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Two-dimensional (2D) anatase titanium dioxide (TiO2) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO2 is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO2 with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS2 for the production of single crystalline 2D anatase TiO2, exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO2 nanoparticles. Because of the strong potential of TiO2 in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO2 with well controlled and highly reactive exposed facets.

A cross-laboratory study on microbial fuel cells (MFC) which involved different institutions around the world is presented. The study aims to assess the development of autochthone microbial pools enriched from domestic wastewater, cultivated in identical single-chamber MFCs, operated in the same way, thereby approaching the idea of developing common standards for MFCs. The MFCs are inoculated with domestic wastewater in different geographic locations. The acclimation stage and, consequently, the startup time are longer or shorter depending on the inoculum, but all MFCs reach similar maximum power outputs (55±22 μW cm-2 ) and COD removal efficiencies (87±9 %), despite the diversity of the bacterial communities. It is inferred that the MFC performance starts when the syntrophic interaction of fermentative and electrogenic bacteria stabilizes under anaerobic conditions at the anode. The generated power is mostly limited by electrolytic conductivity, electrode overpotentials, and an unbalanced external resistance. The enriched microbial consortia, although composed of different bacterial groups, share similar functions both on the anode and the cathode of the different MFCs, resulting in similar electrochemical output.

BACKGROUND: In this work, a small-scale ceramic microbial fuel cell (MFC) with a novel type of metal-carbon-derived electrocatalyst containing iron and nicarbazin (Fe-NCB) was developed, to enhance electricity generation from neat human urine. Substrate oxidation at the anode provides energy for the separation of ions and recovery from urine without any chemical or external power additions. RESULTS: The catalyst was shown to be effective in clear electrolyte synthesis of high pH, compared with a range of carbon-based metal-free materials. Polarisation curves of tested MFCs showed up to 53% improvement (44.8 W m-3) in performance with the use of Fe-NCB catalyst.Catholyte production rate and pH directly increased with power performance while the conductivity decreased showing visually clear extracted liquid in the best-performing MFCs. CONCLUSIONS: Iron based catalyst Fe-NCB was shown to be a suitable electrocatalyst for the air-breathing cathode, improving power production from urine-fed MFCs. The results suggest electrochemical treatment through electro-osmotic drag while the electricity is produced and not consumed. Electro-osmotic production of clear catholyte is shown to extract water from urine against osmotic pressure. Recovering valuable resources from urine would help to transform energy intensive treatments to resource production, and will create opportunities for new technology development. © 2018 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

In recent years, the microbial fuel cell (MFC) technology has drawn the attention of the scientific community due to its ability to produce clean energy and treat different types of waste at the same time. Often, expensive catalysts are required to facilitate the oxygen reduction reaction (ORR) and this hinders their large-scale commercialisation. In this work, a novel iron-based catalyst (Fe-STR) synthesised from iron salt and streptomycin as a nitrogen-rich organic precursor was chemically, morphologically and electrochemically studied. The kinetics of Fe-STR with and without being doped with carbon nanotubes (CNT) was initially screened through rotating disk electrode (RDE) analysis. Then, the catalysts were integrated into air-breathing cathodes and placed into ceramic-type MFCs continuously fed with human urine. The half-wave potential showed the following trend Fe-STR > Fe-STR-CNT ≫ AC, indicating better kinetics towards ORR in the case of Fe-STR. In terms of MFC performance, the results showed that cathodes containing Fe-based catalyst outperformed AC-based cathodes after 3 months of operation. The long-term test reported that Fe-STR-based cathodes allow MFCs to reach a stable power output of 104.5 ± 0.0 μW cm-2, 74% higher than AC-based cathodes (60.4 ± 3.9 μW cm-2). To the best of the Authors knowledge, this power performance is the highest recorded from ceramic-type MFCs fed with human urine.

The anode and cathode electrodes of a microbial fuel cell (MFC) stack, composed of 28 single MFCs, were used as the negative and positive electrodes, respectively of an internal self-charged supercapacitor. Particularly, carbon veil was used as the negative electrode and activated carbon with a Fe-based catalyst as the positive electrode. The red-ox reactions on the anode and cathode, self-charged these electrodes creating an internal electrochemical double layer capacitor. Galvanostatic discharges were performed at different current and time pulses. Supercapacitive-MFC (SC-MFC) was also tested at four different solution conductivities. SC-MFC had an equivalent series resistance (ESR) decreasing from 6.00 Ω to 3.42 Ω in four solutions with conductivity between 2.5 mScm-1 and 40 mScm-1. The ohmic resistance of the positive electrode corresponded to 75-80% of the overall ESR. The highest performance was achieved with a solution conductivity of 40 mS cm-1 and this was due to the positive electrode potential enhancement for the utilization of Fe-based catalysts. Maximum power was 36.9 mW (36.9 W m-3) that decreased with increasing pulse time. SC-MFC was subjected to 4520 cycles (8 days) with a pulse time of 5 s (ipulse 55 mA) and a self-recharging time of 150 s showing robust reproducibility.

In this work, benzimidazole (BZIM) and aminobenzimidazole (ABZIM) were used as organic-rich in nitrogen precursors during the synthesis of iron-nitrogen-carbon (Fe-N-C) based catalysts by sacrificial support method (SSM) technique. The catalysts obtained, denoted Fe-ABZIM and Fe-BZIM, were characterized morphologically and chemically through SEM, TEM, and XPS. Moreover, these catalysts were initially tested in rotating ring disk electrode (RRDE) configuration, resulting in similar high electrocatalytic activity toward oxygen reduction reaction (ORR) having low hydrogen peroxide generated (

In this work, a platinum group metal-free (PGM-free) catalyst based on iron as transitional metal and Nicarbazin (NCB) as low cost organic precursor was synthesized using Sacrificial Support Method (SSM). The catalyst was then incorporated into a large area air-breathing cathode fabricated by pressing with a large diameter pellet die. The electrochemical tests in abiotic conditions revealed that after a couple of weeks of successful operation, the electrode experienced drop in performances in reason of electrolyte leakage, which was not an issue with the smaller electrodes. A decrease in the hydrophobic properties over time and a consequent cathode flooding was suspected to be the cause. On the other side, in the present work, for the first time, it was demonstrated the proof of principle and provided initial guidance for manufacturing MFC electrodes with large geometric areas. The tests in MFCs showed a maximum power density of 1.85 W m-2. The MFCs performances due to the addition of Fe-NCB were much higher compared to the iron-free material. A numerical model using Nernst-Monod and Butler-Volmer equations were used to predict the effect of electrolyte solution conductivity and distance anode-cathode on the overall MFC power output. Considering the existing conditions, the higher overall power predicted was 3.6 mW at 22.2 S m-1 and at inter-electrode distance of 1 cm.

Microbial desalination cell (MDC) is a bioelectrochemical system capable of oxidizing organics, generating electricity, while reducing the salinity content of brine streams. As it is designed, anion and cation exchange membranes play an important role on the selective removal of ions from the desalination chamber. In this work, sulfonated sodium (Na+) poly(ether ether ketone) (SPEEK) cation exchange membranes (CEM) were tested in combination with quaternary ammonium chloride poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membrane (AEM). Non-patterned and patterned (varying topographical features) CEMs were investigated and assessed in this work. The results were contrasted against a commercially available CEM. This work used real seawater from the Pacific Ocean in the desalination chamber. The results displayed a high desalination rate and power generation for all the membranes, with a maximum of 78.6±2.0% in salinity reduction and 235±7mWm-2 in power generation for the MDCs with the SPEEK CEM. Desalination rate and power generation achieved are higher with synthesized SPEEK membranes when compared with an available commercial CEM. An optimized combination of these types of membranes substantially improves the performances of MDC, making the system more suitable for real applications.

Iron aminoantipyrine (Fe-AAPyr), graphene nanosheets (GNSs) derived catalysts and their physical mixture Fe-AAPyr-GNS were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR) with the activated carbon (AC) as a baseline. Fe-AAPyr catalyst was prepared by Sacrificial Support Method (SSM) with silica as a template and aminoantipyrine (AAPyr) as the organic precursor. 3D-GNS was prepared using modified Hummers method technique. The Oxygen Reduction Reaction (ORR) activity of these catalysts at different loadings was investigated by using rotating ring disk (RRDE) electrode setup in the neutral electrolyte. The performance of the catalysts integrated into air-breathing cathode was also investigated. The co-presence of GNS (2 mg cm-2) and Fe-AAPyr (2 mg cm-2) catalyst within the air-breathing cathode resulted in the higher power generation recorded in MFC of 235 ± 1 μW cm-2. Fe-AAPyr catalyst itself showed high performance (217 ± 1 μW cm-2), higher compared to GNS (150 ± 5 μW cm-2) while AC generated power of roughly 104 μW cm-2.

Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e- transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm-2 and 10 mgcm-2. Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm-2 and 262 ± 4 μWcm-2 with catalyst loading of 0.1 mgcm-2 and 10 mgcm-2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

In this work, a microbial fuel cell (MFC) stack containing 28 ceramic MFCs was tested in both standard and supercapacitive modes. The MFCs consisted of carbon veil anodes wrapped around the ceramic separator and air-breathing cathodes based on activated carbon catalyst pressed on a stainless steel mesh. The anodes and cathodes were connected in parallel. The electrolytes utilized had different solution conductivities ranging from 2.0 mScm-1 to 40.1 mScm-1, simulating diverse wastewaters. Polarization curves of MFCs showed a general enhancement in performance with the increase of the electrolyte solution conductivity. The maximum stationary power density was 3.2 mW (3.2 Wm-3) at 2.0 mScm-1 that increased to 10.6 mW (10.6 Wm-3) at the highest solution conductivity (40.1 mScm-1). For the first time, MFCs stack with 1 L operating volume was also tested in supercapacitive mode, where full galvanostatic discharges are presented. Also in the latter case, performance once again improved with the increase in solution conductivity. Particularly, the increase in solution conductivity decreased dramatically the ohmic resistance and therefore the time for complete discharge was elongated, with a resultant increase in power. Maximum power achieved varied between 7.6 mW (7.6 Wm-3) at 2.0 mScm-1 and 27.4 mW (27.4 Wm-3) at 40.1 mScm-1.

Power output limitation is one of the main challenges that needs to be addressed for full-scale applications of the Microbial Fuel Cell (MFC) technology. Previous studies have examined electrochemical performance of different cathode electrodes including the development of novel iron based electrocatalysts, however the long-term investigation into continuously operating systems is rare. This work aims to study the application of platinum group metals-free (PGM-free) catalysts integrated into an air-breathing cathode of the microbial fuel cell operating on activated sewage sludge and supplemented with acetate as the carbon energy source. The maximum power density up to 1.3 Wm-2 (54 Wm-3) obtained with iron aminoantipyrine (Fe-AAPyr) catalyst is the highest reported in this type of MFC and shows stability and improvement in long term operation when continuously operated on wastewater. It also investigates the ability of this catalyst to facilitate water extraction from the anode and electroosmotic production of clean catholyte. The electrochemical kinetic extraction of catholyte in the cathode chamber shows correlation with power performance and produces a newly synthesised solution with a high pH > 13, suggesting caustic content. This shows an active electrolytic treatment of wastewater by active ionic and pH splitting in an electricity producing MFC.

Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

Quaternary ammonium poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membranes (AEMs) with topographically patterned surfaces were assessed in a microbial desalination cell (MDC) system. The MDC results with these QAPPO AEMs were benchmarked against a commercially available AEM. The MDC with the non-patterned QAPPO AEM (Q1) displayed the best desalination rate (a reduction of salinity by 53 ± 2.7%) and power generation (189 ± 5 mW m- 2) when compared against the commercially available AEM and the patterned AEMs. The enhanced performance with the Q1 AEM was attributed to its higher ionic conductivity and smaller thickness leading to a reduced area specific resistance. It is important to note that Real Pacific Ocean seawater and activated sludge were used into the desalination chamber and anode chamber respectively for the MDC - which mimicked realistic conditions. Although the non-patterned QAPPO AEM displayed better performance over the patterned QAPPO AEMs, it was observed that the anodic overpotential was smaller when the MDCs featured QAPPO AEMs with larger lateral feature sizes. The results from this study have important implications for the continuous improvements necessary for developing cheaper and better performing membranes in order to optimize the MDC.

In this work, the electrodes of a microbial desalination cell (MDC) are investigated as the positive and negative electrodes of an internal supercapacitor. The resulting system has been named a supercapacitive microbial desalination cell (SC-MDC). The electrodes are self-polarized by the red-ox reactions and therefore the anode acts as a negative electrode and the cathode as a positive electrode of the internal supercapacitor. In order to overcome cathodic losses, an additional capacitive electrode (AdE) was added and short-circuited with the SC-MDC cathode (SC-MDC-AdE). A total of 7600 discharge/self-recharge cycles (equivalent to 44 h of operation) of SC-MDC-AdE with a desalination chamber filled with an aqueous solution of 30 g L-1 NaCl are reported. The same reactor system was operated with real seawater collected from Pacific Ocean for 88 h (15,100 cycles). Maximum power generated was 1.63 ± 0.04 W m-2 for SC-MDC and 3.01 ± 0.01 W m-2 for SC-MDC-AdE. Solution conductivity in the desalination reactor decreased by ∼50% after 23 h and by more than 60% after 44 h. There was no observable change in the pH during cell operation. Power/current pulses were generated without an external power supply.

M1-M2-N-C bimetallic catalysts with M1 as Fe and Co and M2 as Fe, Co, Ni and Mn were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR). The catalysts were prepared by Sacrificial Support Method in which silica was the template and aminoantipyrine (AAPyr) was the organic precursor. The electro-catalytic properties of these catalysts were investigated by using rotating ring disk (RRDE) electrode setup in neutral electrolyte. Fe-Mn-AAPyr outperformed Fe-AAPyr that showed higher performances compared to Fe-Co-AAPyr and Fe-Ni-AAPyr in terms of half-wave potential. In parallel, Fe-Co-AAPyr, Co-Mn-AAPyr and Co-Ni-AAPyr outperformed Co-AAPyr. The presence of Co within the catalyst contributed to high peroxide production not desired for efficient ORR. The catalytic capability of the catalysts integrated in air-breathing cathode was also verified. It was found that Co-based catalysts showed an improvement in performance by the addition of second metal compared to simple Co- AAPyr. Fe-based bimetallic materials didnt show improvement compared to Fe-AAPyr with the exception of Fe-Mn-AAPyr catalyst that had the highest performance recorded in this study with maximum power density of 221.8 ± 6.6 μWcm-2. Activated carbon (AC) was used as control and had the lowest performances in RRDE and achieved only 95.6 ± 5.8 μWcm-2 when tested in MFC.

Iron(II) phthalocyanine (FePc) deposited onto two different carbonaceous supports was synthesized through an unconventional pyrolysis-free method. The obtained materials were studied in the oxygen reduction reaction (ORR) in neutral media through incorporation in an air-breathing cathode structure and tested in an operating microbial fuel cell (MFC) configuration. Rotating ring disk electrode (RRDE) analysis revealed high performances of the Fe-based catalysts compared with that of activated carbon (AC). The FePc supported on Black-Pearl carbon black [Fe-BP(N)] exhibits the highest performance in terms of its more positive onset potential, positive shift of the half-wave potential, and higher limiting current as well as the highest power density in the operating MFC of (243±7) μW cm-2 , which was 33 % higher than that of FePc supported on nitrogen-doped carbon nanotubes (Fe-CNT(N); 182±5 μW cm-2 ). The power density generated by Fe-BP(N) was 92 % higher than that of the MFC utilizing AC; therefore, the utilization of platinum group metal-free catalysts can boost the performances of MFCs significantly.

Three-dimensional graphene nanosheets (3D-GNS) were used as cathode catalysts for microbial fuel cells (MFCs) operating in neutral conditions. 3D-GNS catalysts showed high performance towards oxygen electroreduction in neutral media with high current densities and low hydrogen peroxide generation compared to activated carbon (AC). 3D-GNS was incorporated into air-breathing cathodes based on AC with three different loadings (2, 6 and 10 mgcm-2). Performances in MFCs showed that 3D-GNS had the highest performances with power densities of 2.059 ± 0.003 Wm-2, 1.855 ± 0.007 Wm-2 and 1.503 ± 0.005 Wm-2 for loading of 10, 6 and 2 mgcm-2 respectively. Plain AC had the lowest performances (1.017 ± 0.009 Wm-2). The different cathodes were also investigated in supercapacitive MFCs (SC-MFCs). The addition of 3D-GNS decreased the ohmic losses by 14-25%. The decrease in ohmic losses allowed the SC-MFC with 3D-GNS (loading 10 mgcm-2) to have the maximum power (Pmax) of 5.746 ± 0.186 Wm-2. At 5 mA, the SC-MFC featured an apparent capacitive response that increased from 0.027 ± 0.007 F with AC to 0.213 ± 0.026 F with 3D-GNS (loading 2 mgcm-2) and further to 1.817 ± 0.040 F with 3D-GNS (loading 10 mgcm-2).

Different iron-based cathode catalysts have been studied for oxygen reduction reaction (ORR) in neutral media and then applied into microbial fuel cells (MFC). The catalysts have been synthesized using sacrificial support method (SSM) using eight different organic precursors named Niclosamide, Ricobendazole, Guanosine, Succinylsulfathiazole, Sulfacetamide, Quinine, Sulfadiazine and Pyrazinamide. Linear Sweep Voltammetry (LSV) curves were obtained for the catalysts using a O2 saturated in 0.1 M potassium phosphate buffer and 0.1 M KCl solution and a Rotating Ring Disk Electrode (RRDE) setup in order to study the ORR characteristics. Additionally, we analyze the peroxide yield obtained for each catalyst which helps us determine the reaction kinetics. Those catalysts have been mixed with activated carbon (AC), carbon black (CB) and PTFE and pressed on a metallic mesh forming a pellet-like gas diffusion electrode (GDE). Results showed that Fe-Ricobendazole, Fe-Niclosamide and Fe-Pyrazinamide had the highest cathode polarization curves and highest power densities output that was above 200 μWcm-2. Fe-Ricobendazole, Fe-Niclosamide, Fe-Pyrazinamide, Fe-Guanosine Fe-Succinylsulfathiazole and Fe-Sulfacetamide outperformed compared to Pt cathode. Fe-Sulfadiazene and Fe-Quinine performed better than AC used as control but less than Pt. Correlation of surface composition with performance showed that power density achieved is directly related to the total amount of nitrogen, and in particularly, N coordinated to metal and pyridinic and pyrrolic types while larger amounts of graphitic nitrogen result in worse performance.

The oxygen reduction reaction (ORR) is one of the major factors that is limiting the overall performance output of microbial fuel cells (MFC). In this study, Platinum Group Metal-free (PGM-free) ORR catalysts based on Fe, Co, Ni, Mn and the same precursor (Aminoantipyrine, AAPyr) were synthesized using identical sacrificial support method (SSM). The catalysts were investigated for their electrochemical performance, and then integrated into an air-breathing cathode to be tested in clean environment and in a working microbial fuel cell (MFC). Their performances were also compared to activated carbon (AC) based cathode under similar conditions. Results showed that the addition of Mn, Fe, Co and Ni to AAPyr increased the performances compared to AC. Fe-AAPyr showed the highest open circuit potential (OCP) that was 0.307 ± 0.001 V (vs. Ag/AgCl) and the highest electrocatalytic activity at pH 7.5. On the contrary, AC had an OCP of 0.203 ± 0.002 V (vs. Ag/AgCl) and had the lowest electrochemical activity. In MFC, Fe-AAPyr also had the highest output of 251 ± 2.3 μWcm-2, followed by Co-AAPyr with 196 ± 1.5 μWcm-2, Ni-AAPyr with 171 ± 3.6 μWcm-2, Mn-AAPyr with 160 ± 2.8 μWcm-2 and AC 129 ± 4.2 μWcm-2. The best performing catalyst (Fe-AAPyr) was then tested in MFC with increasing solution conductivity from 12.4 mScm-1 to 63.1 mScm-1. A maximum power density of 482 ± 5 μWcm-2 was obtained with increasing solution conductivity, which is one of the highest values reported in the field.