Pulsed Electrolysis with a Nickel Molecular Catalyst Improves Selectivity for Carbon Dioxide Reduction.

Pulsed electrolysis can significantly improve carbon dioxide reduction on metal electrodes, but the effect of short (millisecond to seconds) voltage steps on molecular electrocatalysts is largely unstudied. In this work, we investigate the effect pulse electrolysis has on the selectivity and stability of the homogeneous electrocatalyst [Ni(cyclam)]2+ at a carbon electrode. By tuning the potential and pulse duration, we achieve a significant improvement in CO Faradaic efficiencies (85%) after 3 h, double that of the system under potentiostatic conditions. The improved activity is due to in situ catalyst regeneration from an intermediate that occurs as part of the catalyst's degradation pathway. This study demonstrates the wider opportunity to apply pulsed electrolysis to molecular electrocatalysts to control activity and improve selectivity.

Zero-Gap Bipolar Membrane Electrolyzer for Carbon Dioxide Reduction Using Acid-Tolerant Molecular Electrocatalysts.

The scaling-up of electrochemical CO2 reduction requires circumventing the CO2 loss as carbonates under alkaline conditions. Zero-gap cell configurations with a reverse-bias bipolar membrane (BPM) represent a possible solution, but the catalyst layer in direct contact with the acidic environment of a BPM usually leads to H2 evolution dominating. Here we show that using acid-tolerant Ni molecular electrocatalysts selective (>60%) CO2 reduction can be achieved in a zero-gap BPM device using a pure water and CO2 feed. At a higher current density (100 mA cm-2), CO selectivity decreases, but was still >30%, due to reversible product inhibition. This study demonstrates the importance of developing acid-tolerant catalysts for use in large-scale CO2 reduction devices.

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.

No re-calibration required? Stability of a bioelectrochemical sensor for biodegradable organic matter over 800 days.

Microbial Fuel Cells (MFCs) operated as biosensors could potentially enable truly low-cost, real-time monitoring of organic loading in wastewaters. The current generated by MFCs has been correlated with conventional measures of organic load such as Biochemical Oxygen Demand (BOD), but much remains to be established in terms of the reliability and applicability of such sensors. In this study, batch-mode and multi-stage, flow-mode MFCs were operated for over 800 days and regularly re-calibrated with synthetic wastewater containing glucose and glutamic acid (GGA). BOD5 calibration curves were obtained by normalising the current measured as a percentage of maximum current. There was little drift between recalibrations and non-linear Hill models of the combined dataset had R2 of 88-95%, exhibiting a stable response over time and across devices. Nonetheless, factors which do affect calibration were also assessed. Increasing external resistance (from 43.5 to 5100 Ω) above the internal resistance determined by polarisation curve decreased the calibration upper limit from 240 to 30 mg/l O2 BOD5. Furthermore, more fermentable carbon sources increased the detection range, as tested with samples of real wastewater and synthetic media containing GGA, glucose-only and glutamic acid-only. Biofilm acclimatisation therefore did not account for differences between aerobic oxygen demand determinations and anaerobic MFC responses; these are likely attributable to competitive processes such as fermentation. This further highlights the potential for MFCs as real-time sensors for organic load monitoring and process control in addition to BOD-compliant measurement systems.

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.

Copper-Indium Binary Catalyst on a Gas Diffusion Electrode for High-Performance CO2 Electrochemical Reduction with Record CO Production Efficiency.

Cu-In metallic hybrid is a promising non-noble catalyst for selective electrochemical CO2 reduction (eCO2R) to CO, but the lack of direct assembly with a gas diffusion electrode (GDE) limits the further development of eCO2R to CO with both high Faradaic efficiency (FE) and high current density. In this study, an in situ electrochemical spontaneous precipitation (ESP) method was applied for the first time to prepare GDE-combined Cu-In electrocatalysts. The optimum Cu-In catalyst consists of a nanoscale "core-shell" structure of polycrystalline CuxO covered by the amorphous In(OH)3 interface. Higher than 90% FE of CO production has been achieved. With the synergy of a GDE flow cell and 1 M KOH catholyte, a current density of ∼200 mA cm-2 was reached at -1.17 V (reversible hydrogen electrode), which enabled a CO yield efficiency record of 3.05 mg min-1(CO2/15 mL min-1 with a 2 cm2 electrode). The ratios between CO and H2 produced can be effectively modulated via fine-tuning ESP conditions demonstrating possibility of generating CO or syngas with tuneable ratios. The present study provides a simple approach for constructing novel catalytic interfaces with dual active centers for eCO2R and other emerging electrochemical catalysis research.

Bioelectrochemical treatment and recovery of copper from distillery waste effluents using power and voltage control strategies.

Copper recovery from distillery effluent was studied in a scalable bioelectro-chemical system with approx. 6.8 L total volume. Two control strategies based on the control of power with maximum power point tracking (MPPT) and the application of 0.5 V using an external power supply were used to investigate the resultant modified electroplating characteristics. The reactor system was constructed from two electrically separated, but hydraulically connected cells, to which the MPPT and 0.5 V control strategies were applied. Three experiments were carried out using a relatively high copper concentration i.e. 1000 mg/L followed by a lower concentration i.e. 50 mg/L, with operational run times defined to meet the treatment requirements for distillery effluents considered. Real distillery waste was introduced into the cathode to reduce ionic copper concentrations. This waste was then recirculated to the anode as a feed stock after the copper depletion step, in order to test the bioenergy self-sustainability of the system. Approx. 60-95% copper was recovered in the form of deposits depending on starting concentration. However, the recovery was low when the anode was supplied with copper depleted distillery waste. Through process control (MPPT or 0.5 V applied voltage) the amount and form of the copper recovered could be manipulated.