Mediating peroxymonosulfate activation path in Fenton-like reaction via doping different metal atoms into g-C3N5.

Peroxymonosulfate (PMS) could be activated by either radical path or non-radical path, how to rationally mediate these two routines was an important unresolved issue. This work has introduced a simple way to address this problem via metal atom doping. It was found that Fe-doped nitrogen-rich graphitic carbon nitride (Fe-C3N5) exhibited high activity towards PMS activation for tetracycline degradation, and the degradation rate was 3.14 times higher than that of Co-doped nitrogen-rich graphitic carbon nitride (Co-C3N5). Radical trapping experiment revealed the contributions of reactive species over two catalysts were different. Electron paramagnetic resonance analysis further uncovered the non-radical activation path played a dominated role on Fe-C3N5 surface, while the radical activation path was the main routine on Co-C3N5 surface. Density functional theory calculations, X-ray photoelectron spectroscopy analysis, and electrochemical experiments provided convincing evidence to support these views. This study supplied a novel method to mediate PMS activation path via changing the doped metal atom in g-C3N5 skeleton, and it allowed us to better optimize the PMS activation efficiency.

An interfacial C-S bond bridged S-scheme ZnS/C3N5 for photocatalytic H2 evolution: Opposite internal-electric-field of ZnS/C3N4, increased field strength, and accelerated surface reaction.

An interfacial C-S bond bridged ZnS/C3N5 heterojunction was constructed for photocatalytic H2 evolution. Different from traditional type-II ZnS/C3N4 heterojunction, the electron transfer followed S-scheme pathway, due to opposite internal-electric-field (IEF) directions in these two heterojunctions. The C-S bond formation was carefully investigated, and they were susceptive to the preparation temperatures. In photocatalytic reaction, C-S bond was functioned as the "high-speed channel" for electron separation and transfer, and the IEF strength in ZnS/C3N5 was 1.86 × 108 V/m, 2.6 times higher than that in ZnS/C3N4. Moreover, the C-S bond also altered the surface molecular structure of ZnS/C3N5, and hence the surface reaction was accelerated via improving H2O adsorption and activation behaviors. Benefiting from the S-scheme pathway, enhanced IEF strength, and accelerated surface reaction, the photocatalytic H2 production over ZnS/C3N5 reached up to 20.18 mmol/g/h, 3.2 and 2.5 times higher than those of ZnS/C3N4 and ZnS/C3N5-300 without C-S bond.

Preparation of double-yolk egg-like nanoreactor: Enhanced catalytic activity in Fenton-like reaction and insight on confinement effect.

Peroxymonosulfate (PMS)-based Fenton-like reaction is an effective technique for the pollutant degradation, and the Co-based metal organic frameworks displayed the excellent activity for the PMS activation. Nevertheless, how to further improve the catalytic activity, suppress the leaching of toxic cobalt ions, and realize the rapid separation were still challenges for practical application. In this work, a novel solution was proposed: encapsulating Fe3O4 and Prussian blue analogue (PBA) into the polypyrrole (PPy) shell and constructing a "double-yolk egg-like" Fe3O4/PBA@PPy as a nanoreactor. In Fe3O4/PBA@PPy-10, the catalytic performance was remarkably enhanced with the help of confinement effect, and the degradation rate (0.38 L·min·mol-1) was 5.1 times than that of reference Fe3O4/PBA-10 (0.074 L·min·mol-1). In addition, the concentration of leached cobalt ions was reduced to only 0.174 mg/L by the protective function from the PPy shell. Moreover, the nanoreactor could be magnetically separated from the reaction solution due to the encapsulation of Fe3O4 nanospheres, and 84.5% of activity still preserved after the 4th cycle. The main active species involved in Fe3O4/PBA@PPy-10 system was 1O2, while that in reference Fe3O4/PBA-10 system was OH. Electron spin resonance analysis and radical trapping experiment revealed that the different catalytic mechanisms were attributed to the confinement effect inside the hollow cavity. This work not only presents a feasible way to prepare rarely-reported double-yolk egg-like nanoreactor, but also provides a new insight to solve the bottlenecks in Fenton-like reaction.

Partially oxidized MXenes-derived C-TiO2/Ti3C2 coupled with Fe-C3N4 as a ternary Z-scheme heterojunction: Enhanced photothermal and photo-Fenton performance.

Photo-Fenton reaction combining the photocatalytic reaction and Fenton reaction showed excellent degradation performance. However, it highly demanded the catalysts to display outstanding activity in these two reactions. Herein, Fe-doped carbon nitride/MXenes-derived C-TiO2/Ti3C2 (Fe-C3N4/Ti3C2/C-TiO2) was prepared via two steps: Fe-C3N4 and Ti3C2 were assembled via face-to-face attachment, following by in-situ partial oxidation of Ti3C2 to C-TiO2. DFT predicted a Z-scheme charge transfer routine via metallic Ti3C2 as bridge, which was verified by EPR and radical trapping experiments. Additionally, PDOS calculation revealed the charge density around the doped-Fe atoms was remarkably increased, leading to better H2O2 activation, which was experimentally confirmed by high yield of •OH. Moreover, Fe-C3N4/Ti3C2/C-TiO2 possessed the high photothermal effect to accelerate the surface reaction. By taking advantage of these merits, the degradation rate of Fe-C3N4/Ti3C2/C-TiO2 was at least 4.2 times higher than the reference catalysts. Our work provided an insight toward the g-C3N4/TiO2-based photo-Fenton catalysts with high performance.

A simple and green method to prepare non-typical yolk/shell nanoreactor with dual-shells and multiple-cores: Enhanced catalytic activity and stability in Fenton-like reaction.

Nowadays, non-typical yolk/shell structure has drawn much attentions due to the better catalytic performance than traditional counterparts (one yolk/one shell). In this study, ZIF-67 @Co2SiO4/SiO2 yolk/shell structure was prepared in one-step at room temperature, in which ZIF-67 was served as the hard-template, H2O was served as etchant and tetraethyl orthosilicat was served as the raw material for Co2SiO4/SiO2. After calcination, the non-typical CoxOy @Co2SiO4/SiO2 yolk/shell nanoreactor with Co2SiO4/SiO2 dual-shells and CoxOy multiple-cores was obtained. On the one hand, more active sites were exposed on multiple-cores surface and better protection were provided by dual-shells. On the other hand, the sheet-like Co2SiO4 inner shell not only extended the travel path and retention time of pollutants trapped in cavity, but also separated the multiple-cores from aggregation. Therefore, the nanoreactor displayed the outstanding catalytic activity and recyclability in Fenton-like reaction. Metronidazole (20 mg/L) was completely degraded after 30 min, rhodamine B (50 mg/L) and methyl orange (20 mg/L) were removed even within 5.0 min. Catalytic mechanism indicated that 1O2 greatly contributed to the pollutant degradation. This paper presented a simple, versatile, green and energy-saving method for non-typical yolk/shell nanoreactor, and it could inspire to prepare other catalysts with high activity and stability for environmental remediation.

Pyrosequencing Reveals Soil Enzyme Activities and Bacterial Communities Impacted by Graphene and Its Oxides.

Graphene (GN) and graphene oxides (GOs) are novel carbon nanomaterial; they have been attracting much attention because of their excellent properties and are widely applied in many areas, including energy, electronics, biomedicine, environmental science, etc. With industrial production and consumption of GN/GO, they will inevitably enter the soil and water environments. GN/GO may directly cause certain harm to microorganisms and lead to ecological and environmental risks. GOs are GN derivatives with abundant oxygen-containing functional groups in their graphitic backbone. The structure and chemistry of GN show obvious differences compared to those of GO, which lead to the different environmental behaviors. In this study, four different types of soil (S1-S4) were employed to investigate the effect of GN and GO on soil enzymatic activity, microbial population, and bacterial community through pyrosequencing of 16S rRNA gene amplicons. The results showed that soil enzyme activity (invertase, protease, catalase, and urease) and microbial population (bacteria, actinomycetes, and fungi) changed after GN/GO release into soils. Soil microbial community species are more rich, and the diversity also increases after GO/GN application. The phylum of Proteobacteria increased at 90 days after treatment (DAT) after GN/GO application. The phylum of Chloroflexi occurred after GN application at 90 DAT in S1 soil and reached 4.6%. Proteobacteria was the most abundant phylum in S2, S3, and S4 soils; it ranged from 43.6 to 71.4% in S2 soil, from 45.6 to 73.7% in S3 soil, and from 38.1 to 56.7% in S4 soil. The most abundant genera were Bacillus (37.5-47.0%) and Lactococcus (28.0-39.0%) in S1 soil, Lysobacter and Flavobacterium in S2 soil, Pedobacter in S3 soil, and Massilia in S4 soil. The effect of GN and GO on the soil microbial community is time-dependent, and there are no significant differences between the samples at 10 and 90 DAT.