Modulation of Electronic States in Bimetallic-doped Nitrogen-Carbon Based Nanoparticles for Enhanced Oxygen Reduction Kinetics

Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.

Theoretical insights into oxygen reduction reaction on Au-based single-atom alloy cluster catalysts

Developing highly active alloy catalysts that surpass the performance of platinum group metals in the oxygen reduction reaction(ORR)is critical in electrocatalysis.Gold-based single-atom alloy(AuSAA)clusters are gaining recognition as promising alternatives due to their potential for high activity.However,enhancing its activity of AuSAA clusters remains challenging due to limited insights into its actual active site in alkaline environments.Herein,we studied a variety of Au_(54)M_(1) SAA cluster catalysts and revealed the operando formed MO_(x)(OH)_(y) complex acts as the crucial active site for catalyzing the ORR under the basic solution condition.The observed volcano plot indicates that Au_(54)Co_(1),Au_(54)M_(1),and Au_(54)Ru_(1) clusters can be the optimal Au_(54)M_(1) SAA cluster catalysts for the ORR.Our findings offer new insights into the actual active sites of AuSAA cluster catalysts,which will inform rational catalyst design in experimental settings.

工业题材创作视角开拓的成功尝试——长篇电视剧《大工匠》审美意义初探

建国初期，随着我国工业建设的大规模展开，工业和工人逐渐成为社会生活的焦点，草明、杜鹏程、艾芜、周立波、雷加，以及一批工人作家胡万春、唐克新、费礼文等，纷纷拿起笔进入了工业题材这个陌生的文学领域。尽管有人评价当时的工业文学是“工地文学”、“车间文学”，但必须看到，从《原动力》到《铁水奔流》和《百炼成钢》，工人的形象和工业建设的内容开始大量出现在文学作品中。

Solid-state reduction kinetics and mechanism of pre-oxidized vanadium-titanium magnetite concentrate

The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows： pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →（FenTi1-n）Ti2O5. M3O5-type（M can be Fe, Ti, Mg, Mn, etc） solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.

Non-isothermal reduction kinetics of Fe_2O_3-NiO composites for formation of Fe-Ni alloy using carbon monoxide

The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.

Kinetics of extracting magnesium from mixture of calcined magnesite and calcined dolomite by vacuum aluminothermic reduction

The vacuum aluminothermic reduction of the mixture of calcined magnesite and calcined dolomite was studied. An isothermal reduction method satisfying the vacuum aluminothermic reduction was proposed. The experiments were carried out at 4 Pa. The results indicate that the reduction rate is increased with increasing temperature, content of aluminum and pellet forming pressure. The XRD patterns of pellets at different reduction stages confirm that the reduction process can be roughly classified into three stages：the formation of MgAl2O4, and Ca12Al14O33 phases;the phase transformation from MgAl2O4 and C12A7 to CaAl2O4;the formation of CaAl4O7 phase. The experimental data were divided into three parts according to the kinetic models. The apparent activation energies of the three parts were determined to be 98.2, 133.0 and 223.3 kJ/mol, respectively.

Application of the generalized quasi-complementary energy principle to the fluid-solid coupling problem

The fluid-solid coupling theory, an interdisciplinary science between hydrodynamics and solid mechanics, is an important tool for response analysis and direct design of structures in naval architecture and ocean engineering. By applying the corresponding relations between generalized forces and generalized displacements, convolutions were performed between the basic equations of elasto-dynamics in the primary space and corresponding virtual quantities. The results were integrated and then added algebraically. In light of the fact that body forces and surface forces are both follower forces, the generalized quasi-complementary energy principle with two kinds of variables for an initial value problem is established in non-conservative systems. Using the generalized quasi-complementary energy principle to deal with the fluid-solid coupling problem and to analyze the dynamic response of structures, a method for using two kinds of variables simultaneously for calculation of force and displacement was derived.

AIRCRAFT FLIGHT SAFETY ANALYSIS IN LOW ALTITUDE AIRSPACE

The low altitude airspace will be open in China, general aviation flights are tremendously increased. Whether aircrafts can fly safely and how to determine the requirements of safety flight are the problems needed to be confirmed. Under this circumstances, based on the international Civil Aviation Organization（ICAO） criteria and the standards made by CAAC, this paper adopts the ＂See and Avoid＂ principle. Under the binding conditions of flight rules, visibility requirements, responding time, the aircraft speed, circle banking angle or the climbing angle, based on its study on aircraft dynamics principles, this paper establishes a mathematical collision avoidance model for head-to-head traffic and crossing converging traffic at the same level. And the safety separation requirements of the aircrafts in low altitude flight are equantitatively analyzed. Finally, the Matlab software is used to analyze the above method. The result shows that the safe traffic avoidance of the converging traffic at the same level meets certain flight conditions, while intersecting the traffic at the same level can safely avoid the collision.

Simulation study on non-linear effects of initial melt temperatures on microstructures during solidification process of liquid Mg_7Zn_3 alloy

The non-linear effects of different initial melt temperatures on the microstructure evolution during the solidification process of liquid Mg7Zn3 alloys were investigated by molecular dynamics simulation, The microstructure transformation mechanisms were analyzed by several methods. The system was found to be solidified into amorphous structures from different initial melt temperatures at the same cooling rate of 1×10^12 K/s, and the 1551 bond-type and the icosahedron basic cluster （12 0 12 0 ） played a key role in the microstructure transition. Different initial melt temperatures had significant effects on the final microstructures. These effects only can be clearly observed below the glass transition temperature Tg; and these effects are non-linearly related to the initial melt temperatures, and fluctuated in a certain range. However, the changes of the average atomic energy of the systems are still linearly related with the initial melt temperatures, namely, the higher the initial melt temperature is, the more stable the amorphous structure is and the stronger the glass forming ability will be.

一起活在好声音里

最近，鹿晗的全新数字专辑《Reloaded＋》全面上线，专辑收录了歌曲《封印》、《原动力》、《致爱》。主打曲《封印》是一首“即兴”却让人非常满意的作品。整首歌曲连beat也充满了悲剧感。歌词讲述了两个恋人被封印在了完全不同的次元，变成储存于赛博世界中的电子脉；中，只能通过启动机器，才能与对方的波频重组成的二维画面得以一见。在叙述上，这是一段无法阶跃的“跨维度”遗憾恋情。歌曲《原动力》则是一首以具备流行要素的旋律为骨架、时髦的节奏和电子音效强调制作质量和细节的歌曲，更通过充满太空感的歌词支撑起更为宏大的世界观中。歌曲《致爱》则是一酋缓缓动听的治愈情歌，温暖人心。凭借这张全新数字专辑《Reloaded＋》，歌手鹿晗华丽返场。

Analysis of Dynamics and Driving Factors of Wetland Landscape in Zoige,Eastern Qinghai-Tibetan Plateau

Zoige Wetland is one of the largest plateau wetlands in the world. This paper provides a dynamic analysis of spatial and temporal patterns of the wetland in Zoige, Eastern Qinghai-Tibetan Plateau, supported by ERDAS8.7 and ArcGIS9.0. It is the first comparative analysis of a system of rapidly changing wetland with landscape patterns in Zoige, using 3 classified landsat Thematic Mapper images of 1977, 1994 and 2001. The classified images were used to generate wetland distributing maps, and shape index （S）, diversity index （H）, dominance index （D）, evenness index （E）, fragmentation index （F） and fractal dimension （Fd） were calculated and analyzed spatiotemporally across pure grazing area in Zoige for each landscape type and in different periods （before 1977, during 1977-1994 and 1994-2001）, as well as the driving forces of natural and anthropogenic. The study shows that for a comprehensive understanding of the shapes and trajectories of the shrinking and desertificated land expansion of the wetland, a spatiotemporal landscape metrics analysis in different periods is an improvement than only with landscape changing rates. This type of analysis can also be used to infer underlying social, economic, and political processes that drive the observed wetland forms. The results indicate that wetland patterns can be changed over relatively short periods of time. The total area of lake reduced by 164.86 km^2, grassland extended by 141.74 km^2, semi-marsh extended by 105.94 km^2, marsh reduced by 86.00 km^2 the number of landscape patches reduced by 56, and their average area decreased by 2.68 km^2, the successions within lake, marsh, semi-marsh and grassland were found obviously. S decreased stepwise： D and F increased but H decreased： The changing rate after 1994 was 2.3 to 2.9 times greater than that before. The change of the wetland landscape patterns resulted in the interaction between socio-ceenomic and natural forces of positive and negative aspects; and natural factors affected as assistant aspect. Some important human activities in this period led to the change of the landscape patterns in this region directly. Some measurements made by government and NGO delayed the converting process partly.

Study on Kinetics of Iron Oxide Reduction by Hydrogen

Kinetics parameters of iron oxide reduction by hydrogen were evaluated by the isothermal method in a differential micro-packed bed. Influence of external diffusion, internal diffusion and heat transfer on the intrinsic reaction rate was investigated and the conditions free of internal and external diffusion resistance have been determined. In the experiments, in order to correctly evaluate the intrinsic kinetics parameters for reducing Fe203 to Fe3O4, the reaction temperatures were set between 440 ℃ and 490 ℃. However, in order to distinguish the reduction of Fe304 to FeO from that of FeO to Fe, the reaction temperature in the experiment was set to be greater than 570 ℃. Intrinsic kinetics of iron oxide reduction by hydrogen was established and the newly established kinetic models were validated by the experimental data.

Kinetics of Reductive Leaching of Low-grade Pyrolusite with Molasses Alcohol Wastewater in H_2SO_4

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.

Recent progress in electronic modulation of electrocatalysts for high-efficient polysulfide conversion of Li-S batteries

With the merits of high energy density,environmental friendliness,and cost effectiveness,lithium-sulfur(Li-S)batteries are considered as one of the most promising next-generation electrochemical storage systems.However,the notorious polysulfide shuttle effect,which results in low active material utilization and serious capacity fading,severely impedes the practical application of Li-S batteries.Utilizing various electrocatalysts to improve the polysulfide redox kinetics has recently emerged as a promising strategy to address the shuttle effect.Specially,the electronic structure of the electrocatalysts plays a decisive role in determining the catalytic activity to facilitate the polysulfide conversion.Therefore,reasonably modulating the electronic structure of electrocatalysts is of paramount significance for improving the electrochemical performance of Li-S batteries.Herein,a comprehensive overview of the fascinating strategies to tailor the electronic structure of electrocatalysts for Li-S batteries is presented,including but not limited to vacancy engineering,heteroatom doping,single atom doping,band regulation,alloying,and heterostructure engineering.The future perspectives and challenges are also proposed for designing high-efficient electrocatalysts to construct high-energy-density and long-lifetime Li-S batteries.

Atomistic simulation of thermal effects and defect structures during nanomachining of copper

Molecular dynamics （MD） simulations of monocrystalline copper （100） surface during nanomachining process were performed based on a new 3D simulation model. The material removal mechanism and system temperature distribution were discussed. The simulation results indicate that the system temperature distribution presents a roughly concentric shape, a steep temperature gradient is observed in diamond cutting tool, and the highest temperature is located in chip. Centrosymmetry parameter method was used to monitor defect structures. Dislocations and vacancies are the two principal types of defect structures. Residual defect structures impose a major change on the workpiece physical properties and machined surface quality. The defect structures in workpiece are temperature dependent. As the temperature increases, the dislocations are mainly mediated from the workpiece surface, while the others are dissociated into point defects. The relatively high cutting speed used in nanomachining results in less defect structures, beneficial to obtain highly machined surface quality.

Reductive kinetics of Panzhihua ilmenite with hydrogen

The hydrogen reduction of Panzhihua ilmenite concentrate in the temperature range of 900?1050 °C was systematicallyinvestigated by thermogravimetric analysis (TG), X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. It wasshown that the products of the Panzhihua ilmenite reduced at 900 °C were metallic iron and rutile. Above 1000 °C, ferrouspseudobrookite solid solution was generated. During the reduction process, element Mg gradually concentrated to form Mg-rich zonewhich can influence the metallization process. The reduction reaction proceeded topochemically and its related reduction kineticswere also discussed. The kinetics of the reduction indicated that the rate-controlling step was the diffusion process. The apparentactivation energy of the hydrogen reduction of Panzhihua ilmenite was calculated to be 117.56 kJ/mol, which was larger than that ofsynthetic ilmenite under the same reduction condition.

Experimental and Modeling Study on de-NO_x Characteristics of Selective Non-catalytic Reduction in O_2/CO_2 Atmosphere

An experimental study of thermal de-NOx using NH3 as reductant in 02/C02 atmosphere with the effect of S02 and different additives was performed in a drop tube furnace. Results show that the optimum temperature win- dow is 841-1184 ℃, and the optimum reaction temperature is about 900 ℃ with a de-NOx efficiency of 95.4%. A certain amount of S02 has an inhibiting effect on NO reduction. The effect of additives, including Na2C03, C2H5OH and FeCI3, on NO reduction by NH3 is also explored. The addition of Na2CO3 and FeCI3 is useful to widen the tem- perature window and shift the reaction to lower temperature for the efficiency is increased from 30.5% to 74.0% and 67.4% respectively at 800 ℃. Qualitatively, the modeling results using a detailed kinetic modeling mecha- nism represent well most of the process features. The effect of Na2CO3, C2H5OH and FeCI3 addition can be reproduced well by the Na2C03, C2H5OH and Fe（CO）5 sub-mechanism respectively. The reaction mechanism analysis shows that the effects of these additives on NO reduction are achieved mainly by promoting the produc- tion of OH radicals at lower temperature.

Mechanism of Calcium Carbonate Scale Deposition under Subcooled Flow Boiling Conditions

Fouling of heat transfer surfaces during subcooled flow boiling is a frequent engineering problem in process industries. It has been generally observed that the deposits in such industrial systems consist mainly of calcium carbonate （CaCO3）, which has inverse solubility characteristics. This investigation focused on the mechanism to control deposition and the morphology of crystalline deposits. A series of experiments were carried out at different surface and bulk temperatures, fluid velocities and salt ion concentrations. It is shown that the deposition rate is controlled by different mechanism in the range of experimental parameters, depending on salt ion concentration. At higher ion concentration, the fouling rate increases linearly with surface temperature and the effect of flow velocity on deposition rate is quite strong, suggesting that mass diffusion controls the fouling process. On the contrary, at lower ion concentration, the fouling rate increases exponentially with surface temperature and is independent of the velocity, illustrating that surface reaction controls the fouling process. By analysis of the morphology of scale, two types of crystal （calcite and aragonite） are formed. The lower the temperature and ion concentration, the longer the induction period and the higher the percentage of calcite nreciDitated.

Isothermal reduction kinetics of zinc calcine under carbon monoxide

The reduction kinetics of zinc calcine under a CO atmosphere was evaluated by isothermal reductive roasting in a temperature range of 600-800℃.The extent of reaction of zinc calcine was measured using thermogravimetry(TG),and the decomposition mechanism of zinc ferrite in zinc calcine was analyzed based on variations in the soluble zinc and ferrous contents.The results indicate that the reaction was controlled by the nucleation of the products,with an apparent activation energy of 65.28 k J/mol.The partial pressure of CO affected the reaction rate more strongly than the CO intensity(defined as PCO/(PCO+PCO2)).The generation rate of zinc oxide was higher than that of ferrous oxide;therefore,the nucleation of ferrous oxide is the rate-determining step of the reaction.

Kinetics of High Cell Density Fed-batch Culture of Recombinant Escherichia coli Producing Human-like Collagen

The kinetics of batch and fed-batch cultures of recombinant Escherichia coli producing human-like collagen was investigated. In the batch culture, a kinetic model of a simple growth-association system was concluded without consideration of cell endogeneous metabolism. The cell lag time, the maximum specific growth rate and Yx/s were determined as 1.75h, 0.65h^-1 and 0.51g·g^-1, respectively. In the fed-batch culture, different specific growth rates were set at （0.15, 0.2, 0.25h^-1） by the method of pseudo-exponential feeding, and the expressions for the specific rate of substrate consumption, the growth kinetics and the product formation kinetics of each phase were obtained. The result shows that the concentrations of cell and product can reach 77.5g·L^-1 and 10.2g·L^-1 respectively. The modal predictions are in good agreement with the experimental data.