A Review on Complete Oxidation of Methane at Low Temperatures

This paper reviews recent developments in complete oxidation of methane at low temperatures over noble metal catalysts in the past 20 years. The Pd/A1203 catalyst system is fully discussed. The review mainly focuses on the kinetic aspects of methane oxidation over this catalyst, and methane activation behavior over Pd and PdO phases (the form of PdO on the surface, transient behavior, the nature of the active sites, the influence of metal particle size and their structure sensitivities, and so on). Some Pd catalysts supported on other oxides besides the Al2O3 support are briefly discussed. Possible routes of non-noble metal catalysts as substitutes for the Pd catalyst are also proposed.     

Reaction mechanism and additional lithium storage of mesoporous MnO_2 anode in Li batteries

Nanostructured transition metal oxides,employed as anode materials for lithium-ion batteries,exhibit a higher capacity than the theoretical capacity based on the conversion reaction.To date,the reasons behind this phenomenon are unclear.For the one-step evolution of anode material for lithium-ion batteries,it is essential to understand the lithium storage reaction mechanism of the anode material.Herein,we provide a detailed report on the lithium storage and release mechanism of MnO2,using synchrotron-based X-ray techniques.X-ray diffraction and X-ray absorption spectroscopy results indicate that during the first discharge,MnO2 is reduced in the order of MnO2→LixMnO2(1相似文献   

A novel Mo-based oxide β-SnMoO_4 as anode for lithium ion battery

Recently,the development of new electrode materials for lithium-ion batteries(LIBs)has received intensive attention.As an important family of inorganic materials,mixed Mo-based transition metal oxides system is focused as anode materials.In the present work,a simple route has been adopted for the synthesis of layered-flake-likeβ-SnMo04 Nano-assemblies,which have been explored as potential anode materials for the first time in lithium-ion battery(LIB).Overall,the current reports on metal molybdate as anode materials are still rarely.As the anode material for LIBs,it was observed that the fabricated anode is capable of delivering a steady state capacity of almost 400 mAh/g up to 300 cycles under the influence of200 mA/g current density.Further,the anode material is suitable for use as a rated capacity anode because of its high current density tolerance.The present study can be further extended for the generation of a wide variety of other novel materials for multidisciplinary energy related applications.     

Synthesis of Diethyl Oxalate by a Coupling—Regeneration Reaction of Carbon Monoxide

This article describes a process for the synthesis of diethyl oxalate by a copling reaction of carbon monoxide,catalyzed by palladium in the presence of ethyl nitrite ,The kinetics and mechanism of the coupling and regeneration reaction are also discussed ,This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.     

Synergistic effect from coaxially integrated CNTs@MoS2/MoO2 composite enables fast and stable lithium storage

Molybdenum oxide/sulfide materials are extensively evaluated as high-capacity anode candidates for lithium ion batteries.However,they suffer from rapid capacity decay and poor kinetics.Herein,we report on synergistic effect from structurally integrated coaxial CNTs@MoS₂/MoO₂ composite material on lithium storage,in which MoS₂/MoO₂ nanosheets are conformally decorated on carbon nanotubes(CNTs).In-situ synchrotron X-ray diffraction measurement is performed to elucidate synergistic effect among three MoS₂,MoO₂ and CNTs components for lithium storage.Reaction mechanism exploration reveals that the MoO₂ component undergoes reversible Li⁺intercalation via forming a stable Li_0.98 MoO₂ phase over a voltage range of 3.0 to 0.01 V vs.Li⁺/Li,without experiencing the conversion reaction into metallic Mo,which contributes to long-term stability during charge/discharge cycles.Meanwhile,lithium storage of MoS₂ is through lithium and sulfur reversible reaction after the initial conversion reaction of lithiated MoS₂ forming Li₂S and Mo.The CNTs component enhances electronic conductivity and structural stability by minimizing volume change and reaction strains in the CNTs@MoS₂/MoO₂ composite anode.A desired 68.2%capacity retention upon 2000 cycles at 10 A/g has been demonstrated for the CNTs@MoS₂/MoO₂ anode,revealing prominent reaction kinetics and structural stability for fast and stable lithium storage,superior to various Mo-based anode materials previously reported.The findings from this study,with the unique insight into the role of structural integrity in combining MoS₂/MoO₂ materials with the CNTs substrate,offers a strategy for designing composite anode materials for superior lithium storage performance.     

Iridium oxide fabrication and application: A review

Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g.,chlorine evolution reaction,detoxification,and oxygen evolution reaction).Such versatility is attributed to the distinct features of iridium oxides,such as their activity,biocompatibility,conductivity,and durability.The features and properties of iridium oxides are strongly dependent on the fabrication method.In this review,methodologies relating to the synthesis and fabrication of solid-state iridium oxides have been thoroughly collected and discussed.Structuring and crystallization techniques for iridium oxides are also noted.At the end of the review,the effects of utilizing a certain fabrication method on the characteristics of the iridium oxide product are recapitulated,together with the recommended application of the product in various fields.     

STUDIES ON BIO-ANTIOXIDANTS——MICELLAR EFFECTS ON THE REDUCTION OF NITROXIDES BY VITAMIN C

The kinetics of reduction of nitroxides including 4-hydroxy-TEMPO, 4-methoxy-TEMPOand 4-hexanoyloxy-TEMPO, which are of different lipophilicities, by vitamin C in cationic,non-ionic and anionic micelles, i. e. CTAB, Triton X-100 and SDS, respectively, have beenstudied by ESR spectroscopy by a stopped-flow technique. A mechanism for the reactionconducted in micelles is proposed and the rate constants for the elementary reactions areevaluated. It is found that the rates of single electron transfer reactions involving the ni-troxides are dependent on the nature of the micelle and the lipophilicity of the nitroxide.The rates are increased in CTAB, decreased in SDS, whereas unaffected in Triton X-100.And the greater the lipophilicity of the nitroxide, the more pronounced the rate variation.As high as a 3600-fold increase in the rate was observed for 4-hexanoyloxy-TEMPO in CTABover that in SDS. The micellar effects are rationalized on the basis of analysis of parame-ters and line shape of the ESR spectra for     

脂族酰基过氧化物分解动力学的分研究 III: 过氧化3,5,5-三甲基己酰在萃中的解动力学和机理

The kinetics of decomposition of 3, 5, 5-trimethylhexanoyl peroxide (1) in benzene has been studied at 30, 40 and 50`C and the cage effect of decomposition has been determined by scavenging method. The relative amounts of the main products of decomposition of 1 at 50`C with change of initial concentration have been determined. The results showed that the decomposition of 1 followed first plus three halves order kinetics as reported for lauroyl peroxide (2), but had a larger cage effect of 0.6. The mechanism of decomposition of 1 is practically the same as what we have proposed for 2. The faster rate and larger cage effect but less induced decomposition of 1 than that of 2 are attributed to the branching of the molecule of 1, especially to the presence of β-methyl group, which causes a larger entropy increase in the transition state.     

Precise in-situ and ex-situ study on thermal behavior of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/graphite coin cell:From part to the whole cell

Multiple mode calorimetry and C80 micro-calorimeter are used to investigate the impact of cathode and anode on heat generation of lithium ion battery.The thermal behaviors of LiNi_xCo_yMn_zO₂/graphite full cell are discussed under normal operating and elevating temperature.Affected by negative entropy change,lithium intercalation presents more exotherms than deintercalation for both electrode materials.The contributions of irreversible and reversible heat to the total heat generation of graphite are evaluated.The phase transitions correlated with voltages and lithium contents are determined.Based on the analysis of half-cell,the effect of two electrodes(with the same capacity)on overall heat generation is nearly the same and anode of full cell plays a key role in charging while cathode dominates in discharging.Thermal behaviors of lithiated graphite and delithiated LiNi_xCo_yMn_zO₂ electrolyte and their coexisting system are identified to further explore their influence on battery safety.The breakdown of solid electrolyte interface(SEI)at around 82℃ is considered as a crucial factor affecting the thermal stability of full cell.The oxidation of electrolyte induced by oxygen released from cathode material turns out to be one of the main heat sources.These accurate results are of great significance to improve the existing thermal management system and provide basic data for the prediction of battery performance.     

A new anode material LiMoS_2 for use in rechargeable Lithium Ion Batteries

The novel applications of molybdenum disulfide in recent research were reviewed, such as in lubricant, catalyst and photoelectrochemical solar cells. Recently, we found that LiMoS2 is a good candidate for new anode materials for lithium ion batteries with high lithium storage capacity. Here, the anode material LiMoS2 was synthesized by a hydrothermal method at 150oC and the electrochemical characterization as an anode material for lithium ion batteries was examined. The preparation procedur…     

Manganese Oxide(MnO) and Cadmium Dioxide(CdO_2) Attached to Carbon Nanotube(8, 0) as Anodes of Metal-ion Batteries: a DFT Study

Performance of carbon nanotube(CNT) and their attached metal oxides(manganese oxide(MnO) and cadmium dioxide(CdO2)) structures as anode electrodes in lithium-ion battery(LIB) and potassium-ion battery(KIB) are investigated. The Gibbs free energy of adsorption of Li and K atoms/ions on surfaces of CNT(8, 0), CNT(8, 0)-MnO and CNT(8, 0)-CdO2 are calculated. The cell voltages(Vcell) of Li and K atoms/ions adsorption on studied surfaces are examined. The Vcell of LIBs with metal-oxides attached to CNT(8, 0) as anode electrodes are higher than those KIBs. The adsorbed metal oxides(MnO and CdO2) on CNT(8, 0) increased the charges, electronic conductivity and Vcell of LIB and KIB, efficiently. The CNT(8, 0)-CdO2 as anode electrodes in LIB and KIB is proposed.     

Aluminum Lon Removal from Monoaluminum Ovotransferrin by Pyrophosphate

The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site.     

Intrinsic Kinetics of Dimethyl Ether Synthesis from Syngas

The intrinsic kinetics of dimethyl ether (DME) synthesis from syngas over a methanol synthesis catalyst mixed with methanol dehydration catalyst has been investigated in a tubular integral reactor at 3-7MPa and 220-260℃. The three reactions including methanol synthesis from CO and H2, CO2 and H2, and methanol dehydration were chosen as the independent reactions. The L-H kinetic model was presented for dimethyl ether synthesis and the parameters of the model were obtained by using simplex method combined with genetic algorithm. The model is reliable according to statistical analysis and residual error analysis. The synergy effect of the reactions over the bifunctional catalyst was compared with the effect for methanol synthesis catalyst under the same conditions based on the model. The effects of syngas containing N2 on the reactions were also simulated.     

High rate and cycling stable Li metal anodes enabled with aluminum-zinc oxides modified copper foam

Metallic Li is a promising anode material for high energy density batteries but it suffers from poor stability and formation of unsafe dendrites. Previous studies demonstrated that 3 D metal foams are able to improve the stability of Li metal but the properties of these foams are inherently limited. Here we report a facile surface modification approach via magnetron sputtering of mixed oxides that effectively modulate the properties of Cu foams for supporting Li metal with remarkable stability. We discovered that hybrid Li anodes with Li metal thermally infused to aluminum-zinc oxides(AZO) coated Cu foams have significantly improved stability and reactivity compared with pristine Li foils and Li infused to unmodified Cu foams. Full cells assembled with a Li Fe PO4 cathode and a hybrid anode maintained low and stable charge-transfer resistance(50) during 500 cycles in carbonate electrolytes, and exhibited superior rate capability(～100 m Ah g-1 at 20 C) along with better electrochemical reversibility and surface stability. The AZO modified Cu foams had superior mechanical strength and afforded the hybrid anodes with minimized volume change without the formation of dendrites during battery cycling. The rational construction of surface architecture to precisely control Li plating and stripping may have great implications for the practical applications of Li metal batteries.     

Self-transforming stainless-steel into the next generation anode material for lithium ion batteries

Here,an extremely cost-effective and simple method is proposed in order to morphologically selftransform stain less steel from a completely inactive material to a fully operati onal,nanowire-structured,3D anode material for lithium ion batteries.The reagentless process of a single heating step of the plain stainless steel in a partially reduci ng atmosphere,converts the stain less steel into an active anode via metal-selective oxidation,creating vast spinel-structured nanowires directly from the electrochemically in active surface.The simple process allows the complete utilizati on of the 3D mesh structure as the electrochemically-active spinel nanowires greatly enhance the active surface area.The novel material and architecture exhibits high capacities(-1000 mAh/g after-400 cycles),long cycle life(>1100 cycles)and fast rate performance(>2C).Simple modulation of the substrate can result in very high areal and volumetric capacities.Thus,areal capacities greater than 10 mAh/cm² and volumetric capacities greater than 1400 mAh/cm³ can be achieved.Using the proposed method,the potential reduction in cost from the use of battery-grade graphite is at least an order of magnitude,with considerable better results achieved in terms of capacity and intrinsic structural benefits of the substrate,which include direct contact of the active material with the current collector,lack of delamination and binder-free performance.This work provides a new paradigm and a key step in the long route to replace the commercial graphite anode as the next-geneation anode material.     

SnS2/graphene nanocomposite: A high rate anode material for lithium ion battery

In this work,via a facile solvothermal route,we synthesized an anode material for lithium ion batteries(LIBs)—SnS_2 nanoparticle/graphene(SnS_2 NP/GNs) nanocomposite.The nanocomposite consists of SnS_2nanoparticles with an average diameter of 4 nm and graphene nanosheets without restacking.The SnS_2 nanoparticles are firmly anchored on the graphene nanosheets.As an anode material for LIBs,the nanocomposite exhibits good Li storage performance especially high rate performance.At the high current rate of 5,10,and 20 A/g,the nanocomposite delivered high capacities of 525,443,and 378 mAh/g,respectively.The good conductivity of the graphene nanosheets and the small particle size of SnS_2contribute to the electrochemical performance of SnS_2 NP/GNs.     

纳米氧化钴－氧化钌复合型超级电容器的研究

A novel type of composite electrode based on sheet like cobalt oxide particles has been used in supercapacitors. Cobalt oxide cathodically deposited from Co（NO3）2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F·g^-1 in 6 mol·L^-1 KOH. A sol-gel process for the preparation of ultrafine RuO2 particles was developed to design electrodes with large surface area. The composite electrodes were developed by the deposition of RuO： on the surface of carbon nanotubes. A specific capacitance of 785 F·g^-1 can be achieved with the 20% carbon nanotubes loaded. To characterize the metal oxide nanocomposite electrode, a cyclic voltammetry and AC impedance test are executed. This study also reports a hybrid capacitor, which consists of cobalt oxide composite as a cathode and ruthenium oxide composite as an anode. The electrochemical performance of the hybrid capacitor is characterized by a dc charge/discharge test and cyclic voltammograms. The hybrid capacitor shows capacitor behavior with an extended operating voltage of 1.4 V. The maximum energy density and specific power density of the cell reach the value of 23.7 and 8.1 kW·g^-1 respectively. The hybrid capacitor exhibits high-energy density and stable power characteristics.     

Hybrid Battery-Capacitor System based on Li4Ti5O12Anode and PTPAn Cathode北大核心CSCD

Owing to its high safe, high rate and long life characteristics, lithium titanate (Li4Ti5O12) anode material has attracted extensive attention in recent years, and many efforts are being made to develop the Li4Ti5O12based high performance hybrid supercapacitors and Li-ion batteries. Herein, we prepared the organic cathode material polytriphenylamine (PTPAn) through chemical oxidation and polymerization of triphenylamine (TPAn), and investigated its charge storage mechanism and electrode kinetics with the typical electrochemical methods in an organic electrolyte. It was demonstrated that the PTPAn exhibited the reversible capacity of 85 mA·g-1. The charge storage depended on the reversible adsorption/desorption of anion, which is not controlled by the diffusion process, and thus, can be considered as the pseudocapacitive behavior. Then, the PTPAn cathode was coupled with the Li4Ti5O12anode to form a hybrid capacitor/battery system with high power and improved energy density. Finally, the inherent drawback and the challenge for practical application of such an organic cathode are briefly discussed. © Journal of Electrochemistry 2018.     

Dehydrogenation activities of highly dispersed transition metal oxides on NaY zeolite

Highly dispersed α-Fe_2O_3/NaY,NiO/NaY,and CuO/NaY catalyst systems were pre-pared by impregnation method.Dispersion thresholds of the transition metal oxides on NaY" zeolitewere determined by XRD phase analysis.The dispersion capacities of the transition metal oxides on NaYzeolite are much lower than that estimated on the basis of a closed packed monolayer in the micropores.The catalytic activity and selectivity of the highly dispersed oxide catalyst systems for ethylben-zene and cyclohexane dehydrogenation reactions were reported.