Atomically Dispersed FeN2 P2 Motif with High Activity and Stability for Oxygen Reduction Reaction Over the Entire pH Range.

The past decade has witnessed the great potential of Fe-based single-atom electrocatalysis in catalyzing oxygen reduction reaction (ORR). However, it remains a grand challenge to substantially improve their intrinsic activity and long-term stability in acidic electrolytes. Herein, we report a facile chemical vapor deposition strategy, by which high-density Fe atoms (3.97 wt%) are coordinated with square-planar para-positioned nitrogen and phosphorus atoms in a hierarchical carbon framework. The as-crafted atomically dispersed Fe catalyst (denoted Fe-SA/PNC) manifests an outstanding activity towards ORR over the entire pH range. Specifically, the half-wave potential of 0.92 V, 0.83 V, and 0.86 V vs. reversible hydrogen electrode (RHE) are attained in alkaline, neutral, and acidic electrolytes, respectively, representing the high performance among reported catalysts to date. Furthermore, after 30,000 durability cycles, the Fe-SA/PNC remains to be stable with no visible performance decay when tested in 0.1 M KOH and 0.5 M H2 SO4 , and only a minor negative shift of 40 mV detected in 0.1 M HClO4 , significantly outperforming commercial Pt/C counterpart. The coordination motif of Fe-SA/PNC is validated by density functional theory (DFT) calculations. This work provides atomic-level insight into improving the activity and stability of non-noble metal ORR catalysts, opening up an avenue to craft the desired single-atom electrocatalysts.

A highly efficient flow-through electro-Fenton system enhanced with nitrilotriacetic acid for phenol removal at neutral pH.

Low pH requirement is one of the biggest limitations of the application of traditional Fenton and electro-Fenton (EF) process because FeII/FeIII would precipitate at high pH. In this study, a flow-through EF system operated in batch recirculation mode was constructed. Nitrilotriacetic acid (NTA) was used as a chelating agent in the EF system (NTA/EF) to keep iron soluble at high pH values, producing OH by reaction of H2O2 generated in situ with FeIINTA that obtained by the reduction of FeIIINTA at the cathode. This flow-through NTA/EF system accelerated the mass transfer of target molecules to the electrode surface and showed high efficiency for phenol removal at pH 5-8 with rate constants (k) at around 0.26 min-1, higher than that of the batch test (k = 0.15 min-1) and EF process without NTA (k = 0.16 min-1). The influences of aeration rate, current, flow rate, Fe dose, the ratio of NTA to Fe, pH, and initial phenol concentration on the phenol removal were investigated. The system could be used for at least 3 times for phenol removal without obvious efficiency decline. The flow-through NTA/EF system is promising for the removal of organic contaminants in a wide pH range.

Simultaneous removal of tetracycline and disinfection by a flow-through electro-peroxone process for reclamation from municipal secondary effluent.

Pharmaceutical and personal care products as one of the micropollutants and bacteria in secondary effluent restrict the water reuse from municipal secondary effluent. Electro-peroxone (EP) process where H2O2 is generated in-situ by electrolysis is an emerging advanced oxidation process and an improvement of traditional peroxone method (O3/H2O2). In this work, a flow-through EP process was compared with ozonation and electrolysis for simultaneous disinfection and degradation of tetracycline (TC). The disinfection effect by EP was higher than the sum of standalone ozone and electrolysis and the coupling coefficient of ozonation and electrolysis in EP process was 1.2. The flow-through EP system presented similar efficiency for separately and simultaneously treating E. coli and TC. For the actual secondary effluent treatment, trihalomethanes, haloacetonitrile and halonitromethanes, the main disinfection by-products, were much lower than the WHO's thresholds for drinking water. TOC and COD removal was 44% and 65%, respectively, at flow rate of 35 mL/min. BOD5, bacteria, pH and other parameters in the effluent could satisfy the recreational landscape water quality standard, and the required energy consumption was 0.47 kW h/m3 at the flow rate 35 mL/min. Most of the degradation products were small-molecule organic acids, and possible degradation pathway of TC was suggested.