Photosensitization of electro-active microbes for solar assisted carbon dioxide transformation.

Tandem bio-inorganic platform by combining efficient light harvesting properties of nano-inorganic semiconductor cadmium sulfide (CdS) with biocatalytic ability of electro-active bacteria (EAB) towards carbon dioxide (CO2) conversion is reported. Sulfur was obtained from either cysteine (EAB-Cys-CdS) or hydrogen sulfide (EAB-H2S-CdS) and experiments were carried out under similar conditions. Anchoring of the nano CdS cluster on the microbe surface was confirmed using electronic microscope. Bio-inorganic hybrid system was able to produce single and multi-carbon compounds from CO2 in visible spectrum (λ > 400 nm). Though, acetic acid was dominant (EAB-Cys-CdS, 1.46 g/l and EAB-H2S-CdS, 1.55 g/l) in both the microbe-CdS hybrids, its concentration as well as product slate varied significantly. EAB-H2S-CdS produced hexanoic acid and less methanol fraction, while the EAB-Cys-CdS produced no hexanoic acid along with almost double the concentration of methanol. Due to easy harvesting process, this bio-inorganic hybrid represents unique sustainable approach for solar-to-chemical production via CO2 transformation.

Long-term operation of electro-biocatalytic reactor for carbon dioxide transformation into organic molecules.

Electro-biocatalytic reactor was operated using selectively enriched mixed culture biofilm for about 320 days with CO2/bicarbonate as C-source. Biocathode consumed higher current (-16.2 ±â€¯0.3 A/m2) for bicarbonate transformation yielding high product synthesis (0.74 g/l/day) compared to CO2 (-9.5 ±â€¯2.8 A/m2; 0.41 g/l/day). Product slate includes butanol and butyric acid when CO2 gets transformed but propionic acid replaced both when bicarbonate gets transformed. Based on electroanalysis, the electron transfer might be H2 mediated along with direct transfer under bicarbonate turnover conditions, while it was restricted to direct under CO2. Efficiency and stability of biofilm was tested by removing the planktonic cells, and also confirmed in terms of Coulombic (85-97%) and carbon conversion efficiencies (42-48%) along with production rate (1.2-1.7 kg/m2 electrode) using bicarbonate as substrate. Selective enrichment of microbes and their growth as biofilm along with soluble CO2 have helped in efficient transformation of CO2 up to C4 organic molecules.

Bio-electrochemical system (BES) as an innovative approach for sustainable waste management in petroleum industry.

Petroleum industry is one of the largest and fast growing industries due to the ever increasing global energy demands. Petroleum refinery produces huge quantities of wastes like oily sludge, wastewater, volatile organic compounds, waste catalyst, heavy metals, etc., because of its high capacity and continuous operation of many units. Major challenge to this industry is to manage the huge quantities of waste generated from different processes due to the complexity of waste as well as changing stringent environmental regulations. To decrease the energy loss for treatment and also to conserve the energy stored in the chemical bonds of these waste organics, bio-electrochemical system (BES) may be an efficient tool that reduce the economics of waste disposal by transforming the waste into energy pool. The present review discusses about the feasibility of using BES as a potential option for harnessing energy from different waste generated from petroleum refineries.

Electro-biocatalytic conversion of carbon dioxide to alcohols using gas diffusion electrode.

Impact of gas diffusion electrodes (GDEs) was evaluated in enhancing the CO2 bio-availability for its transformation to C4-organics, especially to alcohols using selective mixed culture. Observed current density was more stable (9-11 A/m2) than submerged experiments reported and significantly varied with pH and respective CO2 solubility. Uncontrolled operating pH (starting with 8.0) showed its impact on shifting/triggering alternate metabolic pathways to increase the carbon length (butyric acid) as well as producing more reduced end products, i.e. alcohols. During the experiments, CO2 was transformed initially to a mixture of volatile fatty acids dominated with formic and acetic acids, and upon their accumulation, ethanol and butanol production was triggered. Overall, 21 g/l of alcohols and 13 g/l of organic acids were accumulated in 90 days with a coulombic efficiency (CE) of 49%. Ethanol and butanol occupied respectively about 45% and 16% of total products, indicating larger potential of this technology.

Enzymatic Electrosynthesis of Formic Acid through Carbon Dioxide Reduction in a Bioelectrochemical System: Effect of Immobilization and Carbonic Anhydrase Addition.

The enzymatic electrosynthesis of formic acid from the reduction of carbon dioxide (CO2 ) by using formate dehydrogenase (FDH) as a catalyst at the cathode in both its free and immobilized forms was studied in detail in a bioelectrochemical system (BES). The essential role of solubilizing CO2 for its conversion was also studied by adding carbonic anhydrase (CA) to the FDH enzyme in both its free and immobilized forms. FDH alone in the free form showed large variation in the reduction current [(-6.2±3.9) A m-2 ], whereas the immobilized form showed less variation [(-3.8±0.5) A m-2 ] due to increased enzyme stability. The addition of CA with FDH increased the consumption of the current in both forms due to the fact that it allowed rapid dissolution of CO2 , which made it available for the catalytic reaction with FDH. Remarkably, stable consumption of the current was observed throughout the operation if both CA and FDH were immobilized onto the electrode [(-3.9±0.2) A m-2 ]. Product formation by the immobilized enzyme was also continued for three repetitive cycles, which revealed the longevity of the enzyme after immobilization. The recyclability of NADH (NAD=nicotinamide adenine dinucleotide) was also clearly evidenced on the derivative voltammetric signature. Extension of this study for continuous and long-term operation may reveal more possibilities for the rapid capture and conversion of CO2 .

Electro-biocatalytic treatment of petroleum refinery wastewater using microbial fuel cell (MFC) in continuous mode operation.

Refinery wastewater (RW) treatment in microbial fuel cell (MFC) was studied in batch mode operation followed by continuous mode operation with 8h and 16h hydraulic retention time (HRT). The MFC performance was evaluated in terms of power density, organics removal, specific contaminants (oil & grease, phenol and sulfide) removal and energy conversion efficiency with respect to operation mode. Higher power density of 225±1.4mW/m2 was observed during continuous mode operation with 16h HRT along with a substrate degradation of 84.4±0.8% including the 95±0.6 of oil content. The columbic efficiency during this operation was about 2±0.8% and the projected power yield was 340±20kWh/kg CODR/day. Batch mode operation also showed good substrate degradation (81±1.8%) but took longer HRT which resulted in significantly low substrate degradation rate (0.036±0.002kgCODR/m3-day) over continuous mode operation (1.05±0.01kgCODR/m3-day). Overall, current study depicted the possibility of utilizing RW as substrate in MFC for power generation along with its treatment.

Bio-electro catalytic treatment of petroleum produced water: Influence of cathode potential upliftment.

Treatment of petroleum produced water (PPW) was studied using bioelectrochemical system (BES) under uplifted cathode potential. The treatment efficiency in terms of COD and hydrocarbon removal was observed at 91.25% and 76.60% respectively, along with the reduction in TDS during BES operation under 400mV of cathode potential. There was also a reduction in concentration of sulfates, however, it was not significant at, since oxidative conditions are being maintained at anode. Improved oxidation of PPW at anode also resulted in good power output (-20.47mA) and also depicted improved fuel cell behaviour. The electrochemical analysis in terms of cyclic/linear sweep voltammetry also showed well correlation with the observed treatment efficiencies. The microbial dynamics of the BES after loading real field wastewater showed the dominance of species that are reported to be effective for petroleum crude oil degradation.

Gas Diffusion Electrodes Manufactured by Casting Evaluation as Air Cathodes for Microbial Fuel Cells (MFC).

One of the most intriguing renewable energy production methods being explored currently is electrical power generation by microbial fuel cells (MFCs). However, to make MFC technology economically feasible, cost efficient electrode manufacturing processes need to be proposed and demonstrated. In this context, VITO has developed an innovative electrode manufacturing process based on film casting and phase inversion. The screening and selection process of electrode compositions was done based on physicochemical properties of the active layer, which in turn maintained a close relation with their composition A dual hydrophilic-hydrophobic character in the active layer was achieved with values of εhydrophilic up to 10% while εTOTAL remained in the range 65 wt % to 75 wt %. Eventually, selected electrodes were tested as air cathodes for MFC in half cell and full cell modes. Reduction currents, up to -0.14 mA·cm2- at -100 mV (vs. Ag/AgCl) were reached in long term experiments in the cathode half-cell. In full MFC, a maximum power density of 380 mW·m-2 was observed at 100 Ω external load.

Development of exoelectrogenic bioanode and study on feasibility of hydrogen production using abiotic VITO-CoRE™ and VITO-CASE™ electrodes in a single chamber microbial electrolysis cell (MEC) at low current densities.

Single chamber membrane-free microbial electrolysis cell (MEC) was operated for the assessment of exoelectrogenic bacteria (EB) growth at carbon felt anode and resultant hydrogen (H2) production at abiotic cathodes, made using cold rolling (VITO-CoRE™) and casting (VITO-CASE™) methods. Progressive enrichment of EB was observed on anode during 70 days of operation at an applied potential of +0.2V vs Ag/AgCl, and a maximum current density (CD) of 330.59 mA/m(2) (1.38 mA) was recorded. H2 production at selected abiotic cathodes was observed, when the enriched bioanode was coupled to them in galvanostat mode between 0.1 and 1.0 mA current range for 10 min each. Higher H2 production of 114.46±3.75 mL/m(2) was documented with VITO-CoRE™ at 0.6 mA, while 102.76±3.75 mL/m(2) was recorded with VITO-CASE™ at 0.8 mA of current application. This study demonstrates the feasibility of H2 production on abiotic cathodes using enriched bioanode at low current densities.

Enzymatic electrosynthesis of formate through CO2 sequestration/reduction in a bioelectrochemical system (BES).

Bioelectrochemical system (BES) was operated using the enzyme formate dehydrogenase as catalyst at cathode in its free form for the reduction of CO2 into formic acid. Electrosynthesis of formic acid was higher at an operational voltage of -1V vs. Ag/AgCl (9.37mgL(-1) CO2) compared to operation at -0.8V (4.73mgL(-1) CO2) which was strongly supported by the reduction catalytic current. Voltammograms also depicted a reversible redox peak throughout operation at -1V, indicating NAD(+) recycling for proton transfer from the source to CO2. Saturation of the product was observed after 45min of enzyme addition and then reversibility commenced, depicting a lower and stable formic acid concentration throughout the subsequent time of operation. Stability of the enzyme activity after immobilization on the electrode and product yield will be studied further.