Electron Paramagnetic Resonance Results Research Articles

Influence of reduction treatment for TiNb2O7 nanoparticles on the electrochemical properties for Li‐ion batteries

AbstractThe discharge capacities and rate capability of TiNb2O7 powders were enhanced through the additional postreduction treatment. X‐ray photoelectron spectroscopy and electron paramagnetic resonance results confirmed the formation of oxygen vacancies in TiNb2O7 powders after a reduction treatment. The appearance of oxygen vacancies in TiNb2O7 powders formed the impurity level in the forbidden gap and decreased the bandgap values of TiNb2O7. Compared with the pristine TiNb2O7 powders, when TiNb2O7 powders were reduced at 400°C for 40 min, the charge transfer resistance of prepared samples was reduced from 43.67 to 19.35 Ω, and the pseudocapacitive contribution of TiNb2O7 was increased from 44% to 59%. In addition, the discharge capacities at 0.1 and 20 C of prepared batteries were increased by 10.84% and 105.85%, respectively. On the other hand, increasing the temperature in the reduction treatment caused the formation of Ti4+/Ti3+ and Nb5+/Nb4+ pairs and decreased the amounts of available redox couples, thereby deteriorating the electrochemical performance of prepared batteries. The results in the present study revealed that the discharge capacities and rate capability of TiNb2O7 powders were enhanced through a postreduction treatment.

UiO-66(Zr)-2OH-Supported Pd0 NP Catalysts Accelerated a Fenton-Like Reaction: Iron Cycling and Hydrogen Peroxide Generation Achieved Simultaneously.

Both the sluggish kinetics of Fe(II) regeneration and usage restriction of H2O2 have severely hindered the scientific progress of the Fenton reaction toward practical applications. Herein, a reduction strategy of activated hydrogen, which was used to simultaneously generate H2O2 and accelerate the regeneration of ferrous in a Fenton-like reaction based on the reduction of activated hydrogen derived from H2, was proposed. Two types of composite catalysts, namely, Pd/UiO-66(Zr)-2OH and Pd@UiO-66(Zr)-2OH, were successfully prepared by loading nano-Pd particles onto the outer and inner pores of UiO-66(Zr)-2OH in different loading modes, respectively. They were used to enhance the reduction of activated hydrogen. The characterization results based on the analysis of scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy revealed that the materials were successfully prepared. By using a trace amount of ferrous iron and without adding H2O2, trimethoprim (C0 = 20 mg·L-1), as a target pollutant, could be nearly 100% degraded within 180 min in the reaction system composed of these two materials. The cycle of iron and the self-generation of H2O2 were verified by the detection of ferrous H2O2 in the system. Density functional theory calculation results further confirmed that the pore-filled Pd0 NPs, as the main catalytic site for Pd@UiO-66(Zr)-2OH, could produce H2O2 under the combined action of hydrogen and oxygen. The Pd@UiO-66(Zr)-2OH system had excellent stability after multiple applications (at least 6 cycles), all of which resulted in 100% removal of trimethoprim. The degradation efficiency of the Pd/UiO-66(Zr)-2OH system for TMP gradually decreased from 97 to 80% after six cycles. The results of electron paramagnetic resonance combined with classical radical burst experiments revealed the degradation pathways in the reaction system with hydroxyl radicals and singlet oxygen as the main reactive oxygen particles.

Atomically Dispersed Cobalt Anchored on Hollow Tubular Carbon Nitride Mediates Direct Electron Transfer and Oxygen-Related Active Species Path for Activation of Permonosulfate.

Atomically dispersed catalysts anchored on nitrogen-rich substrates present promising application potential for the persulfate-based advanced oxidation process. Nevertheless, efficient activation efficiency and a clear activated mechanism of persulfate remain challenging in carbon nitride-based single-atom catalysts (SACs). To these, combined with the regulation strategy of metal-ligand section and carrier's architecture, an atomically dispersed Co single-atom catalyst anchored on regular hollow tubular carbon nitride (Co/TCN SAC) herein was devised and utilized to activate permonosulfate. As a result, Co/TCN SACs show excellent catalytic performance for the degradation of common antibiotics. Combined with X-ray absorption fine structure and theory calculation, it is confirmed that superficially anchored CoO3 sites of the Co2N2O2-CoO3 unit are the catalytic active center for peroxymonosulfate (PMS) activation. The electrochemical test and in situ electron paramagnetic resonance results demonstrate radical (SO4•- and •OH) and nonradical (electron transfer process and 1O2) paths contributing to the superior catalytic performance. In addition, the catalyst exhibits high reaction efficiency and structural stability considering water quality parameters. Finally, a continuous and efficient device was operated on a laboratory scale, which exhibited satisfactory efficiency in continuously removing electron-rich antibiotics such as tetracycline. This work reveals the atomic-level modulation of cobalt atomic sites on hollow tubular carbon nitride and their structure-activity relationship with persulfate activation.

Efficient activation of N and S co‐doped magnetic biochar for peroxomonosulfate degradation of tetracycline

AbstractN‐S co‐doped magnetic biochar (NSMBC) was synthesized by a two‐step pyrolysis technique and used for the degradation of tetracycline (TC) by activated persulfate (peroxomonosulfate [PMS]). Batch experiments showed that the pyrolysis temperature and doping ratio affected the catalytic performance of NSMBC. The degradation rate of TC in the NSMBC/PMS system prepared at 350°C with a doping ratio of 33% was up to 94.50%, and the system exhibited strong pH adaptability and resistance to environmental interference. The results of free radical burst and electron paramagnetic resonance (EPR) spectroscopy experiments indicated the free radical pathway (SO4•−) for TC degradation. In addition, NSMBC has good stability and excellent magnetic properties favorable for separation and recovery. This study not only provides a new idea for the synthesis of efficient and stable catalysts but also provides a green pathway for the resourceization of pomelo peel waste.

High-efficient separation of photoinduced charge carriers in CoFe2O4-ZnO magnetic heterostructures mediated by oxygen vacancies

In this work, magnetic heterostructures were obtained by the in-situ growth of various ZnO amounts on the preformed CoFe2O4 nanoparticles. The X-ray diffraction characterization shows the presence of both ZnO and CoFe2O4 crystalline phases, and the crystallite size is about 13–14 nm for both components. X-Ray Photoelectron Spectroscopy (XPS) analysis revealed a CoFe2O4 inversion degree of 0.7. The composite samples demonstrated an extended absorption edge into the visible range. The sample’s magnetic properties were investigated by vibrating-sample magnetometer (VSM) and correlated with Electron Paramagnetic Resonance (EPR) results. The magnetic behavior was attributed to the combination of CoFe2O4 and ferromagnetic ZnO. The emergence of a ferromagnetic phase within ZnO was elucidated to originate from charge/spin transfer of spin-up polarized states from the CoFe2O4 Fermi level into empty oxygen vacancies of ZnO. High efficiency in Rhodamine B (RhB) degradation under visible light was observed in the prepared composite materials, particularly with an optimal CoFe2O4-ZnO ratio of 1:5, achieving an 81 % degradation rate within 6 h. The proposed photodegradation mechanism, based on various spectroscopic and magnetic investigations, highlights the role of spin transfer and oxygen vacancies in facilitating reactive oxygen species (ROS) generation for pollutant degradation.

Solution-processed wide band gap transparent conducting Sr0.94La0.06SnO3 films

Pseudo-cubic perovskite La-doped SrSnO3 has been proposed as a promising alternative for ultra-violet (UV) transparent conductors due to its favorable electrical transport properties and UV transparency. However, the difficulty in fabricating large-size La-doped SrSnO3 films with high electrical mobility continues to hinder the development of practical applications. In this work, Sr0.94La0.06SnO3 (SLSO) thin films with wide bandgap of ∼4.5 eV were fabricated by using solution deposition route. Emphasis was placed on creating oxygen-poor environments and selecting appropriate post-annealing temperatures, which were determined based on the kinetic energy of relevant defects and second-phase impurities. Post-annealing treatment was applied to refine the microstructure and enhance electrical transport properties. As a result, a relatively high carrier mobility of 25.9 cm2 V−1 s−1 and a low resistivity of 1.15 mΩ cm at a carrier concentration of 2.08 × 1020 cm−3 were achieved. Enhanced electrical properties were attributed to the increased presence of oxygen vacancies, as confirmed by electron paramagnetic resonance results. This study presents a straightforward approach for the production of large-scale epitaxial UV transparent conducting SLSO thin films.

Highly selective photocatalytic CO2 reduction into C2H4 enabled by metal–organic framework-derived catalysts with high Cu+ content

The highly selective conversion of CO2 into valuable C2H4 is a highly important but particularly challenging reaction. Herein, the metal–organic frameworks MOF-74(Cu) with infinite Cu(II)-O chains and Cu-BTC (BTC=benzene-1,3,5-tricarboxylate) with paddle-wheel binuclear Cu(II) clusters are used as precursors. These MOFs are reduced by NaBH4 to obtain Cu0/Cuδ+-based photocatalysts denoted as R-MOF-74(Cu) and R-Cu-BTC, respectively. Significantly, R-MOF-74(Cu) achieves a high selectivity of 90.2 % for C2H4 with a yield rate of 6.5 μmol g−1 within 5 h due to its high Cu+ content. To the best of our knowledge, this C2H4 product selectivity is a record high among all the photocatalysts reported so far for photocatalytic CO2 reduction. In contrast, R-Cu-BTC only forms CO as a product with a cumulative yield of 0.7 μmol g−1 within 5 h. Photoelectrochemical characterization and electron paramagnetic resonance results show that R-MOF-74(Cu) has low interfacial transfer resistance, high photogenerated electron separation efficiency, and excellent CO2 activation and water oxidation performance. In addition, in situ Fourier transform infrared spectroscopy is used to determine the possible reaction pathway from CO2 to C2H4 over R-MOF-74(Cu). This work demonstrates the great potential of MOF-derived photocatalysts for the conversion of CO2 into C2H4 and provides guidance for future photocatalyst development.

Donor Defect Induced Ferromagnetism in Nb‐Doped ZnO Thin Films Grown by RF Magnetron Sputtering

The effect of Nb doping concentration (0, 1, 2, and 4 at. %) on donor defect‐induced ferromagnetism in ZnO thin films is investigated. The films are deposited on Si(111) substrates utilizing the radio frequency magnetron sputtering. X‐ray diffraction pattern unveils that the films show a pronounced orientation along the (002) direction. The relative intensities of defect‐related bands with that of the ultraviolet band from photoluminescence (PL) spectra show that 2 at. % Nb doping results in a greater number of donor defects (Zni+ and VO+) in the ZnO lattice. The parameters extracted from the electron paramagnetic resonance spectra follow a similar trend. The results from vibrating sample magnetometer measurement indicate that pure ZnO displays diamagnetic nature, whereas Nb‐doped ZnO exhibits a ferromagnetic nature. The saturation magnetization value is found highest for 2 at. % Nb doping, which correlates with the presence of a greater number of donor defects, as supported by the PL and electron paramagnetic resonance results. Images obtained from atomic force microscopy show that the surface roughness of the ZnO thin film reduces upon Nb doping. X‐ray photoelectron spectroscopy validates that Nb is doped in 2 at. % Nb‐doped ZnO thin film with Nb oxidation state of +5.

High sensitive ratiometric optical thermometer based on different multi-photon processes of upconversion luminescence in scheelite Ca1-xMgxWO4:Er3+/Yb3+ phosphors

The relative fluorescence intensity from different multi-photon processes is affected by the excitation light source fluctuation, which reduces the anti-interference and sensitivity of thermometers based on fluorescence intensity ratio (FIR) in upconversion (UC) luminescence. Ca1-xMgxWO4: Yb3+, Er3+ phosphors with scheelite structure were synthesized to investigate their anti-interference and higher temperature sensitivity. With x increasing from 0 to 1, the Bragg angle shifted toward higher angle, indicating that the larger disorders were introduced into the phosphors. The emissions assigned to Er3+ were enhanced with Mg2+ concentration increasing, attributed to oxygen vacancies according to the results of electron paramagnetic resonance. The photon numbers of upconversion luminescence assigned to 2H11/2 → 4I15/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions of Er3+ were three- and two-photon processes, respectively. The ratio between the cube of 4S3/2 and the square of 2H11/2 emissions revealed higher temperature sensing performance and anti-interference on the excitation source power than the that between 4S3/2 and 2H11/2. The maximum relative sensitivity was 0.66 % K−1 at 300 K based on the common optical ratiometric thermometry. The maximum relative sensitivity based on the emissions assigned to different multi-photon processes was 7.2 % K−1 at 573 K. The dopants of Mg2+ composited of oxygen vacancies in CaWO4 crystals improved the luminous intensity and temperature sensing performance. This suggested the potential application of optical ratiometric thermometers based on different multi-photons of UC luminescence in temperature sensing field.

Enhancing degradation of sulfamethoxazole by layered double hydroxide/carbon nanotubes catalyst via synergistic effect of photocatalysis/persulfate activation

A Co3Mn-LDHs and carbon nanotube (Co3Mn-LDHs/CNT) composite catalyst was constructed for permonosulfate (PMS) activation and degrading sulfamethoxazole (SMX) under Vis light irradiation. The introduction of CNTs into Co3Mn-LDHs facilitate the exciton dissociation and carrier migration, and the e− and h+ were readily separated from Co3Mn-LDHs/CNT in the photocatalysis process, which promoted the production rate of reactive oxygen species (ROS), so the Co3Mn-LDHs + Vis + PMS system exhibited better activity with an SMX degradation ratio of 61.25% than those of Co3Mn-LDHs + Vis system (42.30%) and Co3Mn-LDHs + PMS system (48.30%). After 10 cycles, the degradation rate of SMX only decreased by 7.16%, indicating the good reusability of the Co3Mn-LDHs/CNTs catalyst. The results of electron paramagnetic resonance (EPR) analysis and radical quenching experiments demonstrated that that the SO4•− played crucial role for SMX removal in Co3Mn-LDHs/CNTs + Vis + PMS system, and both e− and h+ made an important contribution to activating PMS to produce ROS. Overall, this work provided an excellent catalyst for photo-assisted PMS activation and suggested the activation mechanism for organic pollutant remediation.

Cu2(OH)3NO3/γ-Al2O3 catalyzes Fenton-like oxidation for the advanced treatment of effluent organic matter (EfOM) in fermentation pharmaceutical wastewater: The synergy of Cu2(OH)3NO3 and γ-Al2O3

The secondary effluent of fermentation pharmaceutical wastewater exhibits high chromaticity, elevated salinity, and abundant refractory effluent organic matter (EfOM), presenting significant treatment challenges and environmental threats. Herein, Cu2(OH)3NO3/γ-Al2O3 was fabricated through ultrasound-assisted impregnation and calcination to catalyze the Fenton-like oxidation for degrading organic pollutants in this secondary effluent. Under neutral conditions, with 400.00 mg/L H2O2, 8 g/L catalyst, and at 30 ℃, the EfOM and CODCr removal efficiencies can reach 96.90 % and 51.56 %, respectively. The Cu2(OH)3NO3/γ-Al2O3 catalyst possesses ideal reusability, maintaining CODCr, chromaticity, and EfOM removal efficiencies at 44.44 %-64.59 %, 85.45 %-93.45 %, and 61.00 %-95.00 % over 220 h in a continuous-flow catalytic oxidation system operated at room temperatures (15–25 ℃). Electron paramagnetic resonance results and density functional theory calculations indicate that •OOH may be the predominant reactive oxygen species, facilitated by the easier elongation of the OH bond in H2O2 compared to the OO bond. The adjusted electronic structure endows Cu2(OH)3NO3/γ-Al2O3 composite sites with superior catalytic selectivity for H2O2 activation compared to Cu2(OH)3NO3 single crystal sites, with γ-Al2O3 additionally facilitating H2O2 activation through electron donation. This research highlights the efficacy of Cu2(OH)3NO3/γ-Al2O3 in the advanced treatment of complex industrial wastewater, elucidating its catalytic mechanisms and potential applications.

Uranium mineralization in the Thrace Basin, NW Türkiye: Evidence from radiation-induced defects in detrital quartz and synchrotron XRF/XANES analysis

The Paleogene-Neogene Thrace Basin in northwestern Türkiye has long been known to host economic gas and oil resources and has recently been reported to potentially host sandstone-type uranium deposits in the Oligocene Süloğlu Formation. The latter discovery raises questions about the source and deposition mechanism of uranium mineralization in the basin. This contribution reports on the results of a detailed electron paramagnetic resonance (EPR) spectroscopic study of detrital quartz from four sandstone and one mudstone samples in the Süloğlu Formation and documents the distribution and speciation of uranium using combined microbeam synchrotron X-ray fluorescence maps (μsXRF) and microbeam X-ray near edge structure spectroscopy (μsXANES). The EPR spectra of quartz separates are characterized by the presence of diagnostic radiation-induced defects (i.e., silicon-vacancy hole centers H′3, H′4, and H′7 with gmax = 2.049, 2.034, and 2.018, respectively, and the oxygen-vacancy electron center E′1), formed by the bombardment of alpha particles emitted from uranium, thorium, and their unstable progenies. Moreover, notable decreases in the intensity of silicon-vacancy hole centers in the EPR spectra of quartz separates after partial dissolution with hydrofluoric acid, provide compelling evidence for the circulation of uranium-bearing fluids in the Thrace Basin. The μsXRF and μsXANES data reveal the occurrences of mixed U6+ and U4+ species in hematite partially replacing pyrite aggregates but dominantly U4+ in disseminated pyrite and illite in sandstones of the Süloğlu Formation. These results provide new insights into uranium transport, reduction, and deposition mechanisms, with important implications for better understanding sandstone-type uranium deposits in general and further exploration in the Thrace Basin.

Insights into enhanced degradation of antibiotic trimethoprim in water using a novel K doped g-C3N4 photocatalyst under vacuum-UV irradiation: Performance and mechanisms

In this work, an innovative strategy combining vacuum ultraviolet (VUV) and K doping graphite carbon nitride (K-g-C3N4) was proposed for antibiotic removal in aqueous. The properties of K-g-C3N4 were systematically characterized by XRD, FT-IR, BET, SEM, UV-vis DRS, and XPS, showing that K-g-C3N4 possessed a larger specific surface and richer functional groups than g-C3N4. The catalytic efficiency of K-g-C3N4 was investigated for the trimethoprim (TMP) removal under VUV irradiation. Compared with UVC photolysis, VUV photolysis, UVC/g-C3N4, VUV/g-C3N4, and UVC/K-g-C3N4 processes, VUV/K-g-C3N4 enhanced the pseudo-first-order reaction rate constant of TMP removal by 2.0–19.7 times and the mineralization rate by 9.0%-38.2%. Electron paramagnetic resonance results and quenching experiments validated that O2•-, •OH, 1O2, h+, and e- were engaged in the VUV/K-g-C3N4 process. The fluorescent spectra of O2•--substituted and •OH-substituted products revealed that the K-g-C3N4 greatly enhanced the quantity of O2•- and •OH during VUV irradiation. The VUV/K-g-C3N4 system produced marginally more H2O2 and •OH than the UVC/K-g-C3N4 system, confirming that K-g-C3N4 predominantly utilized the UVC and other ultraviolet–visible light emitted by the VUV lamp, with VUV having a minor effect. Furthermore, K-g-C3N4 had exceptional stability and reusability, efficiently degrading various contaminants under VUV irradiation. This work offered a comprehensive insight into VUV/K-g-C3N4 process as a novel approach for antibiotic removal from water.

Spatial confinement and erbium-mediated electronic modulation for enhanced 4-nitrophenol destruction through peroxymonosulfate activation

The development of efficient strategies to modulate the electron structure of active sites in heterogeneous catalysts is crucial but remains challenging for enhancing peroxomonosulfate (PMS) activation to degrade organic contaminants. In this study, Co-Er-N-doped carbon black materials are successfully synthesized by pyrolyzing the CB@Er/Co-complex precursor. Er-doping does not enhance the defect level or graphitization degree of the carbon matrix, but rather regulates the electronic structure of Co sites, thereby generating abundant metallic Co species for activating PMS and yield increased reactive oxygen species towards 4-nitrophenol (4-NP) degradation. The optimal Er/Co@NCB-0.6 catalyst exhibits a removal efficiency of 97.9 % in 20 min. Furthermore, this catalyst exhibits broad degradation capabilities against various organic contaminants. Due to the spatial confinement effect from carbon layers, the encapsulated Co nanoparticles in the Er/Co@NCB-0.6 catalyst demonstrate excellent stability and reusability for the reaction. Radical quenching and electron paramagnetic resonance results indicate that the Er/Co@NCB-0.6/PMS system involves radical and non-radical pathways, and 1O2 and SO4•− play essential role in degrading 4-NP. The pollutant is degraded into seventeen intermediates via two plausible pathways. This study provides a valuable rare metal-mediated strategy to regulate the electronic structure of Co-based catalytic materials towards activating PMS in removing persistent organic pollutants.

Selective C-H Bond Activation in Propane with Molecular Oxygen over Cu(I)-ZSM-5 at Ambient Conditions.

Selective activation of C-H bonds in light alkanes under mild conditions is challenging but holds the promise of efficient upgrading of abundant hydrocarbons. In this work, we report the conversion of propane to propylene with ∼95% selectivity on Cu(I)-ZSM-5 with O2 at room temperature and pressure. The intraporous Cu(I) species was oxidized to Cu(II) during the reaction but could be regenerated with H2 at 220 °C. Diffuse reflectance ultraviolet spectroscopy indicated the presence of both Cu+-O2 and Cu2(μ-O2)2+ species in the zeolite pores during the reaction, and electron paramagnetic resonance results showed that propane activation occurred via a radical-mediated pathway distinct from that with H2O2 as the oxidant. Correlation between spectroscopic and reactivity results on Cu(I)-ZSM-5 with different Cu loadings suggests that the isolated intraporous Cu(I) species is the main active species in propane activation.

Nanoconfinement-induced high activity of ZIF-8 derived atomic Zn-N-C materials for fenton-like reactions

Atomic Zn-N-C materials are synthesized by direct carbonization of ZIF-8, which maintains the rhombic dodecahedron morphology (RDM) with abundant nanopores. Zn-N-C-RDM shows enhanced catalytic activity with bisphenol A (BPA) as model pollutant and peroxydisulfate (PDS) as oxidant. Molecular dynamic (MD) calculations show that mean square displacement (MSD) of PDS, BPA, and H2O molecules in the nanotunnels decreases obviously with smaller pore size. Due to the confinement, the BPA (di = 1.0 nm) and PDS (di = 0.5 nm) can easily enter and confined in the cavities of Zn-N-C-RDM. PDS can be therefore activated more easily to degrade BPA due to their faster diffusion and shorter transfer routes. > 97 % degradation of BPA can therefore be achieved by Zn-N-C-RDM within 20 min. Quenching experiments, electron paramagnetic resonance (EPR) and open circuit potential (OCP) results indicate that O2•− radical dominate the degradation. According to the density functional theory (DFT) results, the binding sites of Zn-pyridinic N are the main active sites. This work provides new insights for improving activity in Fenton-like reactions in the field of environmental remediation.

Synthesis of coal slime-based catalytic material for peroxymonosulfate activation through molten salt thermal treatment

Coal slime-based peroxymonosulfate (PMS) catalytic materials were synthesized utilizing coal slime (CS) as raw material under the N2 atmosphere in this study. Raw and calcined coal slime were systematically characterized concerning morphologies, pore structures, chemical bonds, phase constituents, and defect density. Results show that after being calcinated with FeCl2∙4H2O at 750 °C, the specific surface area increased by nearly 21.0 times higher than that of CS. The addition of FeCl2∙4H2O has certain effect on the chemical bonds of calcined coal slime, i.e. the Fe elements can be fixed by the silicon aluminum skeleton with sekaninaite (Fe2Al4Si5O18) and aluminum iron silicon (Al0.5Fe3Si0.5, above 650 °C) generation, and the ID/IG values increase to 2.96 for CS-FeCl2-750. In addition, the degradation percentage of phenol by using CS-FeCl2 can achieve 100% in 25 min under optimized conditions. Furthermore, 1O2 plays a major role in phenol degradation, followed by •OH and SO4•− in the CS-FeCl2/PMS system from the quenching experiments and electron paramagnetic resonance results. Overall, the novel CS-FeCl2 material displays good application prospects in the field of effluent treatment, with efficient utilization of carbonaceous and silicon aluminum skeleton in coal slime.

A novel NiFe-LDH/AC three-dimensional particle electrode system and its application for degradation of N-nitrosamines: Condition optimization and degradation mechanism

A green and sustainable three-dimensional particle electrodes system with nickel-iron layered double hydroxide mixing activated carbon particles (NiFe-LDH/AC) as particle electrodes is used in this work. Its employment in degradation of N-Nitrosodiethylamine (NDEA), A type of nitrosamines disinfection byproducts (NAs) widely present in water bodies, exhibiting significant degradation efficiency at close to neutral pH. Response surface methodology (RSM) is used to analyze the interaction effects and predict optimal conditions of four operating parameters (influent water flow, electrolyte concentration, current density and initial concentration) on the NDEA degradation efficiency. Calculated coefficients of determination (R2) are higher than 0.997 for all responses according to analysis of variance. At optimum conditions, a maximum degradation efficiency of 71.88% is achieved for NDEA. The results of electron paramagnetic resonance (EPR) and free radical quenching experiments indicate that the degradation of NDEA in the 3D AER system is dominated by •OH. Furthermore, based on the recognition of main reaction intermediates by GC-MS and density functional theory (DFT), possible degradation pathway is proposed and toxicological evaluation of degradation products is made. Our research provides a promising alternative method for the efficient and environmentally friendly removal of NAs from water.

Study on the Inhibition Characteristics of Coal Spontaneous Combustion by Silica Gel Foam.

The spontaneous combustion of residual coal in abandoned mining areas severely affects the safe and efficient extraction of coal, employee occupational health, and regional environmental ecology. A technical measure for preventing and controlling the spontaneous combustion of residual coal involves injecting antispontaneous combustion materials into abandoned areas. In this study, the composition, preparation, and mechanism of action of silica gel foam, a material used to suppress spontaneous combustion during coal mining, were investigated to improve the performance of materials designed to prevent spontaneous combustion in abandoned areas. The inhibitory efficiency improved, and the mechanical strength and stability of the foam liquid film increased upon adding modified antioxidants and nanosilica particles to the gel foam. Macro performance tests, microstructural characterization, and chemical inhibition mechanism analyses verified the efficacy of silica gel foam for suppressing spontaneous combustion. The air leakage resistance of the silica gel foam effectively increased the air leakage resistance of the coal samples at different pressures. New radicals formed during the spontaneous combustion of coal comprising different inhibitors, as indicated by the g-factor results of electron paramagnetic resonance (EPR) spectroscopy analysis; the formation of radicals initially decreased and then increased when the inhibitor material changed. The concentration of free radicals decreased markedly during the spontaneous combustion process of both raw and inhibited coal samples at low oxidation temperatures (∼60-100 °C), indicating a marked inhibitory effect.

MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline.

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2g/L M88A/MX-0.2, 1.0mM PS, 20ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217min-1, which was much higher than that of MIL-88A(Fe) (0.00159min-1) and MXene (0.00626min-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO4-, and ·O2- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.