Data for Enhancing hydrogen production through anode fed-batch mode and controlled cell voltage Chemsphere

Data for the Figures of the manuscript

Data for Enhanced bio-production from CO₂ by Microbial electrosynthesis (MES) with Continuous operational mode

This raw data is used to support the paper published in Faraday Discussions: https://doi.org/10.1039/D0FD00132E

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 day-1 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 day-1 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.</p

The effect of the polarised cathode, formate and ethanol on chain elongation of acetate in microbial electrosynthesis

Reduction of CO2 to acetate in microbial electrosynthesis has been widely studied. However, the selective and quantitative production of longer chain chemicals and biofuels is still a bottleneck. Lack of sufficient energy provided by only the cathode electrode in Bio-electrochemical systems during chain elongation is one of the key challenges. It is assumed that additional electron donors than a polarised cathode is required to steer the production towards longer chain of carboxylates than acetate. In this study, formate and ethanol were supplied separately in the reactors fed by CO2 for 45 days in addition to the cathodes poised at −1.0 V vs. Ag/AgCl to investigate their effect on production. Although acetate was still the major product, supplying electron donors directed the production towards more diverse and longer chain organic chemicals than that in presence of the polarised cathode only. Significant improvement in the production of butyrate (×3.8 increase in maximum concentration) and butanol (maximum of 6.8 ± 0.3 mmol C L−1) was observed after supplying formate, while ethanol increased the diversity of the products. Supplying formate and ethanol in reactors for another 30 days under open circuit potential clarified that only ethanol could provide sufficient energy for butyrate production from acetate in the absence of polarised cathode, which reached the highest butyrate concentration of 19.1 ± 2.3 mmol C L−1. Formate was only consumed in presence of polarised cathode. It is proposed in our study that production of C4 products in presence of only cathodic electrode or cathodic electrode and formate could be associated to initial reduction of acetate to ethanol, consumed for production of C4 products through acetate. Trace levels of caproate and hexanol were detected in both reactors supplied with formate and ethanol only in the presence of polarised cathode

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

Data for Gas diffusion electrodes modified with binary doped polyaniline for enhanced CO₂ conversion during microbial electrosynthesis

This data was used for describing our latest research results published in Electrochimical Acta: https://doi.org/10.1016/j.electacta.2021.137853

Supplementary Information files for Zinc removal and recovery from industrial wastewater with a microbial fuel cell: Experimental investigation and theoretical prediction

Supplementary Information files for Zinc removal and recovery from industrial wastewater with a microbial fuel cell: Experimental investigation and theoretical predictionMicrobial 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.<br

Gas diffusion electrodes modified with binary doped polyaniline for enhanced CO₂ conversion during microbial electrosynthesis

Microbial electrosynthesis (MES) is a promising technology to convert CO2 into value-added chemicals. Enhancing the interactions between biofilms and electrodes is the key of bioelectrochemical systems (BES). In this work, we studied the conversion of CO2 by MES in reactors equipped with novel gas diffusion electrodes (GDEs) modified with a polyaniline (PANI) polymer binary doped with H2SO4 and ammonium lauryl sulfate. The enhanced conductive and hydrophilic properties of the polymer increased the biocompatibility of the PANI-modified GDEs compared to the non-modified carbon GDEs. This increased biocompatibility resulted in faster start-up and higher bioproduction of volatile fatty acids (VFAs) such as acetate and butyrate. Up to 4400 ppm acetate was produced in PANI-modified reactors after 24 days of operation, compared to 408 ppm in reactors equipped with non-modified GDEs. A maximum acetate concentration of 7500 ppm (production rate of 554.8 ± 267.5 ppm day−1) was reached in reactors equipped with PANI-GDEs. After 60 days, apart from acetate, 245 ppm butyrate was produced in reactors equipped with the electrodes modified with PANI, while less than 60 ppm was produced with non-modified GDEs. SEM analysis revealed the development of biofilms on both modified and non-modified electrodes, but the images also suggest differences in compositions

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

How to go beyond C₁ products with electrochemical reduction of CO₂

The electrochemical reduction of CO2to produce fuels and value-added organic chemicals is of great potential, providing a mechanism to convert and store renewable energy within a carbon-neutral energy circle. Currently the majority of studies report C1products such as carbon monoxide and formate as the major CO2reduction products. A particularly challenging goal within CO2electrochemical reduction is the pursuit of multi-carbon (C2+) products which have been proposed to enable a more economically viable value chain. This review summaries recent development across electro-, photoelectro- and bioelectro-catalyst developments. It also explores the role of device design and operating conditions in enabling C-C bond generation