In heterogeneous Fenton system, the Heterogeneous-Homogeneous reaction type induced by surface-bonded or dissolved catalytic center plays a vital role in determining Fenton performance. However, how to directionally control the reaction type with facile method still remains challenging. Herein, a novel crystallinity control strategy based on wet-mechanochemical synthesis combined with heat-treatment was applied to synthesize FeS2 nanoparticles with different crystallinity. The different crystalline FeS2 based Fenton system exhibited superior sulfamethoxazole removal performance at wide pH range (5.6-11) with center dot OH as dominating reactive oxygen species. The relative degradation contribution of homogeneous and heterogeneous Fenton reaction was semi-quantitatively evaluated, and the relationship between crystallinity indexes of FeS2 and degradation kinetic constants was established. It's found that FeS2 crystallinity was directly correlated with its degradation efficiency, which first increased and then declined with crystallinity increasing. Crystallinity control strategy effectively determined dominating reaction type (homogeneous or heterogeneous) and further regulated catalytic performance in FeS2 Fenton system based on the interaction of specific surface area and Fe2+ dissolution ability. This work provides a novel crystallinity control strategy to build a correlative bridge among crystallinity, dominating reaction type and catalytic performance in FeS2 Fenton system.
In this paper, cobalt-doped MnFe2O4 (CMFO-0.4) with oxygen vacancies was successfully synthesised by the sol-gel method and applied as a high-performance catalyst for the activation of peroxomonosulfate (PMS). The catalyst showed an excellent catalytic effect for the degradation of sulfadiazine (SDZ) by activated PMS, and the degradation rate can reach 100% in 10 minutes. The effects of different conditions on the degradation of SDZ were investigated, and it was determined that the optimal concentrations of catalyst and PMS were 0.2 g L-1 and 1 mM, respectively, and had good degradation effects in the pH 5-11 range. Free radical quenching experiments, XPS, and electron paramagnetic resonance (EPR) analyses revealed the presence of hydroxyl radicals ((OH)-O-center dot), sulphate radicals (SO4(center dot)-), singlet oxygen (1O2), and superoxide radicals ((center dot)O2-) in the CMFO-0.4/PMS system, with 1O2 being the main reactive oxygen species (ROS). In addition, CMFO-0.4 has good reusability and adaptability to the presence of other substances. Mechanistic diagram of the activation of PMS degradation of SDZ by magnetic cobalt-doped ferromanganese oxide (CMFO-0.4) through singlet oxygen and radical pathways.
In this research, iron phosphide quantum dots (FeP QDs) are synthesized and anchored on the microporous spongy BxCN uniformly through a novel hydrothermal-phosphorization processes. FeP@BxCN shows excellent photo-self-Fenton capability and applies to eliminate CIP from aqueous solution. Results indicate both photocatalysis and self-Fenton processes contribute to CIP degradation (photocatalysis: 69.1 %; self-Fenton: 28.2 %). The decoration of FeP QDs could effectively suppress the recombination of photogenerated carriers and improve the photocatalysis performance. They also accelerate the transformation of in situ H2O2 to center dot OH radicals thus enhance the efficiency of self-Fenton process. Furthermore, FeP QDs shows pretty low consumption during the self-Fenton process because of the regeneration mechanism between cationic iron species, H2O2 and anionic phosphorus. The existence of intermediate valence iron (Fe epsilon+) and anionic phosphorus (P epsilon-) ensured the regeneration of Fe(II) and the circulation between Fe(II), Fe epsilon+ and Fe(III). Optimal CIP degradation efficiency could be achieved under neutral condition and the corresponding CIP removal efficiency are 97.3 % when the initial concentration is 30 mg center dot L-1 and reaction within 120 min. Results propose a meaningful exploration for antibiotics degradation via photocatalytic-self-Fenton technology.
FeS2-biochar composites have been considered as promising heterogeneous Fenton materials for pollutants removal. However, the chemical synthesis of element-doped FeS2-biochar composite with superior performance and the comprehensive investigation for its underlying multiple synergistic mechanism remain a difficult endeavor. Herein, a novel FeS2/Biochar nanocomposite with mutual element doping was firstly synthesized by facile wet-mechanochemical method using iron, sulfur and bamboo-biochar for efficient organic pollutant (sulfamonomethoxine, SMM) removal. Experiment and DFT calculation results revealed that multiple synergistic effect between FeS2 and biochar derived from newly formed Fe-C and C-S-C bonds induced the abundant reactive oxygen species (ROS) and excellent electron transfer capacity. Fe-C sites facilitated the H2O2 adsorption and populated O-O bond in H2O2 for its barrierless dissociation into center dot OH via forming bridging C-Fe-O-O-Fe bond. Oxygen vacancy, C-S-C and Fe-C bonds, persistent free radicals (PFRs) accelerated the generation and transformation of ROS, which resulted in dominating free radical (center dot OH, center dot O2-, center dot SO4-) and auxiliary non-radical (1O2) pathway. Meanwhile, Fe3+/Fe2+ redox-cycle was expedited by electron donor/shuttle (S22-, BC, center dot O2-, C-S-C and Fe-C bonds). All these specialties contributed to the superior performance of FeS2/Biochar Fenton system for SMM removal at wide pH range (3-11) with negligible Fe release. Completely SMM (50 mg/L) removal was achieved within 20 min for 8 successive reuses. This work emphasized the concept of building mutual element doping on molecular level in enhancing FeS2-Biochar synergy towards efficient environmental remediation.
Nano zero valent iron (nZVI) is widely used in traditional hydrogen peroxide (H2O2)-based Fenton reactions for the degradation of persistent organic pollutants in aqueous environments. How to restrain the blocked electron transfer aroused from thickening of the iron oxide passivation layer and reinforce the Fe(III)/Fe(II) dynamic cycling is essential for Fenton reactions. In this work, a novel core-shell structural nZVI@Fe2P was fabricated and employed for the degradation of sulfadiazine (SDZ). Compared to nZVI, the nZVI@Fe2P demonstrated a significant performance and stability in the degradation of SDZ. Completed SDZ removal is achieved in less than 15 min and the SDZ removal kept over 60% even in the ninth consecutive cycles. Although the SDZ removal decreased dramatically to only 27.4% in the tenth cycle, the value could be restored to 80.6% after a facile rephosphorization process. Both experimental and density function theory (DFT) calculation revealed the dominant role of Fe2P in promoting H2O2 activation and strengthening the Fe(III)/Fe(II) dynamic cycling. In the nZVI@Fe2P/H2O2 system, the low impedance and high proton conductivity of the Fe2P shell layer played a dual function, i.e., accelerating electron transfer and donating electrons for the continuous Fenton reaction. This implication of these findings provides a novel strategy by integrating the state-of-the-art material science, advanced oxidation process, and mechanism elucidation for practical environmental wastewater remediation.
The present investigation involved the synthesis of sulfur-doped CoFe2O4 (S-CoFe2O4) catalysts by a straightforward co-precipitation and calcination technique. These catalysts were subsequently employed for the degradation of norfloxacin (NOR) utilizing activated perodisulfate (PDS). At the optimal level of sulfur doping, the efficiency of NOR removal in the S-CoFe2O4-3/PDS system can achieve a high percentage of 98.2%. Furthermore, the study also examined the impact of starting pH, catalyst dosage, PDS dose, several common inorganic anions, and humic acid on the breakdown of NOR. The study of free radicals and singlet oxygen activation mechanisms in the S-CoFe2O4/PDS system is facilitated through the implementation of free radical quenching experiments and electron paramagnetic resonance (EPR) techniques. The suggested breakdown mechanism of NOR in the S-CoFe2O4/PDS system was determined through the analysis of degradation products using high-performance liquid chromatography-mass spectrometry (HPLC-MS). The Biotoxicity Analysis Software (TEST) was employed to assess the toxicity of NOR and its breakdown products.
A novel lotus seedpod shaped Cu 2 O/g-C 3 N 4 p–n heterojunction composite was fabricated by in situ filling the g-C 3 N 4 framework with Cu 2 O hollow nanospheres for efficient photocatalytic hydrogen evolution.
Chitosan modified AGQD (amine modified graphene oxide quantum dots) and then combined with H3PW12O40 to obtain CSx@AGQD-HPW12 via facile process and applied for CIP removal through pre-adsorption and photocatalytic processes. The application of chitosan could regulate the morphology and photoelectric properties effectively. CS0.5@AGQD-HPW12 was found to have the optimal CIP removal performance among all the products, the corresponding adsorption removal efficiency and pre-adsorption photocatalysis process were 72.1 % and 98.8 %, respectively. Results of toxicity assessment confirmed photocatalytic degradation process could mitigate the ecotoxicity of CIP effectively. The optimal TOC (total organic carbon) removal efficiency was about 52.1 %. Possible pathways for CIP degradation and reaction mechanism were proposed based on the results of intermediates analysis and trapping experiments. This demonstrated a novel approach to chitosan application and an eco-friendly way to remove CIP by adsorption-photocatalysis process.
Recovery of surfactants in the soil washing effluent (SWE) can significantly reduce the cost of the soil washing (SW) technology. This paper consists of two parts experiments. The first part constructed a selective oxidation system of active chlorine by electrochemical technology to treat SWE. Three factors, current density, NaCl concentration and TW 80 to aniline concentration ratio (T/A), were set up for a total of nine sets of experiments after orthogonal design. The results of ANOVA analysis and visual analysis showed that the NaCl concentration greatly affected the aniline removal efficiency (ARE) and the TW 80 retention efficiency (TW 80 RE), and the effects were in opposite directions. The biotoxicity of the SWE decreased as the experiment progressed, and at the end of the experiment, 30%-45% of TW 80 was still present in each set. And the oxidation group quenching experiments determined that the degradation of aniline was mainly contributed by active chlorine. Because active chlorine slowed the loss rate of TW 80, the electrochemical treatment of SWE + soil in-situ sequential batch recirculation washing method was designed, and 50% of aniline in the soil was washed out after 125h. At the end of the experiment, the less biotoxic SWE was collected where no aniline and TW 80 were present, and only small organic acids were present after the GC-MS test. The method has a great potential to be applied as it shows good results in the treatment of soil pollution incidents.
The key component of electrochemical advanced oxidation technology are high-efficiency anodes, and highly efficient and simple-to-prepare materials have generated a lot of interest. In this study, novel self-supported Ti3+-doped titanium dioxide nanotube arrays (R-TNTs) anodes were successfully prepared by a two-step anodic oxidation and straightforward electrochemical reduction technique. The electrochemical reduction self-doping treatment produced more Ti3+ sites with stronger absorption in the UV-vis region, a band gap reduction from 2.86 to 2.48 ev, and a significant increase in electron transport rate. The electrochemical degradation effect of R-TNTs electrode on chloramphenicol (CAP) simulated wastewater was investigated. At pH = 5, current density of 8 mA cm−2, electrolyte concentration of 0.1 M sodium sulfate (Na2SO4), initial CAP concentration of 10 mg L−1, CAP degradation efficiency exceeded 95% after 40 min. In addition, molecular probe experiments and electron paramagnetic resonance (EPR) tests revealed that the active species were mainly •OH and SO4−, among which •OH played a major role. The CAP degradation intermediates were discovered using high-performance liquid chromatography-mass spectrometry (HPLC-MS), and three possible degradation mechanisms were postulated. In cycling experiments, the R-TNTs anode demonstrated good stability. The R-TNTs prepared in this paper were an anode electrocatalytic material with high catalytic activity and stability, which could provide a new approach for the preparation of electrochemical anode materials for difficult-to-degrade organic compounds.
Livestock farming has led to the rapid accumulation of antibiotic resistance genes in the environment. Chloramphenicol (CAP) was chosen as a model compound to investigate its degradation during electrochemical treatment. Ti/PbO2 electrodes were prepared using electrodeposition. The prepared Ti/PbO2-La electrodes had a denser surface and a more complete PbO2 crystal structure. Ti/PbO2-Co electrodes exhibited improved electrochemical catalytic activity and lifetime in practice. The impact of different conditions on the effectiveness of CAP electrochemical degradation was investigated, and the most favorable conditions were identified (current density: I = 15.0 mA/cm, electrolyte concentration: c = 0.125 mol/L, solution pH = 5). Most importantly, we investigated the effects of the different stages of treatment with CAP solutions on the abundance of resistance genes in natural river substrates (intI1, cmlA, cmle3, and cata2). When CAP was completely degraded (100% TOC removal), no effect on resistance gene abundance was observed in the river substrate; incomplete CAP degradation significantly increased the absolute abundance of resistance genes. This suggests that when treating solutions with antibiotics, they must be completely degraded (100% TOC removal) before discharge into the environment to reduce secondary pollution. This study provides insights into the deep treatment of wastewater containing antibiotics and assesses the environmental impact of the resulting treated wastewater.
Electron efficiency (or electron selectivity, ɛe) is an important quantitative criterion for zero-valent iron treatment of organohalide contaminated groundwater. The aim of this quantitative study was the systematic exploration and comparison of the effects of the Pd/Fe and S/Fe molar ratios (i.e., [Pd/Fe] and [S/Fe]), trichloroethylene (TCE) concentrations ([TCE]), pH solution, aging time, and water matrices on the ɛe of Pd-nZVI and S-nZVI. To this end, we used TCE as a probe contaminant. The ɛe of Pd-nZVI increased and then decreased with [Pd/Fe], while that of S-nZVI increased with [S/Fe], as more hydrophobic FeS2 was formed on S-nZVI at higher [S/Fe]. The εe of S-nZVI and Pd-nZVI increased with increasing [TCE]. Specifically, the εe of S-nZVI and Pd-nZVI at [TCE] of 200 ppm increased by 24.9 % and 79.3 %, respectively, compared with that at [TCE] of 10 ppm. As the H2 evolution reaction (HER) was more sensitive to surface passivation than TCE dechlorination, the εe of S-nZVI and Pd-nZVI under alkaline conditions was higher than that under basic conditions, and increased by 11.7 % and 37.8 %, respectively, at pH 10 relative to that at pH 6. The εe also increased with the aging time of the S-nZVI and Pd-nZVI particles; the increase was by 27.2 % and 59.6 %, respectively, at aging time of 30 d compared with that of the fresh ones. The ɛe of both particles were higher in artificial groundwater (AGW) than in real groundwater (RGW). For all batch experiments, the εe of S-nZVI increased over the reaction time and tended to outperform that of Pd-nZVI, even though the εe of Pd-nZVI was higher than that of S-nZVI at the initial stage of TCE dechlorination, thereby justifying the longevity of S-nZVI.
Pyrite have been recognized as a promising Fenton reagent to degrade multitudinous organic contaminants. However, the dominating contribution of heterogeneous and homogeneous Fenton reaction to degradation in pyrite Fenton system is ambiguous. In this work, pyrite FeS2 nanoparticles were newly prepared by a wet ball milling method with iron, sulfur and ethanol without protective gas. A subsequent heat-treatment was used to optimize the pyrite crystallinity. The degradation performance of synthesized FeS2 Fenton system for sulfadiazine were systematically investigated for the first time. The synthesized FeS2 Fenton system exhibited ultra-fast and superior degradation ability at wide pH range (3-9) compared with current pyrite Fenton system and 100% sulfadiazine was removed in 4 min with 0.4 g/L FeS2, 2.5 mmol/L H2O2 and initial pH of 7. It's found that ball milling process and heat-treatment affect the performance of synthesized FeS2 Fenton system. The pH self-adjustment induced by accelerated dissolution of amorphous FeS2 and the Fe2+/Fe3+ cyclic regeneration ability resulted in the dominating homogeneous Fenton reaction to degrade sulfadiazine. The maintained excellent degradation ability of synthesized FeS2 after reused three times, in scale-up system, exposed in air for 5 weeks or in real water system (tap water and river water) indicated its promising application possibility and the possible degradation pathways of sulfadiazine by synthesized FeS2 Fenton system were also proposed.
In this work, a novel cuprous sulfide (Cu2S) and cuprous oxide (Cu2O) decorated iron-based nanoparticles (INPs) were developed (Cu2S/Cu2O-nZVI@B, B denote bentonite) and applied for 2,4-dichlorophenol (2,4-DCP) degradation. The physicochemical properties of the as-prepared catalyst were characterized via SEM, TEM, BET, DRS, and EIS. Results of TEM images exhibited the deposition of copper species could improve the morphology and reduce the mean particles size effectively. Cu2S/Cu2O-nZVI@B exhibited excellent catalytic performance to degrade 2,4-DCP by adsorption, Fenton-like oxidation and photocatalytic processes. Under optimal conditions, the degradation percentages caused by adsorption, adsorption-Fenton like and adsorption-Fenton like-photocatalytic processes were about 27.6%, 74.58% and 99.8%, respectively. Furthermore, GC-MS served to identify the intermediates and final products, a possible mechanism and degradation pathway for 2,4-DCP were proposed based on the intermediate by-products detection and active radicals’ detection. The reusability of Cu2S/Cu2O-nZVI@B was achieved with four successive runs. Research provides a promising approach for the treatment of chlorophenols polluted water.
analysis results show of the average of who accept the traditional education mode, engineering education certification and engineering education certification with psychological 9044 and 11630 respectively, the is 54.63% 28.59% respectively, the method of educational be into the engineering certification education mode of science and engineering for adjustment. It students ’ employment competitiveness. will to the methods progress in the process to the ’ educational psychological auxiliary teaching tools practical operation of Background: Humanistic psychology, the full name of humanistic psychology, is a discipline developed in the academic confrontation between the two major psychological schools of behaviorism psychology and psychoanalysis. Humanistic psychology opposes the study of human individuals in isolation without considering human psychological phenomena, and also opposes the understanding of individuals solely from the functions of various elements of human existence, or the interpretation of human words and deeds from the perspective of chemistry and neurology. Humanistic psychology attempts to build a comprehensive human analysis model, and take this as the basis to comprehensively analyze individual psychological laws and psychological conditions. With the development of economy, people ’ s requirements for living environment are not limited to material aspects. More and more residents put forward aesthetic requirements for living space environment. Therefore, in interior design and environmental
Mechanistic role of NO3- in trichloroethylene (TCE) dechlorination by ball milled, micro-scale sulfidated and unsulfidated ZVI (e.g., S-mZVIbm and mZVIbm) was explored through experiments and density functional theory (DFT) calculations. Sulfidation inhibited NO3- reduction by mZVIbm as S weakened its interaction with NO3-. mZVIbm reduced NO3- within 2 h. This just resulted in a short-term electron competition during the dechlorination process by mZVIbm and hardly affected its sluggish dechlorination kinetics (complete TCE dechlorination in 11 d). On the contrary, NO3- suppressed TCE dechlorination by S-mZVIbm. This was attributed to that inhibited NO3- reduction by S-mZVIbm (40 % reduction in 6 h) induced continuous electron competition with TCE during the time span of its dechlorination by S-mZVIbm. NO3- reduction was also observed to facilitate formation/crystallization of Fe3O4 on both ZVI particles, promoting dechlorination by mZVIbm after 4 d while not taking effect to the S-mZVIbm/TCE system, as its dechlorination time was too short for the surface of S-mZVIbm to transform. This observation has important implication on groundwater remediation by ZVI or sulfidated ZVI PRBs under a scenario of upgradient anthropogenic release of NO3-.
Manganese oxides (MnO2) are widely applied in heavy metal ions removal due to their low-cost, environmental-friendly and biocompatibility. However, the adsorption capacity of MnO2 need to be further improved to satisfy the demand of practical application. Herein, a highly dispersed single layer NaxKyMnO2 nanosheet was synthesized by a facile wet-chemical method with sodium dodecyl sulfonate as surfactant. The high surface specific area, excellent dispersibility and abundant oxygen vacancies endowed NaxKyMnO2 nanosheets with potential in heavy metal ions adsorption. The adsorption experiments results showed that NaxKyMnO2 nanosheets possessed high efficiency and selectivity towards lead ion (Pb2+) with a high adsorption capacity of 2091.8 μmol g-1. The NaxKyMnO2 also showed an excellent reusability with the removal rate of 95.4% for Pb2+ even after five cycles. Moreover, both the theoretical calculation and experimental data illustrated that the single layer NaxKyMnO2 nanosheets possess high selectivity to Pb2+ adsorption.
Non-reducible solution anions have been well recognized to affect reactivity of ZVI in dechlorinating chlorinated hydrocarbons. However, their effects and corresponding functional mechanisms on electron efficiency (epsilon(e)) of ZVI remain unclear. In this study, mechanochemically modified microscale sulfidated and unsulfidated ZVI particles (i.e., S-mZVI(bm) and mZVI(bm)) and trichloroethylene (TCE) were used as model particles and contaminant to explore such effects. PO43- as a corrosion promoter enhanced initial dechlorination rate by both particles. However, its passivating role as a surface complex agent became significant at the later stage of dechlorination by mZVI(bm), while sulfidation alleviated this effect without inhibition of dechlorination. Compared with enhancing dechlorination, PO43- promoted hydrogen evolution reaction (HER) to a higher extent, decreasing E. for both particles by 17-73 %. HCO3- negligibly affected dechlorination by both particles, while elevated HER. Thus, HCO3- [5 mM] decreased E. for S-mZVI(bm) and mZVI(bm) by 1.9 % and 22 %. Different from PO43- and HCO3-, Cl- and SO42- showed no significant effects on dechlorination, HER, and therefore E. for both particles. These results imply that even though some co-existing anions (i.e., PO43- and HCO3-) acting as corrosion promoters could improve the dechlorination by ZVIs, they would lead to decreased E. and shortened particle reactive lifetime.
Groundwater pH is one of the most important geochemical parameters in controlling the interfacial reactions of zero-valent iron (ZVI) with water and contaminants. Ball milled, microscale ZVI (mZVIbm) efficiently dechlorinated TCE at initial stage (<24 h) at pH 6–7 but got passivated at later stage due to pH rise caused by iron corrosion. At pH > 9, mZVIbm almost completely lost its reactivity. In contrast, ball milled, sulfidated microscale ZVI (S-mZVIbm) didn't experience any reactivity loss during the whole reaction stage across pH 6–10 and could efficiently dechlorinate TCE at pH 10 with a reaction rate of 0.03 h−1. Increasing pH from 6 to 9 also enhanced electron utilization efficiency from 0.95% to 5.3%, and from 3.2% to 22%, for mZVIbm and S-mZVIbm, respectively. SEM images of the reacted particles showed that the corrosion product layer on S-mZVIbm had a puffy/porous structure while that on mZVIbm was dense, which may account for the mitigated passivation of S-mZVIbm under alkaline pHs. Density functional theory calculations show that covered S atoms on the Fe(100) surface weaken the interactions of H2O molecules with Fe surfaces, which renders the sulfidated Fe surface inefficient for H2O dissociation and resistant to surface passivation. The observation from this study provides important implication that natural sulfidation of ZVI may largely contribute to the long-term (>10 years) efficiency of TCE decontamination by permeable reactive barriers with pore water pH above 9.