Co, N co-doped hierarchical porous carbon as efficient cathode electrocatalyst and its impact on microbial community of anode biofilm in microbial fuel cell.

The exploration of low-cost, long-term stable, and highly electrochemically active cathode catalysts is important for the practical application of microbial fuel cell (MFC). In this work, a series of the 3D hierarchical porous Co-N-C (3DHP Co-N-C) materials are designed and synthesized by a metal-organic framework ZIF-67 as a precursor and SiO2 sphere of different sizes as the hard template. The 3DHP Co-N-C-2 with 129 nm macropore exhibits excellent ORR performance in 0.1 M KOH solution with a half-wave potential of 0.80 V vs. RHE and superior durability than Pt/C (20%) due to the specific macropore-mesopore-micropore structure that exposes a large number of active sites and accelerates the electrolyte transport and oxygen diffusion. The MFC with 3DHP Co-N-C-2 as the cathode catalysts shows excellent performance with a maximum power density of 426.9±7.87 mW m-2 and favorable durability after 50 d of operation. In addition, 16s rDNA results reveal the presence of different dominant electrogenic bacteria and different abundance of important non-electrogenic bacteria in the anode biofilm in MFCs using cathode catalysts with different ORR activity. And 3DHP Co-N-C-2 was found to be beneficial to the synergistic effect of electrogenic and non-electrogenic bacteria. This study explores electrocatalysts in terms of both electrocatalytic activity and anode microorganisms, providing new and comprehensive insights into the power generation of MFC.

Superior Na-Storage Properties of Nickel-Substituted Na2FeSiO4@C Microspheres Encapsulated with the In Situ-Synthesized Alveolation-like Carbon Matrix.

The poor electronic conductivity of Na2FeSiO4 always limits its electrochemical reactivities and no effective solution has been found to date. Herein, the novel Ni-substituted Na2Fe1-xNixSiO4@C nanospheres (50-100 nm) encapsulated with a 3D hierarchical porous skeleton (named as alveolation-like configuration) constructed using in situ carbon are first synthesized via a facile sol-gel method, and the effects of Ni substitution combined with the design of a unique carbon network on Na-storage properties are assessed systematically, focusing on alleviating the inherent defects of the Na2FeSiO4 cathode material. A series of characterization technologies such as X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and so forth, coupled with the electrochemical measurements and first-principles calculations, are used to explore the structure, morphology and electrochemical behaviors of the as-prepared materials. The results show that the synergism between Ni substitution and the special alveolation-like configuration enables fast Na ions mobility (from 10-14 to 10-12 cm2 s-1), reduces band gap energy (from 2.82 to 1.79 eV) and lowers Na-ion diffusion barriers, finally reciprocating the vigorous electrochemical kinetics of the electrode. Especially, the elaborately designed material-Na2Fe0.97Ni0.03SiO4@C-displays superior Na-storage properties of around 197.51 mA h g-1 (corresponding to 1.43 Na+ intercalation) at 0.1 C within 1.5-4.5 V along with desirable capacity retention (84.44% after 100 cycles), and the rate capability is also markedly enhanced (a capacity of 133.62 mA h g-1 at 2 C). Such the effective methodology employed in this work opens a potential pathway to synthesize the silicate cathode material with excellent electrochemical properties.