Regulating electronic structure of Fe single-atom site by S/N dual-coordination for efficient Fenton-like catalysis.

The activity of single-atom catalysts in peroxymonosulfate activation process is bound up with the local electronic state of metal center. However, the large electronegativity of N atoms in Metal-N4 restricts the electron transfer between center metal atom and peroxymonosulfate. Herein, we constructed Fe-SN-C catalyst by incorporating S atom in the first coordination sphere of Fe single-atom site (Fe-S1N3) for Fenton-like catalysis. The Fe-SN-C with a low valent Fe is found to exhibit excellent catalytic activity for bisphenol A degradation, and the corresponding rate constant reaches 0.405 min-1, 11.9-fold higher than the original Fe-N-C. Besides, the Fe-SN-C/PMS system exhibits ideal catalytic stability under the effect of wide pH range and background substrates by the fast generation of high-valent Fe species. Experimental results and theoretical calculations reveal that the dual coordination of S and N atoms notably increases the local electron density of Fe atoms and electron filling in eg orbital, causing a d band center shifting close to the fermi level and thereby optimizes the activation energy for peroxymonosulfate decomposition via Fe 3d-O 2p orbital interaction. This work provides further development of promising SACs for the efficient activation of peroxymonosulfate based on direct regulation of the coordination environment of active center metal atoms.

Activation of peroxymonosulfate by Cu-Ni-Fe layered double oxides for degradation of butyl 4-hydroxybenzoate: Synergistic effect of oxygen vacancy and Cu(I).

In this study, Cu hybridization coupling oxygen defect engineering was adopted to synthesis of CuNiFe layered double oxides (CuNiFe-LDOs) in peroxymonosulfate (PMS) activation for degradation of methyl 4-hydroxybenzoate. The morphology and crystal structure of CuNiFe-LDOs was characterized in detail, which exhibited regular layered-structure at a Cu:Ni doping ratio of 1:1 and annealing temperature of 400 °C, and presented the crystal of CuxO@Fe3O4-NiO. Besides, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrated that abundant oxygen vacancies (OVs) and low oxidation state Cu species were composed in CuNiFe-LDOs400. The Cu1·5Ni1·5Fe1-LDOs400/PMS system showed excellent catalytic performance toward the degradation of butyl 4-hydroxybenzoate (BuP), and resistant to the effect of pH value and background inorganic anions. Based on quenching experiments and EPR measurements, singlet oxygen (1O2) was identified as the dominant active species during the heterogeneous catalytic process, which was generated by the synergistic interaction between OVs-Cu(I) site and PMS. In this process, the electron-drawing property of OVs promoted the adsorption of PMS molecule on Cu(I) site, followed by the accumulation of electron and cleavage of O-O bond to generate intermediate oxygen radical species, which donated one electron to eventually generate singlet oxygen.

Oxalate regulate the redox cycle of iron in heterogeneous UV-Fenton system with Fe3O4 nanoparticles as catalyst: Critical role of homogeneous reaction.

The redox cycle of iron is a well-known rate-determining step for hydroxyl radical generation in photo-Fenton system. In this study, oxalate was employed as regulator to enhance the degradation of Orange II in Fe3O4 magnetic nanoparticles (NPs)-catalyzed heterogeneous UV-Fenton system. Results showed that the oxalate could interact with the surface ≡FeIII species of catalyst, which weakened the bond of ≡FeIII-O and promoted the leaching of iron ions. Then the redox cycle of iron and generation of HO· would be accelerated via the homogeneous UV-Fenton reaction. The degradation rate constant of Orange II reached 0.220 min-1 when additional oxalate concentration was 0.4 mM, which was 2.5 times as high as that without oxalate in heterogeneous UV-Fenton system. In this case, the removal efficiencies of color and TOC were 99.3% and 92.0% after 30 and 120 min treatment, respectively. In addition, based on the results of XRD and XPS characterization, it could be deduced that the crystal structure and elemental configuration of Fe3O4 magnetic nanoparticles could be maintained after reaction. Besides, the results of FTIR and magnetization characterization indicated that the C2O42- on surface of catalyst could be degraded and the catalyst could be easily separated from aqueous by applying an external magnetic field. The Fe3O4 magnetic nanoparticles showed high catalytic stability and reusability under the regulation of oxalate due to the fact that the leached iron ions could be re-adsorbed on the catalyst after treatment.

Even Incorporation of Nitrogen into Fe0 Nanoparticles as Crystalline Fe4N for Efficient and Selective Trichloroethylene Degradation.

Surface modification of microscale Fe powder with nitrogen has emerged recently to improve the reactivity of Fe0 for dechlorination. However, it is unclear how an even incorporation of a crystalline iron nitride phase into Fe0 nanoparticles affects their physicochemical properties and performance, or if Fe0 nanoparticles with a varied nitridation degree will act differently. Here, we synthesized nitridated Fe0 nanoparticles with an even distribution of N via a sol-gel and pyrolysis method. Nitridation expanded the Fe0 lattice and provided the Fe4N species, making the materials more hydrophobic and accelerating the electron transfer, compared to un-nitridated Fe0. These properties well explain their reactivity and selectivity toward trichloroethylene (TCE). The TCE degradation rate by nitridated Fe0 (up to 4.8 × 10-2 L m-2 h-1) was much higher (up to 27-fold) than that by un-nitridated Fe0, depending on the nitridation degree. The materials maintained a high electron efficiency (87-95%) due to the greatly suppressed water reactivity (109-127 times lower than un-nitridated Fe0). Acetylene was accumulated as the major product of TCE dechlorination via ß-elimination. These findings suggest that the nitridation of Fe0 nanoparticles can change the materials' physicochemical properties, providing high reactivity and selectivity toward chlorinated contaminants for in situ groundwater remediation.

Unveiling the role of cobalt species in the Co/N-C catalysts-induced peroxymonosulfate activation process.

In this study, three Co/N-C catalysts were prepared by pyrolysis of bimetallic zeolitic imidazole frameworks with different Co/Zn ratio, and the critical active Co species in peroxymonosulfate (PMS) activation was investigated. The three catalysts had distinct cobalt species but similar N configuration and graphitization degree. The Co species were distributed as single atoms (Co SAs) at a Co/Zn molar ratio of 1:8, while Co nanoclusters (Co NCs) and Co nanoparticles (NPs) would be formed with further increase in Co content. The degradation efficiency of BPA did not show correlation with the increasing of Co content in catalyst. Based on the catalytic performance comparison and reactive species detection, Co SAs was identified as active sites, which could interact with PMS to generate 1O2 via path of PMS→HOO*→O*→1O2. However, the role of NCs and NPs in directly activating PMS was negligible. In addition, the increase of Co content in Co/N-C catalyst would result in mass cobalt leaching, which enhanced the BPA degradation via homogeneous catalytic reactions with CoIV as reactive species. It is an effective way to design the Co/N-C catalyst with high catalytic activity and stability via regulating the formation of Co SAs.

[Experiment to Enhance Catalytic Activity of α-FeOOH in Heterogeneous UV-Fenton System by Addition of Oxalate].

α-FeOOH was prepared by a symmetrical precipitation method and characterized by XRD, FT-IR, SEM, BET, and EDS techniques. The oxalate enhanced experiment for the catalytic activity of α-FeOOH during the degradation of Orange Ⅱ by the heterogeneous UV-Fenton process was evaluated. The results showed that the rate of Orange Ⅱ degradation in this heterogeneous UV-Fenton system could increase significantly with oxalate as an enhancing reagent, with the peak values of enhanced efficiency reaching 116.9% when the concentration of additional oxalate was 0.4 mmol·L-1. Under this condition, more than 99% of Orange Ⅱ (0.2 mmol·L-1) was degraded in 15 min. However, under the same condition, the inhibition ratios of malonate, acetate, EDTA and citrate were 5.2%, 8.1%, 23.2%, and 25.7%, respectively. Compared with the basic system, the enhanced efficiency of the mineralization rate constant can reach 69.9% when the concentration of additional oxalate was 0.4 mmol·L-1. As a result, the time required for mineralization could be reduced greatly. In the heterogeneous UV-Fenton system, the additional oxalate could provide a new photo-reduction pathway for Fe3+ to Fe2+, enhancing the ratio of the homogeneous UV-Fenton process by increasing the Fe leaching of α-FeOOH and the concentration of hydroxyl radicals, leading to higher degradation efficiency of Orange Ⅱ. As a result, an enhancement effect of 101.5% could be obtained even after three cycles. The iron ions leached from catalysts could be re-adsorbed after treatment, avoiding the loss of active species from catalysts and additional pollution caused by iron ions. The results indicated that additional oxalate was a stable and reliable enhancing reagent on the catalytic activity of α-FeOOH in the heterogeneous UV-Fenton system.

Oxalate enhanced degradation of Orange II in heterogeneous UV-Fenton system catalyzed by Fe3O4@γ-Fe2O3 composite.

Oxalate enhanced mechanism of Fe3O4@γ-Fe2O3 was developed to provide novel insight into catalytic process regulation of iron oxide catalysts in heterogeneous UV-Fenton system. And the iron oxide composite of Fe3O4@γ-Fe2O3 was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fourier transform infrared (FTIR) spectroscopy and nitrogen adsorption-desorption isotherms. The results showed that large amount of iron could be leached from catalyst in the presence of oxalate, which promoted the homogeneous UV-Fenton reactions in solution. Orange II degradation could be significantly enhanced with the increase of the ratio of homogeneous UV-Fenton process to heterogeneous UV-Fenton process. The optimum concentration of oxalate determined by experiment was 0.5 mM in oxalate enhanced heterogeneous UV-Fenton system. On this condition, the pseudo-first-order rate constant value of Orange II degradation was 0.314 min-1, which was 2.3 times as high as that in heterogeneous UV-Fenton system. The removal rates of color and TOC were 100% and 86.6% after 20 min and 120 min treatment, respectively. In addition, the iron ions in solution could be almost completely adsorbed back to the catalyst surface in later degradation stages of Orange II. During the recycle experiments, the results showed that the increase of pH in solution and the sorption of intermediates on the catalyst surface would hinder oxalate enhanced process and lead to a decrease of degradation rate of Orange II in oxalate enhanced heterogeneous UV-Fenton system.