(2)) than a control cathode (0.3 A/m(2), graphite felt without biofilm) in an electrochemical half cell. This indicates that hydrogen production is catalyzed at the biocathode, likely by electrochemically active microorganisms. The cathodic hydrogen recovery was 17% for MEC 1 and 21% for MEC 2. Hydrogen losses were ascribed to diffusion through membrane and tubing, and methane formation. After 1600 h of operation, the current density of the MECs had decreased to 0.6 A/m(2), probably caused by precipitation of calcium phosphate on the biocathode. The slow deteriorating effect of calcium phosphate, and the production of methane show the importance of studying the combination of bioanode and biocathode in one electrochemical cell, and of studying long term performance of such an MEC.

New applications and performance of bioelectrochemical systems.

Bioelectrochemical systems (BESs) are emerging technologies which use microorganisms to catalyze the reactions at the anode and/or cathode. BES research is advancing rapidly, and a whole range of applications using different electron donors and acceptors has already been developed. In this mini review, we focus on technological aspects of the expanding application of BESs. We will analyze the anode and cathode half-reactions in terms of their standard and actual potential and report the overpotentials of these half-reactions by comparing the reported potentials with their theoretical potentials. When combining anodes with cathodes in a BES, new bottlenecks and opportunities arise. For application of BESs, it is crucial to lower the internal energy losses and increase productivity at the same time. Membranes are a crucial element to obtain high efficiencies and pure products but increase the internal resistance of BESs. The comparison between production of fuels and chemicals in BESs and in present production processes should gain more attention in future BES research. By making this comparison, it will become clear if the scope of BESs can and should be further developed into the field of biorefineries.

Use of biocompatible buffers to reduce the concentration overpotential for hydrogen evolution.

The hydrogen evolution reaction (HER) at Pt-cathodes of microbial electrolysis cells (MEC) has been associated with overpotentials of several hundred millivolts. The high overpotentials challenge the sustainability of an MEC. This paper shows that the HER overpotential at MEC relevant pH values is reduced if buffer is present At 15 A/m2 and 50 mM buffer, the lowest overpotential for phosphate was -0.05 V at pH 6.2, for ammonia was -0.05 V at pH 9.0, for carbonate was -0.09 V at pH 9.3, for Tris(hydroxymethyl)aminomethane was -0.07 V at pH 7.8, and for N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid was -0.08 V at pH 7.2. It was shown that the effect of buffer on the overpotentialis strongly pH dependent Furthermore, experimental data and a mass transport equation showed that by increasing the buffer concentration or linear flow speed (i.e., pump speed), or decreasing the current density (i) the overpotential reduces and (ii) the minimum overpotential is reached at a pH that approaches the buffer dissociation constant (pKa). Thus, to reduce the HER overpotential of an MEC, buffer (i.e., pKa), buffer concentration, linear flow speed, and current density must be well balanced with the expected operational pH.

Hydrogen production with a microbial biocathode.

This paper, for the first time, describes the development of a microbial biocathode for hydrogen production that is based on a naturally selected mixed culture of electrochemically active micro-organisms. This is achieved through a three-phase biocathode startup procedure that effectively turned an acetate- and hydrogen-oxidizing bioanode into a hydrogen-producing biocathode by reversing the polarity of the electrode. The microbial biocathode that was obtained in this way had a current density of about -1.2 A/Nm2 at a potential of -0.7 V. This was 3.6 times higher than that of a control electrode (-0.3 A/m2). Furthermore, the microbial biocathode produced about 0.63 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 49% during hydrogen yield tests, whereas the control electrode produced 0.08 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 25%. The effluent of the biocathode chamber could be used to inoculate another electrochemical cell that subsequently also developed an identical hydrogen-producing biocathode (-1.1 A/m2 at a potential of -0.7 V). Scanning electron micrographs of both microbial biocathodes showed a well-developed biofilm on the electrode surface.

Microbial electrolysis cells for high yield hydrogen gas production from organic matter.

The use of electrochemically active bacteria to break down organic matter, combined with the addition of a small voltage (> 0.2 V in practice) in specially designed microbial electrolysis cells (MECs), can result in a high yield of hydrogen gas. While microbial electrolysis was invented only a few years ago, rapid developments have led to hydrogen yields approaching 100%, energy yields based on electrical energy input many times greater than that possible by water electrolysis, and increased gas production rates. MECs used to make hydrogen gas are similar in design to microbial fuel cells (MFCs) that produce electricity, but there are important differences in architecture and analytical methods used to evaluate performance. We review here the materials, architectures, performance, and energy efficiencies of these MEC systems that show promise as a method for renewable and sustainable energy production, and wastewater treatment.