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

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          Highlights

          • PGM-free catalysts were synthesized using sacrificial support method.

          • Catalysts were made with Fe, Co, Mn and Ni as metal center and AAPyr as precursor.

          • Fe-catalysts showed highest performance for ORR in microbial fuel cell.

          • Increase in solution conductivity led to a maximum power of 482 ± 5 μWcm −2

          Abstract

          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.

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          Most cited references64

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          Oxygen Reduction in Alkaline Media: From Mechanisms to Recent Advances of Catalysts

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            Chemistry of Multitudinous Active Sites for Oxygen Reduction Reaction in Transition Metal–Nitrogen–Carbon Electrocatalysts

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              Stability of Fe-N-C Catalysts in Acidic Medium Studied by Operando Spectroscopy.

              Fundamental understanding of non-precious metal catalysts for the oxygen reduction reaction (ORR) is the nub for the successful replacement of noble Pt in fuel cells and, therefore, of central importance for a technological breakthrough. Herein, the degradation mechanisms of a model high-performance Fe-N-C catalyst have been studied with online inductively coupled plasma mass spectrometry (ICP-MS) and differential electrochemical mass spectroscopy (DEMS) coupled to a modified scanning flow cell (SFC) system. We demonstrate that Fe leaching from iron particles occurs at low potential ( 0.9 V) with a destruction of active sites such as FeNx Cy species. Operando techniques combined with identical location-scanning transmission electron spectroscopy (IL-STEM) identify that the latter mechanism leads to a major ORR activity decay, depending on the upper potential limit and electrolyte temperature. Stable operando potential windows and operational strategies are suggested for avoiding degradation of Fe-N-C catalysts in acidic medium.
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                Author and article information

                Contributors
                Journal
                Electrochim Acta
                Electrochim. Acta
                Electrochimica Acta
                Pergamon Press
                0013-4686
                20 March 2017
                20 March 2017
                : 231
                : 115-124
                Affiliations
                [a ]Center Micro-Engineered Materials (CMEM), Department of Chemical and Biological Engineering, University of New Mexico, Albuquerque, NM, USA
                [b ]Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
                Author notes
                Article
                S0013-4686(17)30294-3
                10.1016/j.electacta.2017.02.033
                5384433
                28413228
                7cc862b3-2e62-4172-bf90-17176a735301
                © 2017 The Authors

                This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

                History
                : 7 September 2016
                : 5 February 2017
                : 6 February 2017
                Categories
                Article

                Electrochemistry
                microbial fuel cells,oxygen reduction reaction,pgm-free catalysts,fe-aapyr,high power generation

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