C-H bond activation of propane on Ga_(2)O_(2)^(2+) in Ga/H-ZSM-5 and its mechanistic implications

Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+) stabilized by framework Al pairs have been identified as the most active species in Ga/H-ZSM-5 for PDH in our recent work.Here we demonstrate a strong correlation between the PDH activity and a fraction of Ga_(2)O_(2)^(2+) species corresponding to the infrared GaH band of higher wavenumber(GaHHW)in reduced Ga/H-ZSM-5,instead of the overall Ga_(2)O_(2)^(2+) species,by employing five H-ZSM-5 supports sourced differently with comparable Si/Al ratio.This disparity in Ga_(2)O_(2)^(2+) species stems from their differing capacity in completing the catalytic cycle.Spectroscopic results suggest that PDH proceeds via a two-step mechanism:(1)C-H bond activation of propane on H-Ga_(2)O_(2)^(2+) species(rate determining step);(2)β-hydride elimination of adsorbed propyl group,which only occurs on active Ga_(2)O_(2)^(2+) species corresponding to GaHHW.

Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation

A straightforward protocol using readily available aromatic amines,N,N,N',N'-tetramethyl-p-phenylenediamine or N,N,N',N'-tetramethylbenzidine,as photocatalysts was developed for theefficient hydrodehalogenation of organic halides,such as 4'-bromoacetophenone,polyfluoroarenes,cholorobenzene,and 2,2',4,4'-tetrabromodiphenyl ether(a resistant and persistent organic pollu-tant).The strongly reducing singlet excited states of the amines enabled diffusion-controlled disso-ciative electron transfer to effectively cleave carbon-halogen bonds,followed by radical hydrogena-tion.Diisopropylethylamine served as the terminal electron/proton donor and regenerated theamine sensitizers.

A Mechanistic Switch in C-H Bond Activation by Elusive Fe^(V)(O)(TAML)Reaction Intermediate:A Theoretical Study

The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calculations.Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates(the aliphatic cyclohexane,2,3-dimethylbutane and the aromatic toluene,ethylbenzene and cumene).For the aliphatic substrates,C-H oxidation by the oxidant Fe^(V)(O)(TAML)is a hydrogen atom transfer process;whereas for the aromatic substrates,C-H oxidation is a proton-coupled electron transfer(PCET)process with a proton transfer character on the transition state,that is,a proton-coupled electron transfer process holding a proton transfer-like transition state(PCET(PT)).This difference is caused by the strongπ-πinteractions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates,which has a“pull”effect to make the electron transfer from substrates to the Fe=O moiety inefficient.

Synthesizing active and durable cubic ceria catalysts(<6 nm)for fast dehydrogenation of bio-polyols to carboxylic acids coproducing green H_(2)

Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.

Density Functional Studies of the Reaction of Ytterbium Monocation with Fluoromethane:C-F Bond Activation and Electron-Transfer Reactivity

The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.

Photocatalytic C-H Bonds Activation:Ambient Carbonylation of Cyclohexane by Co(acac)_2 Under Ultraviolet Irradiation

A high turnover number was achieved in the photocatalytic carbonylation of C - H bonds of cyclohexane catalyzed by Co (acac)2 under ambient conditions (1 atm,25℃) to give mainly cyclohexanecarboxaldehyde.

The Effect of Elevated Temperature on Bond Performance of Alkali-activated GGBFS Paste

The main reaction products were investigated by analysis of microstructure of alkali-activated ground granulated blast furnace slag （GGBFS） paste. An experimental research was performed on bond performance of alkali-activated GGBFS paste as a construction adhesive after exposure to 20-500℃. Through XRD analysis, a few calcium silicate hydrate, hydrotalcite and tetracalcium aluminate hydrate were determined as end products, and they were filled and packed each other at room temperature. In addition, akermanite dramatically increased at 800 ~C and above. The two key parameters, the ultimate load Pu.T and effective bond length Le, were determined using test data of carbon fiber-reinforced polymer （CFRP）-to-concrete bonded joints at elevated temperature. The experimental results indicate that the ultimate load Pu.T remains relatively stable initially and then decreases with increasing temperature. The effective bond length Le increases with increasing temperature except at 300℃. The proposed temperature-dependent effective bond length formula is shown to closely represent the test data.

Biphasical Force-Dependent CD40 L Ligation-Induced Activation of Integrin α5β1 under Flows

As a key regulator of immune response,CD40 L is usually associated with chronic disease-related inflammation,autoimmune diseases and malignant diseases.Receptor recognition of platelet CD40 L is the initial event that mediates platelet aggregation and leukocyte immune response.Unlike soluble CD40 L,the interaction between transmembrane platelet CD40 L and its receptors occurs within the cell junction surface,usually,in a physiological and pathological high blood flow shear stress environment.This two-dimensional reaction kinetics should be a mechano-chemical coupling process.In addition to its classical receptor CD40,CD40 L also binds to receptorα5β1,CD40 L can bind to the resting state of integrinα5β1,but the mechanical regulation mechanism of integrinα5β1 activation under fluid shear stress remains unclear.We assume that the force can promote CD40 L-inducedα5β1 activation.To check this hypothesis,we performed flow chamber experiment to investigate interaction of CD40 L andα5β1.In experiments,the bottom of the flow chamber is functionalized by a suitable concentration of CD40 L,and the fiber spheres of 6μm diameter was coated withα5β1.The selection of CD40 L concentration was based on the observation that as many tether events ofα5β1-coated spheres as possible were observed rather than stable adhesion events of these spheres.Theα5β1-coated sphere suspension was poured over the CD40 L-coated substrates in the flow chamber under different shear rates.A high-speed camera was used to observe and record tether events of fiber spheres at a rate of 100 frames per second.According to our affinity state transition model for integrin,the data were analyzed to obtain the rate of integrin activation and its mechanical regulation characteristics.Our results demonstrated that the interaction betweenα5β1 and CD40 L is biphasic force-dependent,showing mechano-chemical regulation mechanism of'Catch-slip bond'transition.The affinity jumping model was well fitted with the data obtained from flow chamber experiment at various wall shear stresses.We found that,CD40 L ligation-induced jumping ofα5β1 affinity state from low to medium(or high)one will occur within 0.5-1.0 second,resulting in prolonging of bond lifetimes.And,frequency distribution of the tether events number with tether lifetime under each force,exhibits obvious doublet peaks,one within 0.5-1 s and second within 1.5-2.5 s,indicating theα5β1 affinity state transform from low to high one.The probability distribution of the tether lifetime under different shear forces are not linear,and exists a turning point,which shows that the rate ofα5β1 dissociation from CD40 L is fast first,and then become slow,showing a force-induced conformation transformation of the integrinα5β1 from low affinity state to high affinity one.Our findings suggest that,the continuous force stimulation will quickly cause the affinity state change of integrinα5β1. The dissociation rate of theα5β1/CD40 L complex decreases first and then increases with wall shear stress,exhibiting a'Catch-slip bond'transformation of interaction betweenα5β1-CD40 L.This mechanical regulation mechanism exists in interaction of CD40 L not only toα5β1 at low affinity state but also to one at high affinity state.Our results should be useful in understanding the mechanical regulation mechanism of a5β1-CD40 L interaction-mediated cellular immune response and inflammatory processes.

High Activated Mineral Admixture Slurry Made by Wet-discharged Fly-ash Promoted by Matrix Bonding Component

The mineral admixture slurry was made by wet-discharged fly-ash （WDFA） promoted by matrix bonding component （MBC）, and the strengths, hydration products change （XRD, SEM） of cement paste made by the slurry were studied. The results indicate that in the process of wet-milling preparation, there is a prime proportion （70︰30） between wet-discharged fly-ash and matrix bonding component in the slurry. The physical activation of wet-milling and chemical activation of modified agents accelerate the hydration of cement including the cement and mineral which has not hydrated completely in the matrix bonding component. And the hydrated part of matrix bonding component can play the function of inducing crystallization, which can accelerate secondary hydration reaction of fly-ash.

Competition between C-C and C-H Activation in Reactions of Neutral Nickel Atom with Cycloalkanes （n = 3-7）

A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.

STUDIES OF QUANTUM CHEMISTRY CALCULATION ON VALENCE-BOND STRUCTURE AND HYDRATION ACTIVTY OF C_(12)A_7

The structure, chemical bonds and hydra-tion activity of C12A were studied by SCC-DV-Xa method of computational quantum chemistry. The calculated results show that Ca-O bond will be first broken off when C12A hydrates, the reactivity of Al(2)O4 tetrahedron is superior to that of Al(1)O4 tet, thedron and the rupture of the Al-O-Al chain composed of two types of AlO4 tetrahedra under the action of water lies in the very weak Al(2)-O(2) bonds. the Al-O bond strength of C12A7 is between C3A and C11A7·CaF2.

Study on Synthesis and Herbicidal Activity of Heterocyclic Compounds Containing P-P Bond

N,N′-diphenylurea reacted with phosphorus trichloride and phenyl dichlorophosphane giving the heterocyclic compounds 1 and 2 with a direct phosphorus-phosphorus bond (P-P bond), respectively. The new compounds were characterized by elementary analysis, NMR and IR spectra. The results of preliminary bioassay showed that these heterocycles possess selective herbicidal activity at 1.5 kg/hm2.

Theoretical verification of intermolecular hydrogen bond induced thermally activated delayed fluorescence in SOBF-OMe

Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_(1))and the first triplet excited state(T_(1))to favor the up-conversion from T_(1)to S_(1).In this paper,a new TADF generation mechanism is revealed based on theoretical simulation.By systematic study of the light-emitting properties of SOBF-OMe in both toluene and in aggregation state,we find that the single SOBF-OMe could not realize TADF emission due to large energy gap as well as small up-conversion rates between S_(1)and T_(1).Through analysis of dimers,we find that dimers with intermolecular hydrogen bond(H-bond)are responsible for the generation of TADF,since smaller energy gap between S_(1)and T_(1)is found and the emission wavelength is in good agreement with experimental counterpart.The emission properties of SOBF-H are also studied for comparison,which reflect the important role of H-bond.Our theoretical results agree ith experimental results well and confirm the mechanism of H-bond induced TADF.

A FACILE SYNTHESIS OF 2-TRIFLUOROMETHYLPYRROLE VIA 1,3-DIPOLAR CYCLOADDITION REACTION OF 2-TRIFLUOROMETHYLOXAZOLONE AND THE ACTIVATED CARBON-CARBON MULTIPLE BOND

The 1.3-dipolar cycloaddition reaction of 2-trifluoromethyl- oxazolone and the activated carbon-carbon multiple bond was studied and gave a convenient way to synthesize 2-trifluoromethylpyrrole derivatives.

Photocatalytic properties of TiO_2 bonded active carbon composites prepared by SOL-GEL

Photocatalyst of TiO2 bonded active carbon （TiO2/AC）, was prepared via sol-gel method from a mixture of TiO2 sol with active carbon. Post heat treatment was performed at 250 ℃ for 2 h in air and then kept at 400 ℃ to 600 ℃ under a flow of nitrogen for 2 h. The TiO2/AC composites obtained were characterized by SEM, XRD, UV-vis and BET. The photocatalytic activities of the TiO2/AC composites were studied in comparison with TiO2, AC, P-25 and a mixture of TiO2 and AC, respectively. The Ramnant rate of Rhodamine B absorbed by the active carbon is found to be almost 70% and the remnant rates of the Rhodamine B decolorized by TiO2 and the mixture of TiO2 and the active carbon are 30% and 25%, respectively. However, nearly complete removal of Rhodamine B is observed for a TiO2/AC composite after 200 min under UV irradiation, which will take the P-25 commercial product 5 h. Therefore, the TiO2/AC composite is much more effective in decolorization of aqueous Rhodamine B. In addition, the composite can be easily separated from solutions.

Ultrathin organic polymer with p-πconjugated structure for simultaneous photocatalytic disulfide bond generation and CO_(2)reduction

Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.

浸水环境下改性氯氧镁砂浆黏结强度变化规律

为了研究经青稞秸秆灰(HBSA)改性的氯氧镁水泥砂浆(MOCM)作为西部盐湖地区普通混凝土的外防护层,抵御盐湖区卤水侵蚀从而延长混凝土服役寿命的可行性,开展了浸水环境下掺入HBSA的MOCM的黏结强度等试验研究.采用普通混凝土作为黏结基层,以混凝土基层涂刷界面剂、MOCM中掺入HBSA以及砂浆层厚度等影响因素为变量,通过黏结拉拔试验分析各因素对MOCM黏结强度的影响规律,确定最优的设计参数,通过多项式模拟以及MATLAB中网格化处理等数值模拟方法,建立氯氧镁水泥黏结强度时变模型,进一步分析了浸水环境下改性MOCM黏结强度的损伤退化规律.采用微观测试技术分析了MOCM的物相组成、官能团结构、微观形貌、元素映射等特征,揭示了HBSA对MOCM黏结性能的影响机理.结果表明,HBSA中有较多的活性SiO2,能够与MOCM中的水化产物发生二次水化反应,生成水化硅酸镁(M―S―H)凝胶,填充MOCM内部孔隙,增强密实性,提高黏结性能.厚度为18 mm、掺入HBSA,且涂刷界面剂的MOCM黏结强度最高,其在浸水环境下的黏结强度退化速率最慢,基于三次多项式的数值模型能较好地反映其黏结强度的退化规律,最优组YY-18的相关性系数R2达到0.98.

实体视角下的资本市场:本源、沿革及发展趋势

资本市场是一种重要的经济组织形式,是金融市场的重要组成部分,它提供了一个平台,可集聚资金、配置资源,并进行投融资活动。通过在资本市场上发行股票或债券等方式,实体可以获得所需的资金,同时投资者可以购买证券来参与经济活动,并分享风险与收益。实体获取资源的手段是资本市场的创新和发展,只有深刻理解资本市场的本源和底层逻辑,才能更好地解决其发展过程中遇到的问题,并从实体逻辑中找到答案。因此,文章对资本市场本源、沿革及发展趋势进行研究,对资本市场的创新和发展具有重要的现实意义。

硅基钽酸锂异质晶圆键合工艺研究

5G移动通信的发展对声表面波滤波器提出了高频、小型化、集成化的要求。相较于传统压电体单晶材料,采用硅基压电单晶薄膜材料制备的声表面波滤波器具有高频、低插入损耗、高温稳定性等优势,是高性能声表面波器件发展的核心基础材料。Smart-Cut^(TM)是制备硅基压电单晶薄膜材料的主要方法,键合工艺是其中的核心工序,键合质量决定了硅基压电单晶薄膜晶圆材料的质量,并影响器件性能。本文通过低温直接键合工艺,对等离子活化、兆声清洗、预键合、键合加固四道工序展开优化,最终实现了键合强度高达1.84 J/m^(2)、键合面积超过99.9%的高质量硅基钽酸锂异质晶圆键合。

2-(甲氧基亚胺基)苯乙酸的合成研究

研究了2-(甲氧基亚胺基)苯乙酸即苯基MIA的合成,并对该工艺的反应条件进行了筛选和优化。将甲氧基胺基盐酸盐和碳酸钠固体分别加入圆底烧瓶中,溶于干燥的二氯甲烷,0℃下加入苯甲酰甲酸,25℃下反应3h。该工艺方法得到72%左右的收率,且反应条件简单温和,工艺设备成本廉价,实现了操作简单、经济实惠和绿色环保的目的。