Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.

An efficient Hauser-base electrolyte for rechargeable magnesium batteries

Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.

A Photonuclear Reaction Model Based on IQMD in Intermediate-Energy Region

A photonuclear reaction transport model based on an isospin-dependent quantum molecular dynamics model （IQMD） is presented in the intermediate energy region, which is named as GiQMD in this study. Methodology to simulate the course of the photonuclear reaction within the IQMD frame is described to study the photo- absorption cross section and π meson production, and the simulation results are compared with some available experimental data as well as the Giessen Boltzmann-Uehling-Uhlenbeck model.

Wettability and interfacial reactions of PdNi-based brazing fillers on C-C composite

The wettability and interfacial reactions of four kinds of PdNi-based brazing fillers on C-C composite were studied with the sessile drop method.The results showed that the wettability of these brazing fillers was improved with the increase of Cr content. Cr distributed at the interface of brazing filler/C-C composite and the formation of Cr23C6 phase was speculated.In the interface between Ni-33Cr-24Pd-4Si brazing filler and C-C composite,element Cr reacted with C-C to form Cr-C reaction layer.Pd together with Si participated in the interfacial reactions and formed Pd2Si and Pd3Si phases.Furthermore,in this reaction zone,the residual brazing alloy became Ni-rich and Pd-depleted.

Proline-based Amino Pyridine Dipeptides as Efficient Organocatalysts for Direct Aldol Reaction

A series of proline-based amino pyridine dipeptide organocatalysts was synthesized and applied in direct asymmetric intermolecular aldol reaction. These catalysts showed good solubility in organic solvents, good yields （73%--97%） and enantioselectivitives（74%--94%）. Among them, dipeptide organocatalyst（2） was found to be the most efficient one for the asymmetric aldol reaction between cyclohexanone and 4-nitrobeznaldehyde. After optimizing the catalytic reaction conditions, we found that the catalyst showed high yield（97%）, enantioselectivity（e.e., up to 92%） and anti-diastcreoselectivity（up to 95：5） at mild room temperature without any additives.

Henry Reaction between Benzaldehyde and Nitromethane over Solid Base Catalysts: A Green Protocol

The development of environmentally benign solid base catalysts instead of the soluble bases for C-C bond formation in organic reactions especially Henry reactions with nitroalkanes compounds is of intense research activity in the bulk and fine chemical chemistry in order to achieve the selectivity of the desired product and the reduction of the salts formed due to soluble bases neutralization. While using of LDHs catalysts in the synthesis of nitro alcohols is of great interest because LDHs (double layered hydroxides) is of unique properties and an excellent catalytic property. The nitroalcohols are obtained in a very good yield while using catalyst either by conventional at 90&#176;C in liquid phase, microwave or sonoenergy without solvent methods, and the results yields are compared. A series of different nitro alcohols from (a - o) were prepared, the catalytic test reaction were carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. A series of LDHs catalysts were prepared also and studying of the catalytic effect on the reactions was carried out. Properties of the compounds prepared were characterized by IR, MNR, and GC-MS.

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS Ⅲ TRANSMETALLATION REACTION OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS WITH METALLIC TIN

The transmetallation reaction of 4 Schiff base type arylmercury compounds with metallic tin has been carried out in refluxing xylene.It was found that the reaction proceeds in the same manner as that of chloro[2-(phenylazo)phenyl]mercury(Ⅱ) to give dichlorobisaryltin(Ⅳ).The ~1H NMR spectra of the products provide evidence for the presence of N→Sn intramolecular coordination.The formation of dichlorobisaryltin(Ⅳ)as a unique product probably arises from the N→Sn intramolecular coordination which results in the increasing of the stability of the molecule.

DFT Study on Reaction Mechanism of DNA Base Pair with Hydroxyl Radical

In order to elucidate the indirect effect by radiation on DNA base pairs, we investigate the mechanism for the attacking reaction of a hydroxyl radical (·OH-radical) to the G-C and A-T base pairs, by the density functional theory (DFT) calculations. The effect of solvation on the mechanism is also revealed by performing the same DFT calculations under the continuum solvation approximation. We find the stable structures for the dehydrogenated G-C and A-T base pairs, in which the hydrogen atom of NH2 group of G or A base is abstracted by the ·OH-radical. The solvation around the base pairs stabilizes the dehydrogenated structures significantly, indicating the acceleration of the attacking reaction by ·OH-radical to the base pairs in water. Therefore, we conclude that the hydrogen atom of the NH2 group of G or A base in the G-C and A-T base pairs is the most preferably abstracted by the ·OH-radical in living cells.

Poly (N-Isopropyl Acrylamide-<i>Co</i>-Vanillin Acrylate) Dual Responsive Functional Copolymers for Grafting Biomolecules by Schiff’s Base Click Reaction

This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.

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.

Symmetrical Palladium (II) N,N,O,O-Schiff Base Complex: Efficient Catalyst for Heck and Suzuki Reactions

Palladium is arguably the most versatile and most widely applied catalytic metal in the field of fine chemicals due to its high selectivity and activity. Palladium catalyst offers an abundance of possibilities of carbon-carbon bond formation in organic synthesis. In this research, three different Schiff base ligands have been prepared by condensation reaction between appropriate aldehyde or ketone with amine namely 2,2-dimethyl-1,3-propanediamine in the molar ratio of 2:1. The corresponding palladium (II) Schiff base complexes were prepared through the reaction between the Schiff base ligand with palladium (II) acetate in a molar ratio 1:1. FTIR, 1H-NMR and 13C-NMR spectroscopic data revealed that the ligands are N,N,O,O-tetradentate coordinated to the Pd atom through both the azomethine N atoms and phenolic O atoms. From X-ray Crystallographic analysis, it showed that the complex exists as square planar geometry. The synthesized palladium (II) Schiff base complexes were then subjected in catalytic Heck and Suzuki reaction of iodobenzene.

Solving Multi-Area Environmental/Economic Dispatch by Pareto-Based Chemical-Reaction Optimization Algorithm

In this study, we present a Pareto-based chemicalreaction optimization(PCRO) algorithm for solving the multiarea environmental/economic dispatch optimization problems.Two objectives are minimized simultaneously, i.e., total fuel cost and emission. In the proposed algorithm, each solution is represented by a chemical molecule. A novel encoding mechanism for solving the multi-area environmental/economic dispatch optimization problems is designed to dynamically enhance the performance of the proposed algorithm. Then, an ensemble of effective neighborhood approaches is developed, and a selfadaptive neighborhood structure selection mechanism is also embedded in PCRO to increase the search ability while maintaining population diversity. In addition, a grid-based crowding distance strategy is introduced, which can obviously enable the algorithm to easily converge near the Pareto front. Furthermore,a kinetic-energy-based search procedure is developed to enhance the global search ability. Finally, the proposed algorithm is tested on sets of the instances that are generated based on realistic production. Through the analysis of experimental results, the highly effective performance of the proposed PCRO algorithm is favorably compared with several algorithms, with regards to both solution quality and diversity.

Mannich-Type Reactions of Aldimines and Hetero Diels-Alder Reactions of Aldehydes Catalyzed by Anion-Type Lewis Bases Derived from a Single Molecule

Mannich-type reactions of aldimines with silyl enolates and hetero Diels-Alder reactions of aldehydes with Danishef-sky’s diene in the presence of anion catalysts derived from proline were performed to afford the corresponding products in high yields.

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

有基于碳的稳固的酸催化剂的同时的 transesterification 和酯化作用的动力学被学习。二稳固的酸催化剂被使碳化的蔬菜油沥青和石油沥青的 sulfonation 准备。这些催化剂根据元素的分析，酸味地点集中， Brunauer-Emmett-Teller (赌注) 表面区域和毛孔尺寸被描绘。有二催化剂的运动参数被决定，并且反应系统能被描述为假同类的催化反应。所有前面、反向的反应跟随第二顺序动力学。从运动方程的计算集中价值在对试验性的价值的好同意。

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

钒基催化剂催化苯羟基化制苯酚反应机理

苯羟基化制苯酚是C—H键向C—O键转化及富有挑战性的课题之一。该文论述了钒基催化剂催化苯羟基化制苯酚反应机理的研究进展。以钒活性中心为主线,着重从自由基、非自由基和双催化活性机理进行了详细介绍,同时分析了双催化活性中心催化剂高效催化的本质和重要性。提出此类催化体系及催化机理能够解决苯环上C—H键难活化和苯酚的深度氧化等问题,是经济与安全并存的苯酚合成方法,依托已有的催化反应机理,开发更稳定且高性能的催化剂,以促进烃类有机化合物资源利用的原始创新。

钴基助催化剂在光催化产氢中的应用研究进展

通过光催化分解水产生的氢气可以用于驱动燃料电池或其他能源转换设备,这有助于减少对化石燃料的依赖,减少温室气体排放。但是实验发现,很多光催化剂存在可见光利用率低和光生电子-空穴易复合的问题。为了抑制光生电子-空穴的复合,提高光催化剂产氢效率,研究者们尝试了多种催化剂改性方式,加入助催化剂是其中最有效的方式之一。传统的贵金属助催化剂虽然有良好的效果,但是价格高,不利于大量生产应用。钴(Co)是一种廉价易得的过渡金属,作为助催化剂其效果有时可与铂(Pt)等贵金属相当。本文总结了不同Co基助催化剂,如Co的硫化物、氧化物、氢氧化物以及磷化物等助催化剂在光解水产氢方面的研究进展,希望对该领域的研究提供一些有价值的参考。

豌豆蛋白酶解-美拉德反应产物的制备及其提升低钠植物肉风味及储藏稳定性的研究

该文探究了豌豆蛋白酶解-美拉德反应产物(Maillard Reaction Products Derived From Pea Protein Enzymatic Hydrolysate,PPIHM)对低钠植物肉品质的影响。以豌豆蛋白为原料,通过蛋白酶水解结合谷氨酰胺转氨酶(Glutamine Transaminase,TG酶)交联,添加质量分数为3.0%谷胱甘肽和1.0%还原糖(木糖:核糖=1:3)进行美拉德反应制备PPIHM,并证明PPIHM的良好烤肉香气,鲜味及抗氧化能力。进一步添加不同质量分数(1%,3%,5%)的PPIHM于低钠植物肉中,系统研究发现添加PPIHM在保持植物肉自身刚性和稳定性的前提下,能显著提升植物肉的肉香感知强度,延缓植物肉中油脂和蛋白的氧化。其中,感官品评人员对3%PPIHM植物肉组的喜好度和接受度最高,5%PPIHM植物肉组抗氧化和贮藏稳定性效果最好,在第12天时,POV值仅为0.0097 g/100 g。研究结果表明添加PPIHM是改善低钠植物肉风味,提高其储藏性能的一种有效途径。该研究为深入探究PPIHM作为天然反应型风味补偿剂在低钠植物肉中的应用提供了理论基础和方法指导。

苯酐合成的反应网络及催化反应机制研究现状与展望

邻苯二甲酸酐(简称苯酐)是合成增塑剂、涂料等高价值精细化学品的重要原料,在工业生产中以邻法苯酐合成工艺为主,萘法合成工艺为辅,其中钒系催化剂因具有高苯酐选择性而备受关注。为了提高苯酐收率、降低床层温度,催化剂在工业应用中已逐步进入多床层、高进料负荷的发展阶段。本文以邻法苯酐为主要研究对象,简要讨论了催化剂的发展历程,重点关注合成工艺路线及催化机制研究进展。工业催化剂易因生成积炭、活性组分流失、TiO_(2)晶相转变等导致其失活,因此也重点探讨了催化剂的失活机制。最后对苯酐工艺的发展提出了展望,为解决当前生产工艺存在的高耗能、高碳排放、催化剂寿命短等挑战,未来苯酐合成应致力于开发新型高效催化剂和绿色反应新工艺,以推动该技术的可持续发展。