Surface Area-Enhanced Cerium and Sulfur-Modified Hierarchical Bismuth Oxide Nanosheets for Electrochemical Carbon Dioxide Reduction to Formate.

Electrochemical carbon dioxide reduction reaction (ECO2RR) is a promising approach to synthesize fuels and value-added chemical feedstocks while reducing atmospheric CO2 levels. Here, high surface area cerium and sulfur-doped hierarchical bismuth oxide nanosheets (Ce@S-Bi2O3) are develpoed by a solvothermal method. The resulting Ce@S-Bi2O3 electrocatalyst shows a maximum formate Faradaic efficiency (FE) of 92.5% and a current density of 42.09 mA cm-2 at -1.16 V versus RHE using a traditional H-cell system. Furthermore, using a three-chamber gas diffusion electrode (GDE) reactor, a maximum formate FE of 85% is achieved in a wide range of applied potentials (-0.86 to -1.36 V vs RHE) using Ce@S-Bi2O3. The density functional theory (DFT) results show that doping of Ce and S in Bi2O3 enhances formate production by weakening the OH* and H* species. Moreover, DFT calculations reveal that *OCHO is a dominant pathway on Ce@S-Bi2O3 that leads to efficient formate production. This study opens up new avenues for designing metal and element-doped electrocatalysts to improve the catalytic activity and selectivity for ECO2RR.

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.

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.

Integrated air cathode microbial fuel cell-aerobic bioreactor set-up for enhanced bioelectrodegradation of azo dye Acid Blue 29.

In this study, an azo dye (Acid Blue 29 or AB29) was efficiently degraded with acetate as co-substrate into less contaminated biodegraded products using an integrated single chamber microbial fuel cell (SMFC)-aerobic bioreactor set-up. The decolorization efficiencies were varied from 91 ± 2% to 94 ± 1.9% and more than 85% of chemical oxygen demand (COD) removal was achieved for all dye concentrations after different operating time. The highest coulombic efficiency (CE) and cell potential were 3.18 ± 0.45% and 287.2 mV, respectively, for SMFC treating 100 mg L-1 of AB29. Electrochemical impedance spectroscopy (EIS) revealed that the anode resistance was 0.3 Ω representing an entirely grown biofilm on the anode surface resulted in higher electron transfer rate. Gas chromatography coupled mass spectrometry (GC-MS) investigation demonstrated that initially biodegradation of AB29 started with the cleavage of the azo bond (-N=N-), resulted the biotransformation into aromatic amines. In successive aerobic treatment stage, these amines were biodegraded into lower molecular weight compounds. The 16S rRNA microbial community analysis indicated that at phylum level, both inoculum and dye acclimated cultures were mainly consisting of Proteobacteria which was 27.9, 53.6 and 68.9% in inoculum, suspension and anodic biofilm, respectively. At genus level, both suspension and biofilm contained decolorization as well as electrochemically active bacteria. The outcomes exhibited that the AB29 decolorization would contest with electrogenic bacteria for electrons.

Effects of Applied Potential and Reactants to Hydrogen-Producing Biocathode in a Microbial Electrolysis Cell.

Understanding the mechanism of electron transfer between the cathode and microorganisms in cathode biofilms in microbial electrolysis cells (MECs) for hydrogen production is important. In this study, biocathodes of MECs were successfully re-enriched and subjected to different operating parameters: applied potential, sulfate use and inorganic carbon consumption. It was hypothesized that biocathode catalytic activity would be affected by the applied potentials that initiate electron transfer. While inorganic carbon, in the form of bicarbonate, could be a main carbon source for biocathode growth, sulfate could be a terminal electron acceptor and thus reduced to elemental sulfurs. It was found that potentials more negative than -0.8 V (vs. standard hydrogen electrode) were required for hydrogen production by the biocathode. In additional, a maximum hydrogen production was observed at sulfate and bicarbonate concentrations of 288 and 610 mg/L respectively. Organic carbons were found in the cathode effluents, suggesting that microbial interactions probably happen between acetogens and sulfate reducing bacteria (SRB). The hydrogen-producing biocathode was sulfate-dependent and hydrogen production could be inhibited by excessive sulfate because more energy was directed to reduce sulfate (E° SO42- /H2S = -0.35 V) than proton (E° H+/H2 = -0.41 V). This resulted in a restriction to the hydrogen production when sulfate concentration was high. Domestic wastewaters contain low amounts of organic compounds and sulfate would be a better medium to enrich and maintain a hydrogen-producing biocathode dominated by SRB. Besides the risks of limited mass transport and precipitation caused by low potential, methane contamination in the hydrogen-rich environment was inevitable in the biocathode after long term operation due to methanogenic activities.

Enzymatic fuel cells with an oxygen resistant variant of pyranose-2-oxidase as anode biocatalyst.

In enzymatic fuel cells (EnFCs), hydrogen peroxide formation is one of the main problems when enzymes, such as, glucose oxidase (GOx) is used due to the conversion of oxygen to hydrogen peroxide in the catalytic reaction. To address this problem, we here report the first demonstration of an EnFC using a variant of pyranose-2-oxidase (P2O-T169G) which has been shown to have low activity towards oxygen. A simple and biocompatible immobilisation approach incorporating multi-walled-carbon nanotubes within ferrocene (Fc)-Nafion film was implemented to construct EnFCs. Successful immobilisation of the enzymes was demonstrated showing 3.2 and 1.7-fold higher current than when P2O-T169G and GOx were used in solution, respectively. P2O-T169G showed 25% higher power output (maximum power density value of 8.45 ± 1.6 µW cm-2) and better stability than GOx in aerated glucose solutions. P2O-T169G maintained > 70% of its initial current whereas GOx lost activity > 90% during the first hour of 12 h operation at 0.15 V (vs Ag/Ag+). A different fuel cell configuration using gas-diffusion cathode and carbon paper electrodes were used to improve the power output of the fuel cell to 29.8 ± 6.1 µW cm-2. This study suggests that P2O-T169G with low oxygen activity could be a promising anode biocatalyst for EnFC applications.

Electrochemical Detection of Plasma Immunoglobulin as a Biomarker for Alzheimer's Disease.

The clinical diagnosis and treatment of Alzheimer's disease (AD) represent a challenge to clinicians due to the variability of clinical symptomatology as well as the unavailability of reliable diagnostic tests. In this study, the development of a novel electrochemical assay and its potential to detect peripheral blood biomarkers to diagnose AD using plasma immunoglobulins is investigated. The immunosensor employs a gold electrode as the immobilizing substrate, albumin depleted plasma immunoglobulin as the biomarker, and polyclonal rabbit Anti-human immunoglobulin (against IgA, IgG, IgM) as the receptor for plasma conjugation. The assay showed good response, sensitivity and reproducibility in differentiating plasma immunoglobulin from AD and control subjects down to 10-9 dilutions of plasma immunoglobulin representing plasma content concentrations in the pg mL-1 range. The newly developed assay is highly sensitive, less time consuming, easy to handle, can be easily modified to detect other dementia-related biomarkers in blood samples, and can be easily integrated into portable devices.

Bioanode as a limiting factor to biocathode performance in microbial electrolysis cells.

The bioanode is important for a microbial electrolysis cell (MEC) and its robustness to maintain its catalytic activity affects the performance of the whole system. Bioanodes enriched at a potential of +0.2V (vs. standard hydrogen electrode) were able to sustain their oxidation activity when the anode potential was varied from -0.3 up to +1.0V. Chronoamperometric test revealed that the bioanode produced peak current density of 0.36A/m2 and 0.37A/m2 at applied potential 0 and +0.6V, respectively. Meanwhile hydrogen production at the biocathode was proportional to the applied potential, in the range from -0.5 to -1.0V. The highest production rate was 7.4L H2/(m2 cathode area)/day at -1.0V cathode potential. A limited current output at the bioanode could halt the biocathode capability to generate hydrogen. Therefore maximum applied potential that can be applied to the biocathode was calculated as -0.84V without overloading the bioanode.

Electrochemical oxidation of glucose using mutant glucose oxidase from directed protein evolution for biosensor and biofuel cell applications.

In this study, electrochemical characterisation of glucose oxidation has been carried out in solution and using enzyme polymer electrodes prepared by mutant glucose oxidase (B11-GOx) obtained from directed protein evolution and wild-type enzymes. Higher glucose oxidation currents were obtained from B11-GOx both in solution and polymer electrodes compared to wt-GOx. This demonstrates an improved electrocatalytic activity towards electrochemical oxidation of glucose from the mutant enzyme. The enzyme electrode with B11-GOx also showed a faster electron transfer indicating a better electronic interaction with the polymer mediator. These encouraging results have shown a promising application of enzymes developed by directed evolution tailored for the applications of biosensors and biofuel cells.

Feasibility study of introducing redox property by modification of PMBN polymer for biofuel cell applications.

In this study, the feasibility of introducing redox property to an amphiphilic phospholipid polymer (PMBN) was investigated. The active ester group in the side chain of the polymer was used to react with pyrroloquinoline quinine (PQQ). Redox peaks that corresponded to PQQ redox potentials were observed after the modification. Glucose oxidase was immobilized to the modified polymer. Electrochemical oxidation of glucose was carried out with the polymer electrode. The oxidation current increased with elevating glucose concentration indicating electron transfer established between the electrode and enzyme. It suggests that by modification, PMBN is possible to use for enzyme electrode for bioelectronics.