Electronic structure regulation of Fe single atom coordinated nitrogen doping MoS2 catalyst enhances the Fenton-like reaction efficient for organic pollutant control.

An efficient cathode for a Fenton-like reaction based on hydrogen peroxide (H2O2) has significant implications for the potential application of the advanced oxidation process. However, the low H2O2 selectivity and efficient activation remain challenging in wastewater treatment. In the present study, a single Fe atom doped, nitrogen-coordinated molybdenum disulfide (Fe1/N/MoS2) cathode that exhibited asymmetric wettability and self-absorption molecular oxygen was successfully prepared for pollutant degradation. The X-ray absorption near-edge structure and extended X-ray absorption fine structure of Fe1N3 in the Fe1/N/MoS2 catalyst were determined. The electronic structure demonstrated favorable H2O2 selectivity (75%) in a neutral solution and the cumulative hydroxyl radical concentration was 14 times higher than the pure carbon felt. After 10 consecutive reaction experiments, the removal ratio of paracetamol still reached 97%, and the catalytic performance did not decrease significantly. This work deeply understands the catalytic mechanism of Fenton-like reaction between single Fe atom and MoS2 double reaction sites, and proves that the regulation of the electronic structure of Fe single atom is an effective strategy to improve the activity of Fenton-like reaction.

Mo-Based Heterogeneous Interface and Sulfur Vacancy Synergistic Effect Enhances the Fenton-like Catalytic Performance for Organic Pollutant Degradation.

Heterogeneous Fenton-like reactions (HFLRs) based on the in situ electrochemical generation of hydrogen peroxide (H2O2) are one of the green methods to remediate organic pollutants in wastewater. However, the design of Fenton-like catalysts with specific active sites and high pollutant degradation rate is still challenging. Here, MoS2-MoC and MoS2-Mo2N catalytic cathodes with heterojunctions were successfully prepared, and the mechanism by which hydroxyl radicals and singlet oxygen (1O2) were generated cleanly without adding chemical additives other than oxygen was clarified. The composite catalysts contained more sulfur vacancies, and the catalytic cathode achieved a high paracetamol pollutant degradation efficiency with 0.17 kWh g-1 TOC specific energy consumption. And almost 5 times higher activity was achieved compared to a pure MoS2 catalytic cathode. Experimental studies confirmed that the production of 1O2 was based on the transformation of superoxide radicals by Mo6+, and 1O2 accounted for approximately 66% of the total degradation and enhanced the nonradical behavior in the reaction. This work provides a sustainable strategy for pollutant utilization, which is valuable for solving the difficult problems of HFLRs and developing new environmental remediation technologies.

Catalysts containing Fe and Mn from dewatered sludge showing enhanced electrocatalytic degradation of triclosan.

The present work demonstrates a simple one-step pyrolysis method for the synthesis of a catalytic sludge-based carbon (SBC) biochar containing Fe and Mn from dehydrated sludge with added KMnO4 and Fe(II). The electrocatalytic degradation of triclosan (TCS) in water was evaluated using an Fe/Mn-SBC cathode to promote a heterogeneous Fenton-like reaction. The catalyst generated at 500 °C exhibited an abundant porous structure and a relatively high surface area, and produced an electrode with better conductivity and electron diffusion. The presence of metal oxides changed the surface structure defects of this biochar and enhanced its catalytic performance while increasing the electrochemically active surface area by 72.68 mF/cm2 compared with plain SBC. TCS was degraded (91.3%) within 180 min by oxygen species generated in situ on an Fe/Mn-SBC cathode because the activation energy for oxygen reduction was lowered by 4.62 kJ/mol. The degradation of TCS followed pseudo first-order kinetics and was controlled by TCS diffusion and interfacial chemical reactions between adsorbed TCS and the electrode. Possible TCS degradation pathways were devised based on the main intermediates, and 1O2 was found to be more important than •OH radicals. Through toxicity test and prediction, the toxicity of degradation was gradually reduced. This study demonstrates a simple and ecofriendly method for the electrocatalytic degradation of organic pollutants.

Synergistic effect of atomically dispersed Fe-Ni pair sites for electrocatalytic reactions to remove chlorinated organic compounds.

Electrocatalysis is a promising and environmentally friendly technology for the removal of refractory organics. Diatomic catalysts with an increased number of active sites have emerged with further expansion of the field of atomic catalysts. Here, a metal diatomic FeNi supported graphene (FeNi/N-rGO) catalyst is successfully synthesized. The atomically dispersed Fe and Ni species on graphene is verified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy. The pollutant degradation efficiencies for the cathode and anode are found to reach 97.6% and 95.8%, respectively, within 90 min in the diatomic catalytic system. According to DFT theoretical calculations, FeNi diatomic catalysts have a lower free energy (ΔG = -0.2 eV), and the higher adsorption energy for the active substance H* is -0.412 eV. This work presents a method for the preparation of high-performance diatomic catalysts and promotes their application in the electrochemical degradation of chlorinated organic pollutants.

Polyethyleneimine-reinforced Sn/Cu foam dendritic self-supporting catalytic cathode for CO2 reduction to HCOOH.

In this work, a novel catalytic cathode of polyethyleneimine (PEI)-Sn/Cu foam with dendritic structure was prepared by electrodeposition and impregnation. It was used in the electrocatalytic reduction of CO2 to HCOOH, and its performance in this process was evaluated. At -0.97 V vs. RHE, the faradaic efficiency and current density reached 92.3% and 57.1 mA cm-2, respectively, in a 0.5 M KHCO3 electrolyte. The HCOOH production rate reached 890.4 µmol h-1 cm-2, which exceeds those for most reported Sn catalysts. Density functional theory calculations showed that use of Sn/Cu foam is more conducive to HCOOH formation than use of Cu or Sn alone, and *OCHO is the main intermediate in HCOOH formation. The results of OH- adsorption experiments confirmed that the introduction of PEI enhanced the catalytic capacity of the Sn/Cu foam, stabilized CO2·- intermediates, and promoted HCOOH generation. These results will provide an attractive strategy for developing efficient catalysts with excellent activities and stabilities for CO2 electroreduction.

Stepwise dechlorination of chlorinated alkenes on an Fe-Ni/rGO/Ni foam cathode: Product control by one-electron-transfer reactions.

Research on the stepwise hydrogenation dechlorination of chlorinated alkenes forms an important basis for eliminating toxic intermediate incomplete dechlorination products. The low-cost Fe-Ni/rGO/Ni foam cathode both supplied electrons and exhibited hydrogen conversion activity, and it was an excellent tool for the study of stepwise dechlorination. Electrochemical reduction experiments were carried out on homologous chlorinated alkenes. The conditions affecting the dechlorination efficiency and the repeatability of the catalytic electrode were analyzed. The trichloroethylene (TCE) removal rates were all above 78.0% over 8 cycles. The maximum EHDC efficiency was as high as 86.1%, and the faradaic efficiency was over 78.8%. Electrochemical methods combined with the calculation of the electron transfer number are proposed to verify the good hydrogenation ability of the electrode and the stepwise reduction ability at proper voltages. The stepwise dechlorination electroreduction characteristics of chlorinated alkenes were explained. The C-Cl bond dissociation enthalpies of chlorinated alkenes were calculated by density functional theory (DFT), and the 4-Cl and 5-Cl of TCE were expected to be removed first. The stepwise cleavage of chlorinated alkenes on Fe-Ni/rGO/Ni foam during dichlorination provided a reference for controlling the reduction products of chlorinated alkenes and preventing the pollution caused by toxic intermediate products formed during incomplete dechlorination.

Nanoscale zero valent iron supported on MgAl-LDH-decorated reduced graphene oxide: Enhanced performance in Cr(VI) removal, mechanism and regeneration.

The scaled application of nanoscale zero-valent iron nanoparticles (nZVI or Fe° NPs) in environmental remediation is challenged by easy surface passivation and particle aggregation. To improve this situation and enhance their performance in Cr(VI) removal from water phase, we present one novel strategy to hybridize nZVI with layered double hydroxide (LDH) decorated reduced graphene oxide (rGO). The as-prepared ternary (Fe@LDH/rGO) composites possess better dispersibility, improved hydrophilicity and more positive surfaces that allows higher removal efficiency and capacity for Cr(VI) oxyanions. Composition proportion are optimized and influences of surroundings (solution pH, Cr(VI) concentration and temperature) are evaluated. Also, we demonstrate that Fe@LDH/rGO can be reused with suitable post-treatments, which combines alkaline solution desorption and NaBH4 revivification possess. Cr desorption and Fe leaching ratio during regeneration should be critical indicators that determine the recovery efficiency. Synergistic effect within this ternary system not only contributes to its superiorities in stability, but also continuous iron corrosion via the formation of micro Fe-C batteries, where rGO acts as cathode and alternative electron conductor. The present work suggests great potentials of Fe@LDH/rGO composites in groundwater remediation.