Kinetics of Burning Side Reaction in the Liquid-phase Oxidation of p-Xylene

During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.

Synergistic Catalytic Action of Cobalt(Ⅱ) Hydroxamates and N-Hydroxyphthalimide in the Aerobic Oxidation of p-Xylene

The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.

Effect of CO2 on oxidation of p-xylene in acetic acids/CO2

The oxidation of p-xylene to terephthalic acid with molecular oxygen in acetic acids modified carbon dioxide over Co/Mn/Br catalyst was studied in a batch reactor. The results showed that the oxidation of p-xylene to terephthalic acid was severely inhibited when carbon dioxide exceeded a certain amount, the conversion of p-xylene decreased rapidly from 100.0% to 3.3% and the yield of terephthalic acid dropped from 42.6% to trace. Whereas the oxidation processes of p-Tolualdchyde to p-Toluic acid and 4-Carboxybenzaldehyde to tcrcphthalic acid were improved when a relative small amount of CO2 v/as added, Further investigation found that this negative effect may be caused by multiphase reactions emerging.

Deciphering Water Oxidation Catalysts:The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion

Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.

Hypidone hydrochloride(YL-0919)ameliorates functional deficits after traumatic brain injury in mice by activating the sigma-1 receptor for antioxidation

Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0919),a self-developed antidepressant with selective sigma-1 receptor agonist properties,and its associated mechanisms and targets in traumatic brain injury.Behavioral experiments to assess functional deficits were followed by assessment of neuronal damage through histological analyses and examination of blood-brain barrier permeability and brain edema.Next,we investigated the antioxidative effects of YL-0919 by assessing the levels of traditional markers of oxidative stress in vivo in mice and in vitro in HT22 cells.Finally,the targeted action of YL-0919 was verified by employing a sigma-1 receptor antagonist(BD-1047).Our findings demonstrated that YL-0919 markedly improved deficits in motor function and spatial cognition on day 3 post traumatic brain injury,while also decreasing neuronal mortality and reversing blood-brain barrier disruption and brain edema.Furthermore,YL-0919 effectively combated oxidative stress both in vivo and in vitro.The protective effects of YL-0919 were partially inhibited by BD-1047.These results indicated that YL-0919 relieved impairments in motor and spatial cognition by restraining oxidative stress,a neuroprotective effect that was partially reversed by the sigma-1 receptor antagonist BD-1047.YL-0919 may have potential as a new treatment for traumatic brain injury.

Modified Self-adaptive Immune Genetic Algorithm for Optimization of Combustion Side Reaction of p-Xylene Oxidation

In recent years, immune genetic algorithm (IGA) is gaining popularity for finding the optimal solution for non-linear optimization problems in many engineering applications. However, IGA with deterministic mutation factor suffers from the problem of premature convergence. In this study, a modified self-adaptive immune genetic algorithm (MSIGA) with two memory bases, in which immune concepts are applied to determine the mutation parameters, is proposed to improve the searching ability of the algorithm and maintain population diversity. Performance comparisons with other well-known population-based iterative algorithms show that the proposed method converges quickly to the global optimum and overcomes premature problem. This algorithm is applied to optimize a feed forward neural network to measure the content of products in the combustion side reaction of p-xylene oxidation, and satisfactory results are obtained.

The preparation of terephthalic acid by solvent-free oxidation of p-xylene with air over T(p-C1)PPMnC1 and Co(OAc)_2

An attempt has been made to prepare terephthalic acid（TPA） by solvent-free oxidation of p-xylene（PX） with air over tetra（pchlorophenylporphinato） manganese chloride（T（p-Cl）PPMnCl） and cobalt acetate.The co-catalysis between T（p-Cl）PPMnCl and Co（OAc）_2 has been discovered under solvent-free conditions.TPA yield could be increased significantly when T（p-Cl）PPMnCl and Co（OAc）_2 were used together.The addition of T（p-Cl）PPMnCl into the reaction mixture over Co（OAc）_2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.

Multi-objective optimization of p-xylene oxidation process using an improved self-adaptive differential evolution algorithm

The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemical process in industry [ 1 ]. PX oxidation reaction involves many complex side reactions, among which acetic acid combustion and PX combustion are the most important. As the target product of this oxidation process, the quality and yield of TPA are of great concern. However, the improvement of the qualified product yield can bring about the high energy consumption, which means that the economic objectives of this process cannot be achieved simulta- neously because the two objectives are in conflict with each other. In this paper, an improved self-adaptive multi-objective differential evolution algorithm was proposed to handle the multi-objective optimization prob- lems. The immune concept is introduced to the self-adaptive multi-objective differential evolution algorithm （SADE） to strengthen the local search ability and optimization accuracy. The proposed algorithm is successfully tested on several benchmark test problems, and the performance measures such as convergence and divergence metrics are calculated. Subsequently, the multi-objective optimization of an industrial PX oxidation process is carried out using the proposed immune self-adaptive multi-objective differential evolution algorithm （ISADE）. Optimization results indicate that application oflSADE can greatly improve the yield of TPA with low combustion loss without degenerating TA quality.

High dimension feature extraction based visualized SOM fault diagnosis method and its application in p-xylene oxidation process

Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a complex process involving three-phase reaction of gas, liquid and solid. To monitor the process and to improve the product quality, as well as to visualize the fault type clearly, a fault diagnosis method based on selforganizing map(SOM) and high dimensional feature extraction method, local tangent space alignment(LTSA),is proposed. In this method, LTSA can reduce the dimension and keep the topology information simultaneously,and SOM distinguishes various states on the output map. Monitoring results of PX oxidation reaction process indicate that the LTSA–SOM can well detect and visualize the fault type.

Design and control of a p-xylene oxidation process

The p-xylene(PX) oxidation process is of great industrial importance because of the strong demand of the global polyester fiber.A steady-state model of the PX oxidation has been studied by many researchers.In our previous work,a novel industrial p-xylene oxidation reactor model using the free radical mechanism based kinetics has been developed.However,the disturbances such as production rate change,feed composition variability and reactor temperature changes widely exist in the industry process.In this paper,dynamic simulation of the PX oxidation reactor was designed by Aspen Dynamics and used to develop an effective plantwide control structure,which was capable of effectively handling the disturbances in the load and the temperature of the reactor.Step responses of the control structure to the disturbances were shown and served as the foundation of the smooth operation and advanced control strategy of this process in our future work.

Competitive oxidation behavior of Ni-based superalloy GH4738 at extreme temperature

A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.

Tuning the reactivity of TiO_(2)layer with uniform distribution of Sub-5 nm Fe_(2)O_(3)particles via in situ voltage-assisted oxidation for robust catalytic reduction

The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.

Electrochemical anodic oxidation assisted fabrication of memristors

Owing to the advantages of simple structure,low power consumption and high-density integration,memristors or memristive devices are attracting increasing attention in the fields such as next generation non-volatile memories,neuromorphic computation and data encryption.However,the deposition of memristive films often requires expensive equipment,strict vacuum conditions,high energy consumption,and extended processing times.In contrast,electrochemical anodizing can produce metal oxide films quickly(e.g.10 s) under ambient conditions.By means of the anodizing technique,oxide films,oxide nanotubes,nanowires and nanodots can be fabricated to prepare memristors.Oxide film thickness,nanostructures,defect concentrations,etc,can be varied to regulate device performances by adjusting oxidation parameters such as voltage,current and time.Thus memristors fabricated by the anodic oxidation technique can achieve high device consistency,low variation,and ultrahigh yield rate.This article provides a comprehensive review of the research progress in the field of anodic oxidation assisted fabrication of memristors.Firstly,the principle of anodic oxidation is introduced;then,different types of memristors produced by anodic oxidation and their applications are presented;finally,features and challenges of anodic oxidation for memristor production are elaborated.

Boosted Electrocatalytic Glucose Oxidation Reaction on Noble-Metal-Free MoO_(3)-Decorated Carbon Nanotubes

Electrocatalytic glucose oxidation reaction(GOR)has attracted much attention owing to its crucial role in biofuel cell fabrication.Herein,we load MoO_(3)nanoparticles on carbon nanotubes(CNTs)and use a discharge process to prepare a noblemetal-free MC-60 catalyst containing MoO_(3),Mo_(2)C,and a Mo_(2)C–MoO_(3)interface.In the GOR,MC-60 shows activity as high as 745μA/(mmol/L cm^(2)),considerably higher than those of the Pt/CNT(270μA/(mmol/L cm^(2)))and Au/CNT catalysts(110μA/(mmol/L cm^(2))).In the GOR,the response minimum on MC-60 is as low as 8μmol/L,with a steady-state response time of only 3 s.Moreover,MC-60 has superior stability and anti-interference ability to impurities in the GOR.The better performance of MC-60 in the GOR is attributed to the abundant Mo sites bonding to C and O atoms at the MoO_(3)–Mo_(2)C interface.These Mo sites create active sites for promoting glucose adsorption and oxidation,enhancing MC-60 performance in the GOR.Thus,these results help to fabricate more effi cient noble-metal-free catalysts for the fabrication of glucose-based biofuel cells.

Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

Electron-distribution control via Pt/NC and MoC/NC dual junction:Boosted hydrogen electro-oxidation and theoretical study

The scarcity,high cost and susceptibility to CO of Platinum severely restrict its application in alkaline hydrogen oxidation reaction(HOR).Hybridizing Pt with other transition metals provides an effective strategy to modulate its catalytic HOR performance,but at the cost of mass activity due to the coverage of modifiers on Pt surface.Herein,we constructed dual junctions'Pt/nitrogen-doped carbon(Pt/NC)andδ-MoC/NC to modify electronic structure of Pt via interfacial electron transfer to acquire Pt-MoC@NC catalyst with electron-deficient Pt nanoparticles,simultaneously endowing it with high mass activity and durability of alkaline HOR.Moreover,the unique structure of Pt-MoC@NC endows Pt with a high COtolerance at 1,000 ppm CO/H_(2),a quality that commercial Pt-C catalyst lacks.The theoretical calculations not only confirm the diffusion of electrons from Pt/NC to Mo C/NC could occur,but also demonstrate the negative shift of Pt d-band center for the optimized binding energies of*H,*OH and CO.

Trace Cobalt Doping and Defect Engineering of High Surface Area α-Ni(OH)_(2) for Electrocatalytic Urea Oxidation

Owing to the intrinsically sluggish kinetics of urea oxidation reaction(UOR)involving a six-electron transfer process,developing efficient UOR electrocatalyst is a great challenge remained to be overwhelmed.Herein,by taking advantage of 2-Methylimidazole,of which is a kind of alkali in water and owns strong coordination ability to Co^(2+)in methanol,trace Co(1.0 mol%)addition was found to induce defect engineering onα-Ni(OH)_(2)in a dual-solvent system of water and methanol.Physical characterization results revealed that the synthesized electrocatalyst(WM-Ni_(0.99)Co_(0.01)(OH)_(2))was a kind of defective nanosheet with thickness around 5-6 nm,attributing to the synergistic effect of Co doping and defect engineering,its electron structure was finely altered,and its specific surface a rea was tremendously enlarged from 68 to 172.3 m^(2)g^(-1).With all these merits,its overpotential to drive 10 mA cm^(-2)was reduced by 110 mV.Besides,the interfacial behavior of UOR was also well deciphered by operando electrochemical impedance spectroscopy.

Microwave-assisted exploration of the electron configuration-dependent electrocatalytic urea oxidation activity of 2D porous NiCo_(2)O_(4) spinel

Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.

Pyridinic-N doping carbon layers coupled with tensile strain of FeNi alloy for activating water and urea oxidation

Exploitation of oxygen evolution reaction(OER)and urea oxidation reaction(UOR)catalysts with high activity and stability at large current density is a major challenge for energy-saving H_(2) production in water electrolysis.Herein,we use the pyridinic-N doping carbon layers coupled with tensile strain of FeNi alloy activated by NiFe_(2)O_(4)(FeNi/NiFe_(2)O_(4)@NC)for efficiently increasing the performance of water and urea oxidation.Due to the tensile strain effect on FeNi/NiFe_(2)O_(4)@NC,it provides a favorable modulation on the electronic properties of the active center,thus enabling amazing OER(η_(100)=196 mV)and UOR(E_(10)=1.32 V)intrinsic activity.Besides,the carbon-coated layers can be used as armor to prevent FeNi alloy from being corroded by the electrolyte for enhancing the OER/UOR stability at large current density,showing high industrial practicability.This work thus provides a simple way to prepare high-efficiency catalyst for activating water and urea oxidation.

Implications of 1.5 K climate warming on warm-season ozone exposure and atmospheric oxidation capacity in China

Surface ozone(O_(3))poses significant threats to public health,agricultural crops,and plants in natural ecosystems.Global warming is likely to increase future O_(3)mainly by altering atmospheric photochemical reactions and enhancing biogenic volatile organic compound(BVOC)emissions.To assess the impacts of the future 1.5 K climate target on O_(3)concentrations and ecological O_(3)exposure in China,numerical simulations were conducted using the CMAQ(Community Multiscale Air Quality)model during April-October 2018.Ecological O_(3)exposure was estimated using six indices(i.e.,M7,M24,N100,SUM60,W126,and AOT40f).The results show that the temperature rise increases the MDA8 O_(3)(maximum daily eight-hour average O_(3))concentrations by∼3 ppb and the number of O_(3)exceedance days by 10-20 days in the North China Plain(NCP),Yangtze River Delta(YRD),and Sichuan Basin(SCB)regions.All O_(3)exposure indices show substantial increases.M24 and M7 in eastern and southern China will rise by 1-3 ppb and 2-4 ppb,respectively.N100 increases by more than 120 h in the surrounding regions of Beijing.SUM60 increases by greater than 9 ppm h^(−1),W126 increases by greater than 15 ppm h^(−1)in Shaanxi and SCB,and AOT40f increases by 6 ppm h^(−1)in NCP and SCB.The temperature increase also promotes atmospheric oxidation capacity(AOC)levels,with the higher AOC contributed by OH radicals in southern China but by NO_(3)radicals in northern China.The change in the reaction rate caused by the temperature increase has a greater influence on O_(3)exposure and AOC than the change in BVOC emissions.