ABSTRACT
Promoting the catalyst performance for oxygen reduction reaction (ORR) in energy conversion devices through controlled manipulation of the structure of catalytic active sites has been a major challenge. In this work, we prepared Fe-N-C single-atom catalysts (SACs) with Fe-N5 active sites and found that the catalytic activity of the catalyst with shrinkable Fe-N5-C11 sites for ORR was significantly improved compared with the catalyst bearing normal Fe-N5-C12 sites. The catalyst C@PVI-(TPC)Fe-800, prepared by pyrolyzing an axial-imidazole-coordinated iron corrole precursor, exhibited positive shifted half-wave potential (E1/2 = 0.89 V vs RHE) and higher peak power density (Pmax = 129 mW/cm2) than the iron porphyrin-derived counterpart C@PVI-(TPP)Fe-800 (E1/2 = 0.81 V, Pmax = 110 mW/cm2) in 0.1 M KOH electrolyte and Zn-air batteries, respectively. X-ray absorption spectroscopy (XAS) analysis of C@PVI-(TPC)Fe-800 revealed a contracted Fe-N5-C11 structure with iron in a higher oxidation state than the porphyrin-derived Fe-N5-C12 counterpart. Density functional theory (DFT) calculations demonstrated that C@PVI-(TPC)Fe-800 possesses a higher HOMO energy level than C@PVI-(TPP)Fe-800, which can increase its electron-donating ability and thus help achieve enhanced O2 adsorption as well as O-O bond activation. This work provides a new approach to tune the active site structure of SACs with unique contracted Fe-N5-C11 sites that remarkably promote the catalyst performance, suggesting significant implications for catalyst design in energy conversion devices.
ABSTRACT
We used polylactic acid (PLA) and starch to develop a slow-release carbon source and biofilm carrier by blending and fusing techniques for removing nitrate contamination from groundwater, investigated the changes of nitrate, nitrite concentrations and COD in denitrification process supplied by the slow-release carbon source in different mass ratios [PLA/starch (P: S) were 8:2, 7:3, 6:4, 5:5, respectively]. The experimental results demonstrated that the best mass ratio of PLA/starch was 5:5, resulting in a nitrate removal rate of more than 99%. A high denitrification performance was achieved in continuous fixed-bed reactor, the effluent nitrate concentration was below 2 mg x L(-1). These experiments provide scientific basis for the development of environmentally-friendly and controllable slow-release carbon source.
