Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Mass Transfer-Promoted Fe^(2+)/Fe^(3+)Circulation Steered by 3D Flow-Through Co-Catalyst System Toward Sustainable Advanced Oxidation Processes

Realizing fast and continuous generation of reactive oxygen species(ROSs)via iron-based advanced oxidation processes(AOPs)is significant in the environmental and biological fields.However,current AOPs assisted by co-catalysts still suffer from the poor mass/electron transfer and non-durable promotion effect,giving rise to the sluggish Fe^(2+)/Fe^(3+)cycle and low dynamic concentration of Fe^(2+)for ROS production.Herein,we present a three-dimensional(3D)macroscale co-catalyst functionalized with molybdenum disulfide(MoS_(2))to achieve ultra-efficient Fe^(2+)regeneration(equilibrium Fe^(2+)ratio of 82.4%)and remarkable stability(more than 20 cycles)via a circulating flow-through process.Unlike the conventional batch-type reactor,experiments and computational fluid dynamics simulations demonstrate that the optimal utilization of the 3D active area under the flow-through mode,initiated by the convectionenhanced mass/charge transfer for Fe^(2+)reduction and then strengthened by MoS_(2)-induced flow rotation for sufficient reactant mixing,is crucial for oxidant activation and subsequent ROS generation.Strikingly,the flow-through co-catalytic system with superwetting capabilities can even tackle the intricate oily wastewater stabilized by different surfactants without the loss of pollutant degradation efficiency.Our findings highlight an innovative co-catalyst system design to expand the applicability of AOPs based technology,especially in large-scale complex wastewater treatment.

Fast and Balanced Charge Transport Enabled by Solution-Processed Metal Oxide Layers for Efficient and Stable Inverted Perovskite Solar Cells

Metal oxide charge transport materials are preferable for realizing long-term stable and potentially low-cost perovskite solar cells(PSCs).However,due to some technical difficulties(e.g.,intricate fabrication protocols,high-temperature heating process,incompatible solvents,etc.),it is still challenging to achieve efficient and reliable all-metal-oxide-based devices.Here,we developed efficient inverted PSCs(IPSCs)based on solution-processed nickel oxide(NiO_(x))and tin oxide(SnO_(2))nanoparticles,working as hole and electron transport materials respectively,enabling a fast and balanced charge transfer for photogenerated charge carriers.Through further understanding and optimizing the perovskite/metal oxide interfaces,we have realized an outstanding power conversion efficiency(PCE)of 23.5%(the bandgap of the perovskite is 1.62 eV),which is the highest efficiency among IPSCs based on all-metal-oxide charge transport materials.Thanks to these stable metal oxides and improved interface properties,ambient stability(retaining 95%of initial PCE after 1 month),thermal stability(retaining 80%of initial PCE after 2 weeks)and light stability(retaining 90%of initial PCE after 1000 hours aging)of resultant devices are enhanced significantly.In addition,owing to the low-temperature fabrication procedures of the entire device,we have obtained a PCE of over 21%for flexible IPSCs with enhanced operational stability.

UV-Based Advanced Oxidation Processes for Antibiotic Resistance Control: Efficiency, Influencing Factors, and Energy Consumption

Antibiotic resistant bacteria(ARB)with antibiotic resistance genes(ARGs)can reduce or eliminate the effectiveness of antibiotics and thus threaten human health.The United Nations Environment Programme considers antibiotic resistance the first of six emerging issues of concern.Advanced oxidation processes(AOPs)that combine ultraviolet(UV)irradiation and chemical oxidation(primarily chlorine,hydrogen peroxide,and persulfate)have attracted increasing interest as advanced water and wastewater treatment technologies.These integrated technologies have been reported to significantly elevate the efficiencies of ARB inactivation and ARG degradation compared with direct UV irradiation or chemical oxidation alone due to the generation of multiple reactive species.In this study,the performance and underlying mechanisms of UV/chlorine,UV/hydrogen peroxide,and UV/persulfate processes for controlling ARB and ARGs were reviewed based on recent studies.Factors affecting the process-specific efficiency in controlling ARB and ARGs were discussed,including biotic factors,oxidant dose,UV fluence,pH,and water matrix properties.In addition,the cost-effectiveness of the UV-based AOPs was evaluated using the concept of electrical energy per order.The UV/chlorine process exhibited a higher efficiency with lower energy consumption than other UV-based AOPs in the wastewater matrix,indicating its potential for ARB inactivation and ARG degradation in wastewater treatment.Further studies are required to address the trade-off between toxic byproduct formation and the energy efficiency of the UV/chlorine process in real wastewater to facilitate its optimization and application in the control of ARB and ARGs.

Mechanism of microarc oxidation on AZ91D Mg alloy induced byβ-Mg_(17)Al_(12) phase

This work proposed a strategy of indirectly inducing uniform microarc discharge by controlling the content and distribution ofβ-Mg_(17)Al_(12)phase in AZ91D Mg alloy.Two kinds of nano-particles(ZrO_(2)and TiO_(2))were designed to be added into the substrate of Mg alloy by friction stir processing(FSP).Then,Mg alloy sample designed with different precipitated morphology ofβ-Mg_(17)Al_(12)phase was treated by microarc oxidation(MAO)in Na_(3)PO_(4)/Na2SiO3electrolyte.The characteristics and performance of the MAO coating was analyzed using scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),contact angle meter,and potentiodynamic polarization.It was found that the coarseα-Mg grains in extruded AZ91D Mg alloy were refined by FSP,and theβ-Mg_(17)Al_(12)phase with reticular structure was broken and dispersed.The nano-ZrO_(2)particles were pinned at the grain boundary by FSP,which refined theα-Mg grain and promoted the precipitation ofβ-Mg_(17)Al_(12)phase in grains.It effectively inhibited the“cascade”phenomenon of microarcs,which induced the uniform distribution of discharge pores.The MAO coating on Zr-FSP sample had good wettability and corrosion resistance.However,TiO_(2)particles were hardly detected in the coating on TiFSP sample.

100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).

Boosting Peroxymonosulfate Activation via Co-Based LDH-Derived Magnetic Catalysts:A Dynamic and Static State Assessment of Efficient Radical-Assisted Electron Transfer Processes

Heterogeneous catalysts promoting efficient production of reactive species and dynamically stabilized electron transfer mechanisms for peroxomonosulfates(PMS)still lack systematic investigation.Herein,a more stable magnetic layered double oxides(CFLDO/N-C),was designed using self-polymerization and high temperature carbonization of dopamine.The CFLDO/N-C/PMS system effectively activated PMS to remove 99%(k=0.737 min^(-1))of tetracycline(TC)within 10 min.The CFLDO/N-C/PMS system exhibited favorable resistance to inorganic anions and natural organics,as well as satisfactory suitability for multiple pollutants.The magnetic properties of the catalyst facilitated the separation of catalysts from the liquid phase,resulting in excellent reproducibility and effectively reducing the leaching of metal ions.An electronic bridge was constructed between cobalt(the active platform of the catalyst)and PMS,inducing PMS to break the O-O bond to generate the active species.The combination of static analysis and dynamic evolution confirmed the effective adsorption of PMS on the catalyst surface as well as the strong radical-assisted electron transfer process.Eventually,we further identified the sites where the reactive species attacked the TC and evaluated the toxicity of the intermediates.These findings offer innovative insights into the rapid degradation of pollutants achieved by transition metals in SR-AOPs and its mechanistic elaboration.

An Application of the Taguchi Method (Robust Design) to Environmental Engineering: Evaluating Advanced Oxidative Processes in Polyester-Resin Wastewater Treatment

This paper presents the Taguchi Method, a statistical design modelling for experiments applied in environmental engineering. This method was applied to optimize the treatment conditions of polyester-resin effluent by means of Advanced Oxidative Processes (AOPs) using chemical oxygen demand (COD) as response parameter. The influence of each independent parameter including respective interactions was evaluated by Taguchi Method, which allowed determining the most statistically significant variables and conditions to best fit the process. Results showed that Taguchi Method is a very useful tool for environmental engineering field and possible simplifications of analysis and calculations through commercially available software.

Conversion of ferric oxide to magnetite by hydrothermal reduction in Bayer digestion process

Digesting aluminum-bearing minerals and converting ferric oxide to magnetite simultaneously in Bayer digestion process is crucially important to deal with high-iron diasporic bauxite economically for alumina production.The reaction behaviors of hydrothermal reduction of ferric oxide in alkali solution were studied by both thermodynamic calculation and experimental investigation.The thermodynamic calculation indicates that Fe3O4 can be formed by the conversion of Fe2O3 at proper redox potentials in alkaline solution.The experimental results show that the formation ratio of Fe3O4 either through the reaction of Fe and Fe2O3 or through the reaction of Fe and H2O in alkaline aqueous solution increases remarkably with raising the temperature and alkali concentration,suggesting that Fe（OH）3- and Fe（OH）4- form by dissolving Fe and Fe2O3,respectively,in alkaline aqueous solution and further react to form Fe3O4.Moreover,aluminate ions have little influence on the hydrothermal reduction of Fe2O3 in alkaline aqueous solution,and converting iron minerals to magnetite can be realized in the Bayer digestion process of diasporic bauxite.

Microstructure and high temperature oxidation resistance of Si-Y co-deposition coatings prepared on TiAl alloy by pack cementation process

In order to improve the high temperature oxidation resistance of TiAl alloy, Y modified silicide coatings were prepared by pack cementation process at 1030, 1080 and 1130 °C, respectively, for 5 h. The microstructures, phase constitutions and oxidation behavior of these coatings were studied. The results show that the coating prepared by co-depositing Si?Y at 1080 °C for 5 h has a multiple layer structure: a superficial zone consisting of Al-rich (Ti,Nb)5Si4 and (Ti,Nb)5Si3, an out layer consisting of (Ti,Nb)Si2, a middle layer consisting of (Ti,Nb)5Si4 and (Ti,Nb)5Si3, and aγ-TiAl inner layer. Co-deposition temperature imposes strong influences on the coating structure. The coating prepared by Si?Y co-depositing at 1080 °C for 5 h shows relatively good oxidation resistance at 1000 °C in air, and the oxidation rate constant of the coating is about two orders of magnitude lower than that of the bare TiAl alloy.

Oxide film on bubble surface of aluminum foams produced by gas injection foaming process

Based on A356 aluminum alloy,aluminum foams were prepared by gas injection foaming process with pure nitrogen,air and some gas mixtures.The oxygen volume fraction of these gas mixtures varied from 0.2%to 8.0%.Optical microscopy,scanning electron microscopy（SEM） and Auger electron spectroscopy（AES） were used to analyze the influence of oxygen content on cell structure,relative density,macro and micro morphology of cell walls,coverage area fraction of oxide film,thickness of oxide film and other aspects.Results indicate that the coverage area fraction of oxide film on bubble surface increases with the increase of oxygen content when the oxygen volume is less than 1.2%.While when the oxygen volume fraction is larger than 1.6%,an oxide film covers the entire bubble surface and aluminum foams with good cell structure can be produced.The thicknesses of oxide films of aluminum foams produced by gas mixtures containing 1.6%-21%oxygen are almost the same.The reasons why the thickness of oxide film nearly does not change with the variation of oxygen content and the amount of oxygen needed to achieve 100%coverage of oxide film are both discussed.In addition,the role of oxide film on bubble surface in foam stability is also analyzed.

Oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process

In the range of 620？710 °C, air was blown into A356 aluminum alloy melt to produce aluminum foams. In order to study the influence of temperature on the thickness of oxide film on bubble surface, Auger electron spectroscopy （AES） was used. Based on the knowledge of corrosion science and hydrodynamics, two oxidation kinetics models of oxide film on bubble surface were established. The thicknesses of oxide films produced at different temperatures were predicted through those two models. Furthermore, the theoretical values were compared with the experimental values. The results indicate that in the range of 620？710 °C, the theoretical values of the thickness of oxide film predicted by the model including the rising process are higher than the experimental values. While, the theoretical values predicted by the model without the rising process are in good agreement with the experimental values, which shows this model objectively describes the oxidation process of oxide film on bubble surface. This work suggests that the oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process follows the Arrhenius equation.

Effects of vacuum pre-oxidation process on thermally-grown oxides layer of CoCrAlY high temperature corrosion resistance coating

The influence of the certain specific vacuum pre-oxidation process on the phase transformation of thermally-grown oxides（TGO） was studied.The CoCrAlY high temperature corrosion resistance coatings were produced onto the nickel-based superalloy substrate by high velocity oxygen fuel（HVOF）.It suggests that the TGO usually consists of a great number of chromium oxides,cobalt oxides and spinel oxides besides alumina during the initial period of the high temperature oxidation if the specimens are not subjected to the appropriate vacuum pre-oxidation process.Furthermore,the amount of alumina is strongly dependent on the partial pressure of oxygen;while the CoCr2O4 spinel oxides are usually formed under the conditions of higher partial pressure of oxygen during the initial period and the lower partial pressure of oxygen during the subsequent period of the isothermal oxidation.After the appropriate vacuum pre-oxidation process,the TGO is mainly composed of alumina that contains lower Y element,while alumina that contains higher Y element sporadically distributes,and the spinel oxides cannot be found.After a longer period of the isothermal oxidation,a small amount of porous CoCr2O4 and the chrome oxide sporadically distribute near the continuous alumina.Additionally,after the appropriate vacuum pre-oxidation process,the TGO growth rate is relatively slow.

Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide： A DFT Study

The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd（PR3）2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd（PR3）n （n=1,2） with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition： less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.

Effects of Co_3O_4 nanocatalyst morphology on CO oxidation:Synthesis process map and catalytic activity

This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.

Degradation of 2,4-dichlorophenoxyacetic acid in water by ozonehydrogen peroxide process

This study reports an investigation into the degradation of 2,4-dichlorophenoxyacetic acid in bubble contactor column by O2/H2O2 process, which is widely used as a principal advanced oxidation process. The degradation of 2,4-dichlorophenoxyacetic acid was studied under different H202/O3 molar ratio and pH value. Meanwhile, TOC removal was investigated both in distilled water and tap water. The influences of ozone transfer and consumed hydrogen peroxide were also discussed. The degradation products and oxidation intermediates were identified by GC-MS and LC-MS. A possible reaction mechanism was thus proposed.

Application of advanced oxidation processes for removing salicylic acid from synthetic wastewaters

In this study,advanced oxidation processes(AOPs) such as anodic oxidation(AO),UV/H_2O_2 and Fenton processes(FP) were investigated for the degradation of salicylic acid(SA) in lab-scale experiments.Boron-doped diamond(BDD) film electrodes using Ta as substrates were employed for AO of SA.In the case of FP and UV/H_2O_2,most favorable experimental conditions were determined for each process and these were used for comparing with AO process.The study showed that the FP was the most effective process under aci...

ROS and oxidative burst:Roots in plant development

Reactive oxygen species(ROS)are widely generated in various redox reactions in plants.In earlier studies.ROS were considered toxic byproducts of aerobic metabolism.In recent years,it has become clear that ROS act as plant signaling molecules that participate in various processes such as growth and development.Several studies have elucidated the roles of ROS from seed germination to senescence.However,there is much to discover about the diverse roles of ROS as signaling molecules and their mechanisms of sensing and response.ROS may provide possible benefits to plant physiological processes by supporting cellular proliferation in cells that maintain basal levels prior to oxidative effects.Although ROS are largely perceived as either negative by-products of aerobic metabolism or makers for plant stress,elucidating the range of functions that ROS play in growth and development still require attention.

Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes

The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes （AOP） had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H202, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand （COD） and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater.

Synthesis of Yttrium Oxide Nanocrystal via Solvothermal Process

Y2O3 nanomaterials have been widely used in transparent ceramics and luminescent devices. Recently there are many studies focusing on controlling the size and morphology of Y2O3 in order to obtain better materials performance. In present study, yttrium oxyhydroxide precursor was synthesized via a facile solvothermal process through the dissolution-re-crystallization mechanism of Y2O3 raw powders in the ethylenediamine solvent, then nanosized yttrium oxide crystal was prepared from the precursor through post heat treatment process. The effects of solvothermal treatment temperature, holding time, solvent kinds and post heat treatment parameters on crystalline structure, grain shape and size of nanocrystal were investigated by XRD, TEM and TGA-DTA measurements. TEM images reveal that the morphology of product after post heat treatment at 460℃for 12 h is rice-like nanocrystal. XRD shows that this product is pure cubic Y2O3 cphase. Present study reveals that high purity Y2O3 with rice-like morphology can be easily prepared with average size around 30 nm under suitable post heat treatment parameters. In addition, the effects of solvents such as water and ethanol etc. on the crystal structure and morphology were also investigated. It is suggested that dissolution-recrystallization process may be the main mechanism for the formation of nano-sized YOOH precursors under solvothermal reaction condition, and the ethylenediamine solvent is likely to play an important role in controlling the transformation process of yttria precursors to the Y2O3 nanocrystal.