Rohan Gokhale

A family of Fe-N-C oxygen reduction electrocatalysts for microbial fuel cell (MFC) application: Relationships between surface chemistry and performances

Graphical abstract Several organic precursors have been used to fabricate Fe-based catalysts using sacrificial support method. Those catalysts were then included in air breathing cathodes for microbial fuel cells working at neutral environment. Electrochemical performances and surface chemistry were measured and related.

Design of iron(II) pthalocyanine (FePc) derived oxygen reduction electrocatalysts for high power density microbial fuel cells

Abstract 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.

Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

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.

Oxygen Reduction Reaction Electrocatalysts Derived from Iron Salt and Benzimidazole and Aminobenzimidazole Precursors and Their Application in Microbial Fuel Cell Cathodes

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 (<3%). The ORR performance was significantly higher compared to activated carbon (AC) that was the control. The catalysts were then integrated into air-breathing (AB) and gas diffusion layer (GDL) cathode electrode and tested in operating microbial fuel cells (MFCs). The presence of Fe–N–C catalysts boosted the power output compared to AC cathode MFC. The AB-type cathode outperformed the GDL type cathode probably because of reduced catalyst layer flooding. The highest performance obtained in this work was 162 ± 3 μWcm–2. Fe-ABZIM and Fe-BZIM had similar performance when incorporated to the same type of cathode configuration. Long-term operations show a decrease up to 50% of the performance in two months operations. Despite the power output decrease, the Fe-BZIM/Fe-ABZIM catalysts gave a significant advantage in fuel cell performance compared to the bare AC.