Carboxylates as green corrosion inhibitors of magnesium alloy for biomedical application

The efficiency of the green inhibitors(sodium salts of fumarate,glycolate and gluconate)in suppressing corrosion of the structural MA8 magnesium alloy(Mg–Mn–Ce)and the biomedical Mg–0.8Ca alloy was studied using the hydrogen evolution measurements,mass loss test,EIS,PDP,SVET/SIET.The analysis of the morphology,chemical composition,and growth kinetic of corrosion films formed in 0.9 wt%NaCl solution with and without corrosion inhibitors was carried out.The most compact surface film with the smallest thickness was formed in a saline solution with sodium fumarate.The Mg alloy samples exhibited the highest polarization resistance,the lowest localized electrochemical activity,and the lowest corrosion rate in saline with the addition of sodium fumarate and sodium glycolate.The efficiency of the applied inhibitors was up to 81%.The model of the corrosion mechanism based on the sorption of molecules of organic inhibitors is proposed.The results show the high compatibility of the used inhibitors with the calcium-phosphate PEO-matrix,indicating the possibility of forming a self-healing coating by means of these active substances.

Stabilized Nickel-Rich-Layered Oxide Electrodes for High-Performance Lithium-Ion Batteries

This work made use of the Aalto University Otanano-Nanomicroscopy Center and RAMI infrastructures.Financial support from Business Finland NextGenBat[grant number 211849]is greatly acknowledged.The tomography experiment was performed at the beamline ID16B of the European Synchrotron Radiation Facility(ESRF),Grenoble,France,in the frame of proposal CH-6644.The patent titled“Stabilized Positive Electrode Material to Enable High Energy and Power Density Lithium-Ion Batteries”(IPD3173)is pertinent to this manuscript.It was filed by Zahra Ahaliabadeh and Tanja Kallio,and the patent rights are held by Aalto University.

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.

Mechanisms of Accelerated Degradation in the Front Cells of PEMFC Stacks and Some Mitigation Strategies

The accelerated degradation in the front ceils of a polymer electrolyte membrane fuel cell（PEMFC） stack seriously reduces the reliability and durability of the whole stack. Most researches only focus on the size and configuration of the gas intake manifold, which may lead to the maldistribution of flow and pressure. In order to find out the mechanisms of the accelerated degradation in the front cells, an extensive program of experimental and simulation work is initiated and the results are reported. It is found that after long-term lifetime tests the accelerated degradation in the front cells occurs in all three fuel cell stacks with different flow-fields under the U-type feed configuration. Compared with the rear cells of the stack, the voltage of the front cells is much lower at the same current densities and the membrane electrode assembly（MEA） has smaller active area, more catalyst particle agglomeration and higher ohmic impedance. For further investigation, a series of three dimensional isothermal numerical models are built to investigate the degradation mechanisms based on the experimental data. The simulation results reveal that the dry working condition of the membrane and the effect of high-speed gas scouting the MEA are the main causes of the accelerated degradation in the front cells of a PEM fuel cell stack under the U-type feed configuration. Several mitigation strategies that would mitigate these phenomena are presented： removing cells that have failed and replacing them with those of the same aging condition as the average of the stack; choosing a Z-type feed pattern instead of a U-type one; putting several air flow-field plates without MEA in the front of the stack; or exchanging the gas inlet and outlet alternately at a certain interval. This paper specifies the causes of the accelerated degradation in the front cells and provides the mitigation strategies.

Unraveling the degradation mechanism of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) at the high cut-off voltage for lithium ion batteries

LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)layered oxides have been regarded as promising alternative cathodes for the next generation of high-energy lithium ion batteries(LIBs)due to high discharge capacities and energy densities at high operation voltage.However,the capacity fading under high operation voltage still restricts the practical application.Herein,the capacity degradation mechanism of NCM811 at atomic-scale is studied in detail under various cut-off voltages using aberration-corrected scanning transmission electron microscopy(STEM).It is observed that the crystal structure of NCM811 evolution from a layered structure to a rock-salt phase is directly accompanied by serious intergranular cracks under 4.9 V,which is distinguished from the generally accepted structure evolution of layered,disordered layered,defect rock salt and rock salt phases,also observed under 4.3 and 4.7 V.The electron energy loss spectroscopy analysis also confirms the reduction of Ni and Co from the surface to the bulk,not the previously reported only Li/Ni interlayer mixing.The degradation mechanism of NCM811 at a high cut-off voltage of4.9 V is attributed to the formation of intergranular cracks induced by defects,the direct formation of the rock salt phase,and the accompanied reduction of Ni^(2+)and Co^(2+)phases from the surface to the bulk.

Degradation of Alkaline Lignin in the Lactic Acid-Choline Chloride System under Mild Conditions

Lignin is a natural polymer,second only to cellulose in natural reserves.Degradation is one of the ways to achieve the high-value transformation of lignin.Deep eutectic solvent(DES)thermal degradation of lignin can be used as an excellent green degradation method.This paper introduces the degradation mechanism and effect of the lactic acid-choline chloride DES system in dissolving and degrading alkaline lignin,and the final solvent recovery.It can also be found from the scanning electron microscope(SEM)images that the surface of the degraded solid product is transformed from smooth to disordered.Fourier transform infrared(FTIR)spectroscopy and 1H-NMR spectroscopy were used to characterize the changes in lignin functional groups during DES treatment.The results showed that the content of phenolic hydroxyl groups increased after degradation,indicating that theβ-O-4 ether bond was broken.The molecular weight of the degraded lignin was observed by gel permeation chromatography(GPC),and the lignin residue with low molecular weight and narrow polydispersity index was obtained.The lowest average molecular weight(Mw)reached 2512 g/mol.The ratio of oxygen to carbon atoms in lignin increased substantially during degradation as measured by X-ray photoelectron spectroscopy(XPS),probably because DES treatment was accompanied by many oxidation reactions,which led to significant structural changes in lignin and a large number of ether bond breakage reactions during the reaction.The main final degradation products are aromatic monomers,vanillin,butyrovanillone,etc.

Interpretable hybrid machine learning demystifies the degradation of practical lithium-sulfur batteries

The ever-increasing future demands of electrification and grid storage have spurred continued research to develop rechargeable battery chemistries for reliable energy storage[1].Beyond current lithium-ion batteries,lithium–sulfur battery represents a promising system due to its high energy density(2600 Wh kg^(-1))and low material cost[2].

Electrochemical oxidation of perfluoroalkyl and polyfluoroalkyl substances:Mechanisms,implications,and challenges

Perfluoroalkyl and polyfluoroalkyl substances(PFASs)have recently gained considerable attention due to their potential risks to human health and ecosystems.The response to these concerns has led to regulations and bans on legacy PFASs,such as perfluorooctanoic acid and perfluorooctane sulfonic acid.Thus,fluoride production has shifted toward short-chain PFASs and emerging fluorinated alternatives.Several technologies are available for PFAS degradation,among which electrochemical oxidation(EO)is a promising method to mineralize legacy PFASs and other emerging fluorinated alternatives in water treatment.This review provides an overview of the recent advancements in EO,comprehensively elucidating PFAS degradation mechanisms at the anode and exploring key factors that influence PFAS removal efficiency,such as anode materials as well as reactor designs and configurations.Moreover,the review elucidates the impact of operating conditions and parameters,including current density,electrolytes,pH,initial PFAS concentrations,and other coexisting pollutants,on the EO process.Finally,the constraints in the EO process are discussed when considering practical implementations,including undesired by-product generation,incomplete mineralization resulting in the accumulation of short-chain PFASs,and low PFAS concentrations in the natural environment leading to mass transfer limitations and low defluorination efficiency.Consequently,this review provides a perspective on potential solutions integrating the pre-concentration steps and EO process for effective PFAS remediation.

Microwave photocatalytic degradation of Rhodamine B using TiO_2 supported on activated carbon:Mechanism implication

The photocatalytic degradation of Rhodamine B （RhB） was carried out using TiO2 supported on activated carbon （TiO2-AC） under microwave irradiation. Composite catalyst TiO2-AC was prepared and characterized using X-ray diffraction （XRD）, transmission electron microscopy （TEM） and Brunauer-Emmett-Teller （BET）. In the process of microwave-enhanced photocatalysis （MPC）, RhB （30 mg/L） was almost completely decoloured in 10 min, and the mineralization efficiency was 96.0% in 20 min. The reaction rate constant of RhB in MPC using TiO2-AC by pseudo first-order reaction kinetics was 4.16 times of that using Degussa P25. Additionally, according to gas chromatography/mass spectrometry （GC/MS） and liquid chromatography/mass spectrometry （LC/MS） identification, the major intermediates of RhB in MPC included two kinds of N-de-ethylation intermediates （N,N-diethyl-N＇-ethyl-rhodamine （DER））, oxalic acid, malonic acid, snccinic acid, and phthalic acid, maleic acid, 3-nitrobenzoic acid, and so on. The degradation of RhB in MPC was mainly attributed to the destruction of the conjugated structure, and then the intermediates transformed to acid molecules which were mineralized to water and carbon dioxide.

Degradation mechanism of 2,4,6-trinitrotoluene in supercritical water oxidation

The 2,4,6-trinitrotoluene （TNT） is a potential carcinogens and TNT contaminated wastewater, which could not be effectively disposed with conventional treatments. The supercritical water oxidation （SCWO） to treat TNT contaminated wastewater was studied in this article, The TNT concentration in wastewater was measured by high-performance liquid chromatograph （HPLC） and the degraded intermediates were analyzed using GC-MS. The results showed that SCWO could degrade TNT efficiently in the presence of oxygen. The reaction temperature, pressure, residence time and oxygen excess were the main contributing factors in the process. The decomposition of TNT was accelerated as the temperature or residence time increased. At 550℃, 24 MPa, 120 s and oxygen excess 300%, TNT removal rate could exceed 99.9%. Partial oxidation occured in SCWO without oxygen. It was concluded that supercritical water was a good solvent and had excellent oxidation capability in the existence of oxygen. The main intermediates of TNT during SCWO included toluene, 1,3,5-trinitrobenzene, nitrophenol, naphthalene, fluorenone, dibutyl phthalate, alkanes and several dimers based on the intermediate analysis. Some side reactions, such as coupled reaction, hydrolysis reaction and isomerization reaction may take place simultaneously when TNT was oxidized by SCWO.

Corrosion resistances of metallic materials in environments containing chloride ions:A review

Corrosion,more specifically,pitting corrosion happening extremely in marine environments,leads to lifespan of materials drastically decreasing in service,which causes enormous economic loss and even environmental disaster and casualties.In the past decade,increasing efforts have been made to study the corrosion behaviors of materials in chloride-containing aqueous environments.Herein,this work provides an overview of recent progress in understanding the degradation mechanism and improving the corrosion resistance and corrosion-wear resistance of materials from bulk metal to surface treatment involving organic coating,metal and its alloy or compound coating.The particular emphasis is given to the periodic layered structures(PLSs),whose anti-corrosion properties outperformed others to some extent,wherever in terms of bulk metal or surface treatment,regardless of aggressive environment(corrosion or corrosion-wear conditions).Numerical simulation based on kinds of models at different scales is introduced to deeply understand the process of corrosion and/or corrosion-wear in chloride-containing aqueous environment.Combined experimental result with numerical simulation,the micro-galvanic corrosion dominated degradation mechanism of PLSs is critically analyzed.Types of setups to realize corrosion-wear in laboratory are also summarized.At last,future research and development are prospected,offering to develop a basic application of PLSs designed by corrosion protection methodology in the near future.

Electrochemical oxidation of rhodamine B by PbO_2/Sb-SnO_2/TiO_2 nanotube arrays electrode

A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.

Synthesis of novel p-n heterojunction m-Bi_2O_4/BiOCl nanocomposite with excellent photocatalytic activity through ion-etching method

A novel p‐n heterostructure photocatalyst m‐Bi2O4/BiOCl was successfully synthetized through a facile ion‐etching method.Via adjusting the added volume of HCl solution,a series of different ratios of composite photocatalysts were obtained.The as‐prepared samples of physical,chemical and optical characteristics were examined by X‐ray diffraction,scanning electron microscope,transmission electron microscope,energy dispersive X‐ray spectroscopy,selected‐area electron diffraction,Fourier transform infrared absorption,Raman microscope,N2 adsorption‐desorption,X‐ray photoelectron spectroscopy and UV‐vis spectrum technologies.The photocatalysts showed high degradation rate and complete mineralization ability for methyl orange and tetracycline solution under visible light.The reaction rate constant of m‐Bi2O4/BiOCl for methyl orange was 52.28 times higher than that of BiOCl.The characterization presented a good stability of materials.Furthermore,the photocurrent response test certified that the heterostructure effectively accelerated the separation and migration of photo‐generated carries.The scavenger experiments evidenced that hole(h+)and superoxide radical(?O2?)were the primary active radicals.A possible photocatalytic mechanism was proposed.This work provided an alternative photocatalyst applied to water environmental remediation.

Complete removal of phenolic contaminants from bismuth-modified TiO2 single-crystal photocatalysts

Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.

Degradation and mineralization of aniline by O_3/Fenton process enhanced using high-gravity technology

The degradation and mineralization of aniline （AN） using ozone combined with Fenton reagent （O3/Fenton） in a rotating packed bed （RPB） was proposed in this study, and the process （RPB-O3/Fenton） was compared with conventional O3/Fenton in a stirred tank reactor （STR-O3/Fenton） or single ozonation in an RPB （RPB-O3）, Effects of high gravity factor, H2O2 dosage, H2O2 dosing method and initial pH on the AN mineralization efficiency were investigated in the RPB-O3/Fenton process, In addition, the behavior of Fe（Ⅱ） was monitored at different H2O2 dosing methods and pH values. Finally, the optimal operation conditions were determined with high gravity factor of 100, initial pH of 5, Fe（Ⅱ） concentration of 0.8 mmol·L-1 and H2O2 dosage of 2.5 ml. Under these conditions, for aniline wastewater at the volume of I L and concentration of 200 mg· L- 1 ,a fast and thorough decay of AN was conducted in 10 min, and the TOC removal efficiency reached 89% in 60 min. The main intermediates of p-benzoquinone, nitrobenzene, maleic acid and oxalic acid were identified by liquid chromatography/mass spectroscopy （LC/MS）, and the degradation pathways of AN in RPB-O3/Fenton system were proposed based on experimental evidence. It could be envisioned that high-gravity technology combined with O3/Fenton processes would be promising in the rapid and efficient mineralization ofwastewater.

Mechanism of progressive failure of a slope with a steep joint under the action of freezing and thawing:model test

The stability of slope rock masses is influenced by freeze-thaw cycles in cold region,and the mechanism of stability deterioration is not clear.In order to understand the damage and progressive failure characteristics of rock masses under the action of freezing and thawing,a model test was conducted on slope with steep joint in this study.The temperature,frost heaving pressure and deformation of slope rock mass were monitored in real-time during the test and the progressive failure mode was studied.The experimental results show that the temperature variations of cracking and the rock mass of a slope are different.There are obvious latent heat stages in the temperature-change plot in the crack,but not in the slope rock masses.The frost heaving effect in the fracture is closely related to the constraint conditions,which change with the deformation of the fracture.The frost heaving pressure fluctuates periodically during freezing and continues to decrease during thawing.The surface deformation of the rock mass increases during freezing,and the deformation is restored when it thaws.Freeze-thaw cycling results in residual deformation of the rock mass which cannot be fully restored.Analysis shows that the rock mass at the free side of the steep-dip joint rotates slightly under the frost heaving effect,causing fracture propagation.The fracture propagation pattern is a circular arc at the beginning,then extends to the possible sliding direction of the rock mass.Frost heaving force and fracture water pressure are the key factors for the failure of the slope,which can cause the crack to penetrate the rock mass,and a landslide ensues when the overall anti-sliding resistance of the rock mass is overcome.

The reliability of AlGaN/GaN high electron mobility transistors under step-electrical stresses

In spite of their extraordinary performance, AlGaN/GaN high electron mobility transistors （HEMTs） still lack solid reliability. Devices under accelerated DC stress tests （off-state, VDS = 0 state, and on-state step-stress） are investigated to help us identify the degradation mechanisms of the AlGaN/GaN HEMTs. All our findings are consistent with the degradation mechanism based on crystallographic-defect formation due to the inverse piezoelectric effects in Ref. [1] （Joh J and del Alamo J A 2006 IEEE IDEM Tech. Digest p. 415）. However, under the on-state condition, the devices are suffering from both inverse piezoelectric effects and hot electron effects, and so to improve the reliability of the devices both effects should be taken into consideration.

The ORR electron transfer kinetics control via Co-N_(x) and graphitic N sites in cobalt single atom catalysts in alkaline and acidic media

Cost-effective 3d transition metal(TM) based single atom catalysts(SACs) for oxygen reduction reaction(ORR) are potential alternatives for Pt-based electrocatalysts in fuel cells and metal-air batteries.Understanding the effects of SACs’ properties and active site composition on the catalytic performance is significant to construct highly efficient catalysts. Here, we successfully promote the activity of cobalt single atoms decorated on N-doped carbon nanosheets via tuning the content of different nitrogen components, which outperforms most reported cobalt SACs. The activity and kinetics show positive correlation trends with the content of Co-Nxand graphitic N, serving as the main active sites.Furthermore, ORR kinetics in alkaline media can be positively affected by the conductivity of catalysts while no similar relation is observed in acidic media. The slight loss of Co-Nxsites engenders a mild change of performance in alkaline media, while the decrease of Co-Nxsite activity due to chemical oxidation of carbon support and the loss of Co-Nxsites in acidic media exacerbate the degradation of performance. Our work provides an insight into the relation between ORR electron transfer kinetics and active sites in 3d TM based SACs.

Complete oxidation of 1,4-dioxane over zeolite-13X-supported Fe catalysts in the presence of air

Zeolite-13X-supported Fe（Fe/zeolite-13X） catalysts with various Fe contents were prepared by the wet impregnation method.The catalysts were characterized by N2 adsorption-desorption isotherms to estimate the Brunauer-Emmett-Teller surface areas and Barrett-Joyner-Hanlenda pore size distributions.X-ray diffraction,scanning electron microscopy,temperature-programmed reduction,and temperature-programmed desorption of NH3 were used to investigate the textural properties of the Fe/zeolite-13 X catalysts.Their catalytic activities were determined for the complete oxidation of1,4-dioxane using air as the oxidant in a fixed-bed flow reactor in the temperature range 100-400℃.The influences of various process parameters,such as reaction temperature,metal loading,and gas hourly space velocity（GHSV）,on the dioxane removal efficiency by catalytic oxidation were investigated.The stability of the catalyst was tested at 400℃ by performing time-on-stream analysis for 50 h.The Fe/zeolite-13 X catalyst with 6 wt%Fe exhibited the best catalytic activity among the Fe/zeolite-13 X catalysts at 400℃ and a GHSV of 24000 h^（-1）,with 97%dioxane conversion and95%selectivity for the formation of carbon oxides（CO and CO2）.Trace amounts（ 3%） of acetaldehyde,ethylene glycol monoformate,ethylene glycol diformate,1,4-dioxane-2-ol,1,4-dioxane-2-one,and 2-methoxy-1,3-dioxalane were also formed as degradation products.A plausible degradation mechanism is proposed based on the products identified by GC-MS analysis.

The Mechanism of Carotenoid Degradation in Flue-Cured Tobacco and Changes in the Related Enzyme Activities at the Leaf-Drying Stage During the Bulk Curing Process

The mechanism of carotenoid degradation and the changes in the activities of related enzymes in flue-cured tobacco at the leaf-drying stage during the bulk-curing process were studied in order to provide theoretical basis for optimization of curing technology. The effect of different rising speeds of temperature on the carotenoid degradation and the related enzymes activities at the color-fixing stage during the bulk curing process was studied by using the electric-heated fluecuring barn designed by Henan Agricultural University, China, based on curing technology with yellowing at low temperature and moderate humidity and leaf drying at moderate humidity. The results showed that the carotenoid degradation components （β-carotene, lutein, neoxanthin, and violaxthin） decreased gradually at the color-fixing stage during the bulk curing process. The carotenoid degradation components viz.,β-carotene, lutein, neoxanthin, and violaxthin at the slow heating curing （T1） were relatively higher than the rapid heating curing （T2） accounting for 10, 2, 32 and 32% respectively, but there were no differences among treatments （P〉 0.05）. The effect of different conditions of curing on the activities of enzymes related to carotenoids degradation were significant. The lipoxygenase, phenylalanine ammonialyase, peroxidase, and polyphenol oxidase enzymes had a bidirectional effect on the quality of tobacco leaves and it was beneficial to form more premise matter of aroma based on the higher enzyme activities at the early leaf-drying stage. The slow heating could regulate the change in various enzymes＇ activities reasonably, making cell redox reaction to reach the dynamic balance and make the degradation of carotenoids adequately. Meanwhile, it could avoid the occurrence of browning reaction and provide foundation for improving the quality of tobacco and optimization of technology for bulk curing and further enhancing aroma.