Electrochemical Properties of Carbon Fibers from Felts.

Electrochemical behaviors of individual carbon fibers coming from carbon felts were investigated using two different redox couples, 1,1'-dimethanolferrocene and potassium ferrocyanide. Electrochemical responses were examined after different oxidation treatments, then simulated and interpreted using the Kissa 1D software and existing models. Our experiments indicate that a crude carbon fiber behaves as an assembly of sites with different electrochemical reactivities. In such case, the Butler-Volmer law is not appropriate to describe the electron transfer kinetics because of the large created overpotential. Oxidation of the fiber erases the effect by increasing the kinetics of the electron transfer probably by a homogenization and increase of the reactivity on all the fiber. Additionally, analysis of the signal shows the large influence of the convection that affects the electrochemical response even at moderate scan rates (typically below 0.1-0.2 V s-1).

Enhancing hydrogen production through anode fed-batch mode and controlled cell voltage in a microbial electrolysis cell fully catalysed by microorganisms.

A microbial electrolysis cell (MEC) fully catalysed by microorganisms is an attractive technology because it incorporates the state-of-the-art concept of converting organic waste to hydrogen with less external energy input than conventional electrolysers. In this work, the impact of the anode feed mode on the production of hydrogen by the biocathode was studied. In the first part, three feed modes and MEC performance in terms of hydrogen production were evaluated. The results showed the highest hydrogen production under the continuous mode (14.6 ± 0.4), followed by the fed-batch (12.7 ± 0.4) and batch (0 L m-2 cathode day-1) modes. On one hand, the continuous mode only increased by 15% even though the hydraulic retention time (HRT) (2.78 h) was lower than the fed-batch mode (HRT 5 h). A total replacement (fed-batch) rather than a constant mix of existing anolyte and fresh medium (continuous) was preferable. On the other hand, no hydrogen was produced in batch mode due to the extensive HRT (24 h) and bioanode starvation. In the second part, the fed-batch mode was further evaluated using a chronoamperometry method under a range of applied cell voltages of 0.3-1.6 V. Based on the potential evolution at the electrodes, three main regions were identified depending on the applied cell voltages: the cathode activation (<0.8 V), transition (0.8-1.1 V), and anode limitation (>1.1 V) regions. The maximum hydrogen production recorded was 12.1 ± 2.1 L m-2 cathode day-1 at 1.0 V applied voltage when the oxidation and reduction reactions at the anode and cathode were optimal (2.38 ± 0.61 A m-2). Microbial community analysis of the biocathode revealed that Alpha-, and Deltaproteobacteria were dominant in the samples with >70% abundance. At the genus level, Desulfovibrio sp. was the most abundant in the samples, showing that these microbes may be responsible for hydrogen evolution.

Enhanced bio-production from CO2 by microbial electrosynthesis (MES) with continuous operational mode.

Technologies able to convert CO2 to various feedstocks for fuels and chemicals are emerging due to the urge of reducing greenhouse gas emissions and de-fossilizing chemical production. Microbial electrosynthesis (MES) has been shown a promising technique to synthesize organic products particularly acetate using microorganisms and electrons. However, the efficiency of the system is low. In this study, we demonstrated the simple yet efficient strategy in enhancing the efficiency of MES by applying continuous feeding regime. Compared to the fed-batch system, continuous operational mode provided better control of pH and constant medium refreshment, resulting in higher acetate production rate and more diverse bio-products, when the cathodic potential of -1.0 V Ag/AgCl and dissolved CO2 were provided. It was observed that hydraulic retention time (HRT) had a direct effect on the pattern of production, acetate production rate and coulombic efficiency. At HRT of 3 days, pH was around 5.2 and acetate was the dominant product with the highest production rate of 651.8 ± 214.2 ppm per day and a significant coulombic efficiency of 90%. However at the HRT of 7 days, pH was lower at around 4.5, and lower but stable acetate production rate of 280 ppm per day and a maximum coulombic efficiency of 80% was obtained. In addition, more diverse and longer chain products, such as butyrate, isovalerate and caproate, were detected with low concentrations only at the HRT of 7 days. Although microbial community analysis showed the change in the planktonic cells communities after switching the fed-batch mode to continuous feeding regime, Acetobacterium still remained as the responsible bacteria for CO2 reduction to acetate, dominating the cathodic biofilm.

Zinc removal and recovery from industrial wastewater with a microbial fuel cell: Experimental investigation and theoretical prediction.

Microbial fuel cells (MFCs) that simultaneously remove organic contaminants and recovering metals provide a potential route for industry to adopt clean technologies. In this work, two goals were set: to study the feasibility of zinc removal from industrial effluents using MFCs and to understand the removal process by using reaction rate models. The removal of Zn2+ in MFC was over 96% for synthetic and industrial samples with initial Zn2+ concentrations less than 2.0 mM after 22 h of operation. However, only 83 and 42% of the zinc recovered from synthetic and industrial samples, respectively, was attached on the cathode surface of the MFCs. The results marked the domination of electroprecipitation rather than the electrodeposition process in the industrial samples. Energy dispersive X-ray (EDX) analysis showed that the recovered compound contained not only Zn but also O, evidence that Zn(OH)2 could be formed. The removal of Zn2+ in the MFC followed a mechanism where oxygen was reduced to hydroxide before reacting with Zn2+. Nernst equations and rate law expressions were derived to understand the mechanism and used to estimate the Zn2+ concentration and removal efficiency. The zero-, first- and second-order rate equations successfully fitted the data, predicted the final Zn2+ removal efficiency, and suggested that possible mechanistic reactions occurred in the electrolysis cell (direct reduction), MFC (O2 reduction), and control (chemisorption) modes. The half-life, t1/2, of the Zn2+ removal reaction using synthetic and industrial samples was estimated to be 7.0 and 2.7 h, respectively. The t1/2 values of the controls (without the power input from the MFC bioanode) were much slower and were recorded as 21.5 and 7.3 h for synthetic and industrial samples, respectively. The study suggests that MFCs can act as a sustainable and environmentally friendly technology for heavy metal removal without electrical energy input or the addition of chemicals.

Parameters influencing the development of highly conductive and efficient biofilm during microbial electrosynthesis: the importance of applied potential and inorganic carbon source.

Cathode-driven applications of bio-electrochemical systems (BESs) have the potential to transform CO2 into value-added chemicals using microorganisms. However, their commercialisation is limited as biocathodes in BESs are characterised by slow start-up and low efficiency. Understanding biosynthesis pathways, electron transfer mechanisms and the effect of operational variables on microbial electrosynthesis (MES) is of fundamental importance to advance these applications of a system that has the capacity to convert CO2 to organics and is potentially sustainable. In this work, we demonstrate that cathodic potential and inorganic carbon source are keys for the development of a dense and conductive biofilm that ensures high efficiency in the overall system. Applying the cathodic potential of -1.0 V vs. Ag/AgCl and providing only gaseous CO2 in our system, a dense biofilm dominated by Acetobacterium (ca. 50% of biofilm) was formed. The superior biofilm density was significantly correlated with a higher production yield of organic chemicals, particularly acetate. Together, a significant decrease in the H2 evolution overpotential (by 200 mV) and abundant nifH genes within the biofilm were observed. This can only be mechanistically explained if intracellular hydrogen production with direct electron uptake from the cathode via nitrogenase within bacterial cells is occurring in addition to the commonly observed extracellular H2 production. Indeed, the enzymatic activity within the biofilm accelerated the electron transfer. This was evidenced by an increase in the coulombic efficiency (ca. 69%) and a 10-fold decrease in the charge transfer resistance. This is the first report of such a significant decrease in the charge resistance via the development of a highly conductive biofilm during MES. The results highlight the fundamental importance of maintaining a highly active autotrophic Acetobacterium population through feeding CO2 in gaseous form, which its dominance in the biocathode leads to a higher efficiency of the system.