Z-scheme Fe@Fe2O3/BiOBr heterojunction with efficient carrier separation for enhanced heterogeneous photo-Fenton activity of tetracycline degradation: Fe2+ regeneration, mechanism insight and toxicity evaluation.

The recombination of photogenerated carrier leads to inefficient Fe2+ regeneration, which limits the extensive application of heterogeneous photo-Fenton. Here, a novel Fe@Fe2O3/BiOBr catalyst with Z-scheme heterojunction structure is designed, and the establishment of the Z-scheme heterojunction facilitates the separation and transfer of photogenerated carrier and maintains the superior redox capability of the system. As-prepared Fe@Fe2O3/BiOBr catalyst exhibits outstanding catalytic performance and stability, especially for the optimum composite FFB-3, its degradation efficiency of tetracycline (TC) achieves 98.22% and the mineralization degree reaches 59.48% within 90 min under natural pH. The preeminent catalytic efficiency benefited from the synergistic of heterogeneous photo-Fenton and Z-scheme carriers transfer mechanism, where Fe2+ regeneration was achieved by photogenerated electrons, and increased hydroxyl radicals were produced with the participation of H2O2 in-situ generated. The results of free-radical scavenging experiment and ESR illustrated that •OH, •O2-, 1O2 and h+ were active species participating in TC degradation. Furthermore, the TC degradation paths were proposed according to LC-MS, and the toxicity evaluation result showed that the toxicity of TC solutions was markedly decreased after degradation. This study provides an innovative strategy for heterogeneous photo-Fenton degradation of antibiotic contaminations by constructing Z-scheme heterojunctions.

Efficient detection of flusilazole by an electrochemical sensor derived from MOF MIL-53(Fe) for food safety.

Flusilazole is a triazole fungicide with residues that are potentially toxic to humans. It enters the human body mainly through food, although its bactericidal activity is substantial. In this study, an electrochemical sensor Fe/Fe2O3@C with a core-shell structure was constructed to efficiently detect flusilazole by annealing MIL-53(Fe) which was prepared by a simple solvothermal method. Transmission electron microscopy and scanning electron microscopy were used to characterize the apparent morphology of MIL-53(Fe) and Fe/Fe2O3@C, and their structures were further characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, powder X-ray diffraction, and the mapping of elements by energy dispersive spectroscopy. The electrochemical behavior of Fe/Fe2O3@C in the detection of flusilazole was evaluated by differential pulse voltammetry under optimal conditions. The results of the study indicate that the Fe/Fe2O3@C electrochemical sensor displayed excellent detection capabilities for flusilazole, where the sensor exhibited a wide detection range from 1.00 × 10-4 to 1.00 × 10-12 mol/L with an incredibly low LOD of 593 fM, making it highly sensitive to trace amounts of flusilazole. Moreover, Fe/Fe2O3@C demonstrated superior reproducibility, stability, and resistance to interference, highlighting its reliability in practical applications. The sensor was also successfully utilized to quantitatively detect flusilazole in various real samples, which suggests that Fe/Fe2O3@C has broad-spectrum environmental resistance and can effectively and rapidly detect flusilazole residues in different types of food items and environmental matrices. The study also delved into the mechanism of Fe/Fe2O3@C for the detection of flusilazole, providing a deeper understanding of the functionality of this sensor. Overall, these findings emphasize the practical significance of Fe/Fe2O3@C as an electrochemical sensor, showcasing its potential for real-world applications in food safety and environmental monitoring.

Construction of urchin-like core-shell Fe/Fe2O3@UiO-66 hybrid for effective tetracycline reduction and photocatalytic oxidation.

Although Fe/Fe2O3 has potential application compared with nanoscale zero-valent iron (nZVI), its smooth structure largely limits the catalytic performance. To address this challenge, we innovatively constructed highly efficient composite Fe/Fe2O3@UiO-66 via employing an urchin-like core-shell structure of Fe/Fe2O3 onto UiO-66 through a facile ion exchange precipitation method without inert gas protection. The characterization results show the urchin-like core-shell configuration can extend the life span of Fe0 and produce more active sites. Besides, the absorption spectrum is broadened by Fe2O3 which has narrow band gap and the high-efficiency separation of photogenerated electron-hole pairs is obtained with the load of Fe/Fe2O3. Moreover, Two-parameter pseudo-first-order decay model fits well with the reduction and adsorption of composites in the dark reaction, and a plausible pathway for tetracycline (TC) degradation is also proposed. The findings of this research provide a promising method for promoting the catalytic properties of MOF-based materials and Fe/Fe2O3.

Interconnecting 3D Conductive Networks with Nanostructured Iron/Iron Oxide Enables a High-Performance Flexible Battery.

Aqueous Ni/Fe alkaline batteries with features of low cost and high safety show great potential for application in portable and wearable electronics. However, the poor kinetics of the Fe-based anode greatly limits the large-scale applications of Ni/Fe batteries. Herein, we report an interconnected 3D conductive network with carbon-coated nanostructured iron/iron oxide (3D-Fe/Fe2O3@C) as an efficient anode for a flexible Ni/Fe battery. A hydrogel precursor is used to molecularly link and confine Fe3+ to spatial networks, resulting in a uniform dispersion of Fe/Fe2O3-heterostructured nanoparticles. Theoretical investigations reveal regulated potential loss and improved delocalized carrier density as a result of carbon coating and the mixed metal/metal oxide structure. In addition to these merits, due to the regulated wettability and electroactive surface areas, the 3D-Fe/Fe2O3@C anode with a high mass loading delivers an extraordinary areal capacity of 3.07 mA h cm-2, as well as the boosted rate capability and Coulombic efficiency. When coupled with the NiCo2O4 cathode, the flexible quasi-solid-state Ni/Fe battery exhibits an admirable energy density of 15.53 mW h cm-3 and a maximum power density of 761.91 W h cm-3. The good stability after 20,000 cycles and severe mechanical deformations of the as-fabricated Ni/Fe battery imply it as a promising flexible energy storage device for practical applications.

Preparation of Fe@Fe2O3/3D graphene composite cathode for electrochemical removal of sulfasalazine.

In the present study, heterogeneous electro-Fenton (EF) process was applied to remove the sulfasalazine (SU) pharmaceutical from aqueous solutions. In the first part, 3D graphene loaded with Fe@Fe2O3 core-shell nanowires (Fe@Fe2O3/3D-GO) was used as a cathode electrode in the EF process. Graphene oxide (GO) was synthesized for the synthesis of 3D graphene nanocomposites using the improved Hummers' method and subsequently 3D graphene synthesized by the hydrothermal method using glycine. Finally, Fe@Fe2O3/3D-GO composite was synthesized and its properties were assessed by Scanning electron microscopy, Atomic force microscopy, Brunauer-Emmett-Teller, Fourier-transform infrared spectroscopy and X-ray diffraction methods. Then, the cathode electrode was prepared using the resulting composite and its performance was evaluated using Cyclic Voltammetry analysis. In the final part of this work, the Fe@Fe2O3/3D-GO electrode was used as the cathode electrode in the heterogeneous EF process to remove SU from aqueous solutions. The effect of operating parameters such as applied current (mA), initial pH of solution, initial pharmaceutical concentration (mg L-1) and process time (min) on pharmaceutical removal efficiency under heterogeneous EF process was investigated by response surface methodology. The results showed that the optimum values for applied current, pH, initial pharmaceutical concentration and electrolysis time were respectively 300 mA, 7, 30 mg L-1 and 100 min, resulting 99.60% of SU removal. Finally, the intermediates of SU degradation were determined by Gas chromatography-mass spectrometry analysis and the amount of mineralization was determined by total organic carbon analysis. About 5.2% drop in the SU removal efficiency was observed within 8 operational runs.

Degradation of orange II by Fe@Fe2O3 core shell nanomaterials assisted by NaHSO3.

Fe@Fe2O3 core shell nanomaterials with different Fe2O3 shell thickness were synthesized and the Fe@Fe2O3/NaHSO3 Fenton-like system was used for the decomposition of Orange II. The consequences are compared with traditional Fenton Fe@Fe2O3/H2O2 system. The Fe@Fe2O3/NaHSO3 system showed extremely good applicability under both strongly acidic and alkaline conditions. The new Fe@Fe2O3-(2)/NaHSO3 system led to more than 99% degradation in 30 s when the pH was 3, which indicated that the Fe@Fe2O3 material was not corroded during the process even under strongly acidic condition. The above Fe@Fe2O3-(2) material was prepared from nano-zero-valent iron aged in solution for 2 h to synthesize the Fe2O3 shell. The reaction mechanism of Fe@Fe2O3/NaHSO3 Fenton-like system was also concluded. The oxidation efficiency was highly improved due to rapid electron transfer between Fe core and Fe2O3 shell, which promoted the direct recycling of ≡Fe3+ and ≡Fe2+ and thus accelerated the generation of SO4- and OH radicals.

Enhanced heterogeneous Fenton-like systems based on highly dispersed Fe0-Fe2O3 nanoparticles embedded ordered mesoporous carbon composite catalyst.

Acceleration of Fe3+/Fe2+ cycle and simultaneous reduction of particle size with enhanced stability is extremely important for iron-based heterogeneous Fenton catalysts. In this work, Fe0-Fe2O3 composite nanoparticles embedded ordered mesoporous carbon hybrid materials (Fe0-Fe2O3/OMC) were rationally designed as efficient heterogeneous Fenton catalysts. Because of the confinement and reduction of OMC, highly dispersed Fe0-Fe2O3 active species with diameter of ∼8 nm were generated by an optimized carbothermic reduction process. In addition, Fe0-Fe2O3/OMC possesses ordered mesoporous structure with uniform mesopore, high surface area and pore volume. For comparison, two other catalysts, including solely Fe0 nanoparticles supported on ordered mesoporous carbon (Fe0/OMC) and solely Fe2O3 nanoparticles supported on ordered mesoporous carbon (Fe2O3/OMC) were also prepared. The Fenton catalytic performance of synthesized catalysts was evaluated by using H2O2 as oxidizing agent to degrade Acid Orange II (AOII). The results show that almost 98.1% of 100 mg L-1 AOII was removed by Fe0-Fe2O3/OMC in condition of neutral pH and nearly room temperature, which is much higher than those of compared catalysts. The enhanced catalytic activity of Fe0-Fe2O3/OMC for AOII removal is due to the efficient electron transfer between the Fe0 and iron oxide and the accelerated Fe3+/Fe2+ cycle. The stability and reusability of the catalyst was also investigated, which showed a good performance even after five consecutive runs. The as-synthesized catalyst is proved to be an attractive candidate in heterogeneous Fenton chemistry and practical application.

Treatment of arsenic in acid wastewater and river sediment by Fe@Fe2O3 nanobunches: The effect of environmental conditions and reaction mechanism.

High concentration of arsenic in acid wastewater and polluted river sediment caused by metallurgical industry has presented a great environmental challenge for decades. Nanoscale zero valent iron (nZVI) can detoxify arsenic-bearing wastewater and groundwater, but the low adsorption capacity and rapid passivation restrict its large-scale application. This study proposed a highly efficient arsenic treatment nanotechnology, using the core-shell Fe@Fe2O3 nanobunches (NBZI) for removal of arsenic in acid wastewater with cyclic stability and transformation of arsenic speciation in sediment. The adsorption capacity of As(III) by NBZI was 60 times as high as that of nanoscale zero valent iron (nZVI) at neutral pH. Characterization of the prepared materials after reaction revealed that the contents of As(III) and As(V) were 65% and 35% under aerobic conditions, respectively, which is the evidence of oxidation included in the reaction process apart from adsorption and co-precipitation. The presence of oxygen was proved to improve the adsorption ability of the prepared NBZI towards As(III) with the removal efficiency increasing from 68% to 92%. In order to further enhance the performance of NBZI-2 in the absence of oxygen, a new Fenton-Like system of NBZI/H2O2 to remove arsenic under the anoxic condition was also proposed. Furthermore, the removal efficiency of arsenic in acid wastewater remained to be 78% after 9 times of cycling. Meanwhile, most of the mobile fraction of arsenic in river sediment was transformed into residues after NBZI treatment for 20 days. The reaction mechanism between NBZI and arsenic was discussed in detail at last, indicating great potential of NBZI for the treatment of arsenic in wastewater and sediment.

Fe@Fe2O3 promoted electrochemical mineralization of atrazine via a triazinon ring opening mechanism.

In this study, an electrochemical/electro-Fenton oxidation (EC/EF) system was designed to degrade atrazine, by utilizing boron-doped diamond (BDD) and Fe@Fe2O3 core-shell nanowires loaded active carbon fiber (Fe@Fe2O3/ACF) as the anode and the cathode, respectively. This EC/EF system exhibited much higher degradation rate, decholorination and mineralization efficiency of atrazine than the electrochemical (EC) and electrochemical/traditional electro-Fenton (EC/TEF) oxidation counterpart systems without Fe@Fe2O3 core-shell nanowires. Active species trapping experiment revealed that Fe@Fe2O3 could activate molecular oxygen to produce more OH through Fenton reaction, which favored the atrazine degradation. High performance liquid chromatography, high performance liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry were applied to probe the decomposition and mineralization of atrazine during this novel EC/EF process, which revealed that two intermediates of triazinons (the isomerization of hydroxylated atrazine) were generated during the electrochemical/electro-Fenton oxidation of atrazine in the presence of Fe@Fe2O3 core-shell nanowires. The experimental and theoretical calculation results suggested that atrazine might be degraded via a triazinon ring opening mechanism, while the presence of Fe@Fe2O3 notably accelerated the decholorination process, and produced more hydroxylated products to promote the generation of trazinons and the subsequent ring cleavage as well as the final complete mineralization. This work provides a deep insight into the triazine ring opening mechanism and the design of efficient electrochemical advanced oxidation technologies (EAOTs) for persistent organic pollutant removal.

Enhanced dewatering of excess activated sludge through decomposing its extracellular polymeric substances by a Fe@Fe2O3-based composite conditioner.

Efficient sludge dewatering methods are highly desired by municipal wastewater treatment plants. In this study, Fe@Fe2O3 nanomaterial, combined with polydiallyldimethylammonium chloride (PDMDAAC) and H2SO4, was used for sludge dewatering. This composite conditioner exhibited an excellent dewatering capability. By using uniform design, the optimized dosages of Fe@Fe2O3, H2SO4 and PDMDAAC were determined to be 40, 136 and 4.8mg/gDS (dry solids), respectively. The moisture content of sludge cake decreased from 78.1% to 64.8%, and the capillary suction time from 56 to 21s. The sludge extracellular polymeric substances (EPS) were decomposed, resulting in greater conversion of the bound water into free water and the release of free water. The electron spin resonance results show that the molecular oxygen activation process induced by Fe@Fe2O3 produced hydroxyl radicals, which were mainly responsible for the EPS decomposition. In this way, an efficient composite conditioner for enhancing sludge dewatering was developed.

Ascorbic acid/Fe@Fe2O3: A highly efficient combined Fenton reagent to remove organic contaminants.

In this study, we demonstrate that the combination of ascorbic acid and Fe@Fe2O3 core-shell nanowires (AA/Fe@Fe2O3) offers a highly efficient Fenton reagent. This combined Fenton reagent exhibited extremely high activity on the decomposition of H2O2 to produce OH for the degradation of various organic contaminants, including rhodamine B, methylene blue, alachlor, atrazine, siduron, lincomycin, and chloroamphenicol. The contaminant degradation constants in the AA/Fe@Fe2O3/H2O2 Fenton systems were 38-53 times higher than those in the conventional homogeneous Fenton system (Fe(II)/H2O2) at pH 3.8. Moreover, the OH generation rate constant in the AA/Fe@Fe2O3/H2O2 Fenton system was 1-3 orders of magnitudes greater than those of heterogeneous Fenton systems developed with other iron-containing materials (α-FeOOH, α-Fe2O3, FeOCl, and so on). The high activity of AA/Fe@Fe2O3 was attributed to the effective Fe(III)/Fe(II) cycle and the iron-ascorbate complex formation to stabilize ferrous ions with desirable and steady concentrations. During the AA/Fe@Fe2O3/H2O2 Fenton process, ascorbic acid served as a reducing and complexing reagent, enabling the reuse of Fe@Fe2O3 nanowires. We systematically investigated the alachlor and ascorbic acid degradation and found that they could be effectively degraded in the AA/Fe@Fe2O3/H2O2 system, accompanying with 100% of dechlorination and 92% of denitrification. This study sheds light on the importance of Fe(III)/Fe(II) cycle for the design of high efficient Fenton system and provides an alternative pathway for the organic contaminants removal.

Negative impact of oxygen molecular activation on Cr(VI) removal with core-shell Fe@Fe2O3 nanowires.

In this study, we demonstrate that the presence of oxygen molecule can inhibit Cr(VI) removal with core-shell Fe@Fe2O3 nanowires at neutral pH of 6.1. 100% of Cr(VI) removal was achieved by the Fe@Fe2O3 nanowires within 60 min in the anoxic condition, in contrast, only 81.2% of Cr(VI) was sequestrated in the oxic condition. Removal kinetics analysis indicated that the presence of oxygen could inhibit the Cr(VI) removal efficiency by near 3 times. XRD, SEM, and XPS analysis revealed that either the anoxic or oxic Cr(VI) removal was involved with adsorption, reduction, co-precipitation, and re-adsorption processes. More Cr(VI) was bound in a reduced state of Cr(III) in the anoxic process, while a thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell, leading to inhibiting the electron transfer, was found under the oxic process. The negative impact of oxygen molecule was attributed to the oxygen molecular activation which competed with Cr(VI) adsorbed for the consumption of donor electrons from Fe(0) core and ferrous ions bound on the iron oxides surface under the oxic condition. This study sheds light on the understanding of the fate and transport of Cr(VI) in oxic and anoxic environment, as well provides helpful guide for optimizing Cr(VI) removal conditions in real applications.

Insight into core-shell dependent anoxic Cr(VI) removal with Fe@Fe2O3 nanowires: indispensable role of surface bound Fe(II).

In this study, we investigated the anoxic Cr(VI) removal with core-shell Fe@Fe2O3 nanowires. It was found the surface area normalized Cr(VI) removal rate constants of Fe@Fe2O3 nanowires first increased with increasing the iron oxide shell thickness and then decreased, suggesting that Fe@Fe2O3 nanowires possessed an interesting core-shell structure dependent Cr(VI) removal property. Meanwhile, the Cr(VI) removal efficiency was positively correlated to the amount of surface bound Fe(II). This result revealed that the core-shell structure dependent Cr(VI) removal property of Fe@Fe2O3 nanowires was mainly attributed to the reduction of Cr(VI) by the surface bound Fe(II) besides the reduction of Cr(VI) adsorbed on the iron oxide shell via the electrons transferred from the iron core. The indispensable role of surface bound Fe(II) was confirmed by Tafel polarization and high-resolution X-ray photoelectron spectroscopic depth profiles analyses. X-ray diffraction patterns and scanning electron microscope images of the fresh and used Fe@Fe2O3 nanowires revealed the formation of Fe(III)/Cr(III)/Cr(VI) composite oxides during the anoxic Cr(VI) removal process. This study sheds a deep insight into the anoxic Cr(VI) removal mechanism of core-shell Fe@Fe2O3 nanowires and also provides an efficient Cr(VI) removal method.

Anoxic and oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires: a comparative study.

In this study we comparatively investigate the removal of humic acids with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions. The products of humic acids after reacting with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions were carefully examined with three-dimensional excitation emission matrix fluorescence spectroscopy and gas chromatography mass spectrometry. It was found that humic acids were removed by Fe@Fe2O3 core-shell nanowires via adsorption under anoxic condition. Langmuir adsorption isotherm was applicable to describe the adsorption processes. Kinetics of humic acids adsorption onto Fe@Fe2O3 core-shell nanowires was found to follow pseudo-second-order rate equation. By contrast, the oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires involved adsorption and subsequent oxidation of humic acids because Fe@Fe2O3 core-shell nanowires could activate molecular oxygen to produce reactive oxygen species to oxidize humic acids. This subsequent oxidation of humic acids could improve the oxic removal rate to 2.5 times that of anoxic removal, accompanying with about 8.4% of mineralization. This study provides a new method for humic acids removal and also sheds light on the effects of humic acids on the pollutant removal by nano zero-valent iron.

Fe@Fe2O3 core-shell nanowires enhanced Fenton oxidation by accelerating the Fe(III)/Fe(II) cycles.

In this study we demonstrate Fe@Fe2O3 core-shell nanowires can improve Fenton oxidation efficiency by two times with rhodamine B as a model pollutant at pH > 4. Active species trapping experiments revealed that the rhodamine B oxidation enhancement was attributed to molecular oxygen activation induced by Fe@Fe2O3 core-shell nanowires. The molecular oxygen activation process could generate superoxide radicals to assist iron core for the reduction of ferric ions to accelerate the Fe(III)/Fe(II) cycles, which favored the H2O2 decomposition to produce more hydroxyl radicals for the rhodamine B oxidation. The combination of Fe@Fe2O3 core-shell nanowires and ferrous ions (Fe@Fe2O3/Fe(2+)) offered a superior Fenton catalyst to decompose H2O2 for producing OH. We employed benzoic acid as a probe reagent to check the generation of OH and found the OH generation rate of Fe@Fe2O3/Fe(2+) was 2-4 orders of magnitude larger than those of commonly used iron based Fenton catalysts and 38 times that of Fe(2+). The reusability and the stability of Fe@Fe2O3 core-shell nanowires were studied. Total organic carbon and ion chromatography analyses revealed the mineralization of rhodamine B and the releasing of nitrate ions. Gas chromatograph-mass spectrometry was used to investigate the degradation intermediates to propose the possible rhodamine B Fenton oxidation pathway in the presence of Fe@Fe2O3 nanowires. This study not only provides a new Fenton oxidation system for pollutant control, but also widen the application of molecular oxygen activation induced by nanoscale zero valent iron.

Microstructure, mechanical property, biodegradation behavior, and biocompatibility of biodegradable Fe-Fe2O3 composites.

In this study, the effects of Fe2O3 (addition, 2, 5, 10, and 50 wt %) on the microstructure, mechanical properties, corrosion behaviors, and in vitro biocompatibility of Fe-Fe2O3 composites fabricated by spark plasma sintering were systematically investigated as a novel-structure biodegradable metallic material. The results of X-ray diffraction analysis and optical microscopy indicated that Fe-Fe2O3 composite is composed of α-Fe and FeO instead of Fe2O3. Both eletrochemical measurements and immersion test showed a faster degradation rate of Fe-2Fe2O3 and Fe-5Fe2O3 composites than pure iron and Fe-5Fe2O3 exhibited the fastest corrosion rate among these composites. Besides, the effect of Fe2O3 on the corrosion behavior of Fe-Fe2O3 composites was discussed. The extracts of Fe-Fe2O3 composite exhibited no cytotoxicity to both ECV304 and L929 cells, whereas greatly reduced cell viabilities of vascular smooth muscle cells. In addition, good hemocompatibility of all Fe-Fe2O3 composites and pure iron was obtained. To sum up, Fe-5Fe2O3 composite is a promising alternative for biodegradable stent material with elevated corrosion rate, enhanced mechanical properties, as well as excellent biocompatibility.