Continuous,efficient and safe synthesis of 1-oxa-2-azaspiro[2.5]octane in a microreaction system

1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.

Selective synthesis of nitrate from air using a plasma-driven gas-liquid relay reaction system

The direct oxidation of nitrogen is a potential pathway to achieving the zero-carbon-emission synthesis of nitric acid or nitrate, because it does not involve ammonia synthesis and additional ammonia oxidation processes. However, the slow kinetics of nitrogen oxidation and the difficult selective control of oxidation products hinder the development of this process. In this study, a plasma-driven gas-liquid relay reaction system was developed to overcome these limitations. A typical feature of this reaction system is that it can efficiently generate NO_x under plasma exposure;moreover, the specific anions in the absorption solution can be oxidized to strong oxidants capable of relay oxidation of low-valence nitrogen oxides. This feature allows for the deep oxidation of nitrogen, thus enabling the oxidation products of nitrogen to exist in high-valence states in the absorption solution. For experimental verification, we achieved the 100% selective synthesis of nitrate under plasma exposure, with air as the supply gas and a sodium sulfate solution as the absorption solution.

Research on development of in situ titanium matrix composites and in situ reaction thermodynamics of the reaction systems

The in situ synthesis method for titanium matrix composites （TMCs） has obvious technical and economical advantages over other traditional methods. Ultrafine reinforcement particles were formed in situ by chemical reaction between elements or between elements and compounds. Using the approach, contamination at the composite matrix/reinforcement particle interface did not occur, interface bonding was good, and the reinforcement particle was thermodynamically stable. The stage of development of the preparation process for in situ TMCs as well as the thermodynamic analysis of the possible in situ reaction systems was described.

Thermokinetic Behaviour Degenerated from Limit Cycle Oscillation of Isothermal B-Z Reaction System due to Temperature Controlling of Heat Compensation Type

The thermokinetic behavior of the B-Z reaction system was influenced by both the chemical reaction-heat conduction coupling and the temperature undulation due to temperature controlling of heat compensation type. Quantitative research indicated that this kind of temperature fluctuation will lead to limit cycle degeneration and the periodic or quasi-periodic response behavior of the focus near a supercritical Hopf bifurcation .

KINETIC AND APPLICATION: STUDIES ON THE REACTION SYSTEM OF OSMIUM(Ⅳ)-ARSENIC(Ⅲ)-CHLORATE

The experiments have proved that Os(Ⅳ) has very strong catalytic effect on the chlorate oxidation of As(Ⅲ) in perchloric acid media, and As(Ⅲ) exhibits a sensitive single-sweep oscillopolarographic wave at-0.75 V vs. SCE. The kinetics of this catalytic reaction has been investigated by the initial rate procedure. The mechanism has been proposed. A new and highly sensitive catalytic reaction-oscillopolarographic method for the determination of ultratrace amounts of osmium has been described, based on the Os(Ⅳ) catalytic effect on the reaction. The linear range of 5.0×10^(-11)-4.4×10^(-9) mol/L and 6.0×10^(-9)-1.3×10^(-7) mol/L Os was obtained using the fixed-time procedure and the initial rate procedure, respectively. Osmium in refined ore was analysed by this method.

Recent Advances in Visible-Light-Driven Photoelectrochemical Water Splitting: Catalyst Nanostructures and Reaction Systems

Photoelectrochemical(PEC) water splitting using solar energy has attracted great attention for generation of renewable hydrogen with less carbon footprint, while there are enormous challenges that still remain for improving solar energy water splitting efficiency, due to limited light harvesting, energy loss associated to fast recombination of photogenerated charge carriers, as well as electrode degradation. This overview focuses on the recent development about catalyst nanomaterials and nanostructures in different PEC water splitting systems. As photoanode, Au nanoparticle-decorated TiO_2 nanowire electrodes exhibited enhanced photoactivity in both the UV and the visible regions due to surface plasmon resonance of Au and showed the largest photocurrent generation of up to 710 nm. Pt/Cd S/CGSe electrodes were developed as photocathode. With the role of p–n heterojunction, the photoelectrode showed high stability and evolved hydrogen continuously for more than 10 days. Further, in the Z-scheme system(Bi_2S_3/TNA as photoanode and Pt/Si PVC as photocathode at the same time), a self-bias(open-circuit voltage Voc= 0.766 V) was formed between two photoelectrodes, which could facilitate photogenerated charge transfers and enhance the photoelectrochemical performance, and which might provide new hints for PEC water splitting. Meanwhile, the existing problems and prospective solutions have also been reviewed.

Application-oriented hydrolysis reaction system of solid-state hydrogen storage materials for high energy density target:A review

Hydrogen storage and delivery technology is still a bottleneck in the hydrogen industry chain.Among all kinds of hydrogen storage methods,light-weight solid-state hydrogen storage(LSHS)materials could become promising due to its intrinsic high hydrogen capacity.Hydrolysis reaction of LSHS materials occurs at moderate conditions,indicating the potential for portable applications.At present,most of review work focuses on the improvement of material performance,especially the catalysts design.This part is important,but the others,such as operation modes,are also vital to to make full use of material potential in the practical applications.Different operation modes of hydrolysis reaction have an impact on hydrogen capacity to various degrees.For example,hydrolysis in solution would decrease the hydrogen capacity of hydrogen generator to a low value due to the excessive water participating in the reaction.Therefore,application-oriented operation modes could become a key problem for hydrolysis reaction of LSHS materials.In this paper,the operation modes of hydrolysis reaction and their practical applications are mainly reviewed.The implements of each operation mode are discussed and compared in detail to determine the suitable one for practical applications with the requirement of high energy density.The current challenges and future directions are also discussed.

Inference of General Mass Action-Based State Equations for Oscillatory Biochemical Reaction Systems Using <i>k</i>-Step Genetic Programming

Systems biology requires the development of algorithms that use omics data to infer interaction networks among biomolecules working within an organism. One major type of evolutionary algorithm, genetic programming (GP), is useful for its high heuristic ability as a search method for obtaining suitable solutions expressed as tree structures. However, because GP determines the values of parameters such as coefficients by random values, it is difficult to apply in the inference of state equations that describe oscillatory biochemical reaction systems with high nonlinearity. Accordingly, in this study, we propose a new GP procedure called “k-step GP” intended for inferring the state equations of oscillatory biochemical reaction systems. The k-step GP procedure consists of two algorithms: 1) Parameter optimization using the modified Powell method—after genetic operations such as crossover and mutation, the values of parameters such as coefficients are optimized by applying the modified Powell method with secondary convergence. 2) GP using divided learning data—to improve the inference efficiency, imposes perturbations through the addition of learning data at various intervals and adaptations to these changes result in state equations with higher fitness. We are confident that k-step GP is an algorithm that is particularly well suited to inferring state equations for oscillatory biochemical reaction systems and contributes to solving inverse problems in systems biology.

The Dynamical Model of Chemical Oscillation in CaF_2-HCl-H_2O Solid-Liquid Reaction System

Based on the physical chemistry principle, this paper proposes that the surface adsorption catalytic mechanism of HF is the key to dissolving the oscillation of the CaF\-2\|HCl\|H\-2O solid\|liquid reaction system. Meanwhile the dynamical model of this system has been established in order to study its non\|linear dynamical genesis. Although this mathematics model is based on CSTR reaction apparatus, it is applicable to the foliate flow reaction apparatus, too.

Molecular-Based Simulation of Feedstock Properties for Complex Reaction System

复杂反应系统的动力学与由集中于深催化的裂开的模拟和结构的面向的 Lumping (两重棉包线) 处理的蒙特卡罗的联合方法在分子的水平上被学习，模型参数借助于一个两重棉包线单位的平淡的分析数据被优化。一个模型被建立与蒙特卡罗模拟转变象两重棉包线那样的复杂反应系统的化工物品到 1000-10000 伪分子，每个分子被 19 个属性表示。模型模拟的结果证明这些伪分子反映了化工物品的特征很好，他们的平均性质与植物数据给了一个好协议。

Kinetic Phase Transition in A_2+2B_2→2B_2A Reaction System with Particle Diffusion

一个格子气体模型为 A 被介绍 2+ 2B 2→ 有在二种尺寸的粒子散开的 2B 2 A 反应系统。在模型， B 2 在随机的暗淡充满的机制分裂， 2 在在端点的更暗淡的充满机制分裂。一扇反应窗户出现，系统从一个反应状态展出连续阶段转变到“一个 B + 空缺”盖住的状态与无穷地许多吸收状态。当粒子 B 的散开被考虑时，仅仅有二吸收状态。连续阶段转变的批评行为与散开(PCPD ) 从指导过滤(DP ) 把班改变到对接触过程，这被发现班。

Comparison of Measurements for Enhanced Diffusion Problem in Chemical Reaction Systems

The problem of molecular diffusion in the soup of chemical reactions attracts mounting interest across fields ranging from chemistry to biophysics to material science.Chemical reactions involve bond breakup and formation,whose time scale is typically on the orders of fs to ps,while molecular diffusion occurs at time scales ofμs to ms.The two processes are often considered orthogonal,given the vastly different scales.The serial results show that the enzyme's diffusion is enhanced in a substrate-dependent manner,which was further extended to small molecule reaction systems,challenging this classical paradigm.However,the results from different groups using different techniques do not quantitatively agree,and a general mechanism is yet to be understood.We summarize experimental studies on diffusion problems and seek to reconcile the interpretation with understanding the limits of measurement tools and the chemical nature of reaction systems.Understanding molecular diffusion in chemical reactions will provide fresh thoughts in designing chemical systems such as molecular machines that harvest work at the nanoscale in a controllable manner.

Exponential Time Differencing Method for a Reaction-Diffusion System with Free Boundary

For reaction-diffusion equations in irregular domains with moving boundaries,the numerical stability constraints from the reaction and diffusion terms often require very restricted time step sizes,while complex geometries may lead to difficulties in the accuracy when discretizing the high-order derivatives on grid points near the boundary.It is very challenging to design numerical methods that can efficiently and accurately handle both difficulties.Applying an implicit scheme may be able to remove the stability constraints on the time step,however,it usually requires solving a large global system of nonlinear equations for each time step,and the computational cost could be significant.Integration factor(IF)or exponential time differencing(ETD)methods are one of the popular methods for temporal partial differential equations(PDEs)among many other methods.In our paper,we couple ETD methods with an embedded boundary method to solve a system of reaction-diffusion equations with complex geometries.In particular,we rewrite all ETD schemes into a linear combination of specificФ-functions and apply one state-of-the-art algorithm to compute the matrix-vector multiplications,which offers significant computational advantages with adaptive Krylov subspaces.In addition,we extend this method by incorporating the level set method to solve the free boundary problem.The accuracy,stability,and efficiency of the developed method are demonstrated by numerical examples.

Comparison of the interface reaction behaviors of CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) solid-state systems based on the diffusion couple method

The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Combination of a reaction cell and an ultra-high vacuum system for the in situ preparation and characterization of a model catalyst

An in-depth understanding of the structure-activity relationship between the surface structure,chemical composition,adsorption and desorption of molecules,and their reaction activity and selectivity is necessary for the rational design of high-performance catalysts.Herein,we present a method for studying catalytic mechanisms using a combination of in situ reaction cells and surface science techniques.The proposed system consists of four parts:preparation chamber,temperatureprogrammed desorption(TPD)chamber,quick load-lock chamber,and in situ reaction cell.The preparation chamber was equipped with setups based on the surface science techniques used for standard sample preparation and characterization,including an Ar+sputter gun,Auger electron spectrometer,and a low-energy electron diffractometer.After a well-defined model catalyst was prepared,the sample was transferred to a TPD chamber to investigate the adsorption and desorption of the probe molecule,or to the reaction cell,to measure the catalytic activity.A thermal desorption experiment for methanol on a clean Cu(111)surface was conducted to demonstrate the functionality of the preparation and TPD chambers.Moreover,the repeatability of the in situ reaction cell experiment was verified by CO_(2) hydrogenation on the Ni(110)surface.At a reaction pressure of 800 Torr at 673 K,turnover frequencies for the methanation reaction and reverse water-gas shift reaction were 0.15 and 7.55 Ni atom^(-1) s^(-1),respectively.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.