Mapping Transition Metal-MN4 Macrocyclic Complex Catalysts Performance for the Critical Reactivity Descriptors

There has been a significant progress towards the development of highly active and stable platinum group metal-free (PGM-free) electrocatalysts for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFC), promising a low-cost replacement for Pt group electrocatalysts. However, the success of such developments depends on the implementation of PGM-free electrocatalysts that are not only highly active but importantly, they also exhibit long-term durability under PEFC operating conditions. This manuscript is an overview of the current status of a specific, most advanced class of PGM-free electrocatalysts: transition metal-nitrogen-carbon (M-N-C) ORR catalysts. We present an overview for the understanding of catalysts’ performance descriptors for M-N-C materials

High performance platinum group metal-free cathode catalysts for microbial fuel cell (MFC)

© The Author(s) 2016. The oxygen reduction reaction (ORR) at the cathode is usually the limiting step in microbial fuel cells and improvements have to be done to increase the performances and reduce the cost. For the first time, iron-based catalysts were synthesized utilizing the polymerization-pyrolysis method and tested successfully in neutral media and in working microbial fuel cells (MFCs). The catalysts were synthesized using polymerization, salt formation, mixed with iron salt and pyrolyzed at 850°C (PABA-850) and 950°C (PABA- 950) respectively. To study the kinetics, electro-activity of the catalysts was investigated using rotating ring disk electrode (RRDE). Results showed that PABA-850 had higher catalytic activity compared to that of PABA-950. Both Fe-catalysts had much better activity compared to activated carbon (AC) used as a baseline. Catalysts were then integrated into air breathing cathodes (loading 1 mg cm-2) and tested in single chamber MFC. The power peak obtained was 178 ± 3 μWcm-2 for PABA-850. Comparable power was produced from PABA-950 (173 ± 3 μWcm-2). AC power output was 131 ± 4 μWcm-2 that was roughly 40% lower compared to Fe-based catalysts. Those results demonstrated that the addition of platinum group metal free (PGM-free) catalysts increased the output of the MFCs substantially. Fe-based catalysts seem to be suitable for large-scale MFC applications

Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs

© 2017 The Authors 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

Air breathing cathodes for Microbial Fuel Cell using Mn-, Fe-, Co- and Ni-containing platinum group metal-free catalysts

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 mWcm"2, followed by Co-AAPyr with 196 ! 1.5 mWcm"2, Ni-AAPyr with 171 !3.6 mWcm"2, Mn-AAPyr with 160 ! 2.8 mWcm"2 and AC 129 ! 4.2 mWcm"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 mWcm"2 was obtained with increasing solution conductivity, which is one of the highest values reported in the field

Carbon-based air-breathing cathodes for microbial fuel cells

© 2016 by the authors; licensee MDPI, Basel, Switzerland. A comparison between different carbon-based gas-diffusion air-breathing cathodes for microbial fuel cells (MFCs) is presented in this work. A micro-porous layer (MPL) based on carbon black (CB) and an activated carbon (AC) layer were used as catalysts and applied on different supporting materials, including carbon cloth (CC), carbon felt (CF), and stainless steel (SS) forming cathode electrodes for MFCs treating urine. Rotating ring disk electrode (RRDE) analyses were done on CB and AC to: (i) understand the kinetics of the carbonaceous catalysts; (ii) evaluate the hydrogen peroxide production; and (iii) estimate the electron transfer. CB and AC were then used to fabricate electrodes. Half-cell electrochemical analysis, as well as MFCs continuous power performance, have been monitored. Generally, the current generated was higher from the MFCs with AC electrodes compared to the MPL electrodes, showing an increase between 34% and 61% in power with the AC layer comparing to the MPL. When the MPL was used, the supporting material showed a slight effect in the power performance, being that the CF is more powerful than the CC and the SS. These differences also agree with the electrochemical analysis performed. However, the different supporting materials showed a bigger effect in the power density when the AC layer was used, being the SS the most efficient, with a power generation of 65.6 mW·m−2, followed by the CC (54 mW·m−2) and the CF (44 mW·m−2)

Air Breathing Cathodes for Microbial Fuel Cell using Mn-, Fe-, Co- and Ni-containing Platinum Group Metal-free Catalysts

© 2017 The Authors 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±0.001V (vs. Ag/AgCl) and the highest electrocatalytic activity at pH 7.5. On the contrary, AC had an OCP of 0.203±0.002V (vs. Ag/AgCl) and had the lowest electrochemical activity. In MFC, Fe-AAPyr also had the highest output of 251±2.3μWcm−2, followed by Co-AAPyr with 196±1.5μWcm−2, Ni-AAPyr with 171±3.6μWcm−2, Mn-AAPyr with 160±2.8μWcm−2and AC 129±4.2μWcm−2. The best performing catalyst (Fe-AAPyr) was then tested in MFC with increasing solution conductivity from 12.4 mScm−1to 63.1 mScm−1. A maximum power density of 482±5μWcm−2was obtained with increasing solution conductivity, which is one of the highest values reported in the field

Microbial desalination cell with sulfonated sodium (poly(ether ether ketone) as cation exchange membranes for enhancing power generation and salt reduction

© 2018 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 ± 7 mW m−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

Investigation of patterned and non-patterned poly(2,6-dimethyl 1,4-phenylene) oxide based anion exchange membranes for enhanced desalination and power generation in a microbial desalination cell

© 2017 The Authors 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

Anodic biofilms as the interphase for electroactive bacterial growth on carbon veil

© 2016 American Vacuum Society. The structure and activity of electrochemically active biofilms (EABs) are usually investigated on flat electrodes. However, real world applications such as wastewater treatment and bioelectrosynthesis require tridimensional electrodes to increase surface area and facilitate EAB attachment. The structure and activity of thick EABs grown on high surface area electrodes are difficult to characterize with electrochemical and microscopy methods. Here, the authors adopt a stacked electrode configuration to simulate the high surface and the tridimensional structure of an electrode for large-scale EAB applications. Each layer of the stacked electrode is independently characterized using confocal laser scanning microscopy (CLSM) and digital image processing. Shewanella oneidensis MR-1 biofilm on stacked carbon veil electrodes is grown under constant oxidative potentials (0, +200, and +400mV versus Ag/AgCl) until a stable current output is obtained. The textural, aerial, and volumetric parameters extracted from CLSM images allow tracking of the evolution of morphological properties within the stacked electrodes. The electrode layers facing the bulk liquid show higher biovolumes compared with the inner layer of the stack. The electrochemical performance of S. oneidensis MR-1 is directly linked to the overall biofilm volume as well as connectivity between cell clusters

Exchange current density as an effective descriptor of poisoning of active sites in platinum group metal-free electrocatalysts for oxygen reduction reaction

The oxygen reduction reaction (ORR) is of primary importance for the direct and clean conversion of energy in fuel cells, necessarily requiring an electrocatalyst to be exploited. At the state of the art, platinum group metal-free (PGM-free) electrocatalysts are the most promising alternative to carbon-supported Pt nanoparticles (Pt/C), which are more expensive and more performing but highly prone to deactivation in a contaminated working environment. The comparison of the two materials is at the level of fine-tuning, requiring specific activity descriptors, namely, turnover frequency (TOF) and site density (SD), to understand how to compare the performance of PGM-free electrocatalysts with Pt/C electrocatalysts. Specific probing molecules that bind with the active sites are required to evaluate the SD of PGM-free electrocatalysts. However, PGM-free electrocatalysts possess not a single active site like Pt/C, but a multitude of primary (metal-containing) and secondary (metal-free) sites arising from the pyrolysis synthesis process, eventually complicating SD evaluation. In this work, we propose a method for evaluating the direct interaction through the chemisorption of probing molecules over the PGM-free primary and secondary sites, the discrimination of which is of paramount importance in an effective SD evaluation. Based on the rotating disk electrode technique, the study investigates the electrochemistry of Fe-based PGM-free electrocatalysts poisoned with hydrogen sulfide at pH 1 in comparison with a Pt/C sample. In addition, X-ray photoelectron spectroscopy (XPS) is used to establish a relationship between the electrochemistry and surface chemistry of the poisoned material. The results identify the exchange current density as a meaningful tool that allows the discrimination of poisoning of specific active sites (metal-containing or metal-free). In addition, the understanding of the interaction phenomenon occurring between sites and probing molecules will be paramount for the selection of those contaminants capable of selectively interacting with the active sites of interest, paving the way to a more accurate SD evaluation