Biomass valorization via electrocatalytic carbon–carbon bond cleavage

Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from biomass.However,it has merely received finite concerns and interests in the biorefinery.This review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification strategies.For the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/scaffolds.The remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also proposed.This review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.

Double linear strain distribution assumption of RC beam strengthened with external-bonded or near-surface mounted fiber reinforced plastic

Rehabilitation of existing structures with fiber reinforced plastic(FRP)has been growing in popularity because they offer superior performance in terms of resistance to corrosion and high specific stiffness.The strain coordination results of 34 reinforced concrete beams(four groups)strengthened with different methods were presented including external-bonded or near-surface mounted glass or carbon FRP or helical rib bar in order to study the strain coordination of the strengthening materials and steel rebar of RC beam.Because there is relative slipping between concrete and strengthening materials(SM),the strain of SM and steel rebar of RC beam satisfies the double linear strain distribution assumption,that is,the strain of longitudinal fiber parallel to the neutral axis of plated beam within the scope of effective height(h0)of the cross section is in direct proportion to the distance from the fiber to the neutral axis.The strain of SM and steel rebar satisfies the equation εGCH=βεsteel,where the value of β is equal to 1.1-1.3 according to the test results.

Double pull specimen more suitable for measuring bond-slip relationship of FRP-to-concrete interface

A new "conceptual" design named "double pull" specimen was proposed in order to measure the bond-slip(δ-τ) relationship of fiber reinforced polymer(FRP)-to-concrete interface more accurately.A finite element analysis(FEA) was performed for preliminarily evaluating the suitability of the proposed conceptual double pull specimen.Through the FEA,it was indicated that the FRP-to-concrete interface of the proposed conceptual specimen might subject to a much higher load level than that of the most commonly used simple shear specimen,showing a great potential for measuring δ-τ relationship more accurately.In the light of the conceptual specimen,a kind of "practical" double pull specimen was developed and proved to be more suitable for measuring δ-τ relationship through an exploratory experimental study with 20 specimens.Consequently,an experimental program with 10 double pull specimens was performed for measuring the ultimate slip δu which was difficult to capture by using the existing specimens.It is shown that the range of δu is 0.31-0.52 mm based on the test results.The suggestion for improving the measure method is also put forward.

DFT Studies on the Isomerization of Butene Double Bond Catalyzed by 1-Butyl-3-methyl-imidazolium in Ionic Liquid

The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.

Theoretical study on non-sequential double ionization of carbon disulfide with different bond lengths in linearly polarizedlaser fields

By using a two-dimensional Monte-Carlo classical ensemble method, we investigate the double ionization（DI） process of the CS_2 molecule with different bond lengths in an 800-nm intense laser field. The double ionization probability presents a ＂knee＂ structure with equilibrium internuclear distance R = 2.9245 a.u.（a.u. is short for atomic unit）. As the bond length of CS increases, the DI probability is enhanced and the ＂knee＂ structure becomes less obvious. In addition,the momentum distribution of double ionized electrons is also investigated, which shows the momentum mostly distributed in the first and third quadrants with equilibrium internuclear distance R = 2.9245 a.u. As the bond length of CS increases,the electron momentum becomes evenly distributed in the four quadrants. Furthermore, the energy distributions and the corresponding trajectories of the double-ionized electrons versus time are also demonstrated, which show that the bond length of CS in the CS_2 molecule plays a key role in the DI process.

LOCATION OF DOUBLE BOND POSITION OF INSECT SEX PHEROMONE BY GC/MS ANALYSIS WITH CHEMICAL IONIZATION

Ozonolysis products of four lepidopteral pheromone were identified by methane CI-MS.The spectra obtained were notably simpler than those of EI-MS,the peak of molecular ion was normally close to the base peak,and the characteristic fragment ions were high in m/z,thereby the interpretation was facilitated.

IDENTIFICATION OF DOUBLE BOND POSITION IN HEXADECENYL ACETATES BY MASS SPECTROMETRY

A method for locating double bond in hexadecenyl acetates has been developed by analyzing the mass spectral patterns on a fuzzy classification. The procedure was tested with the spectra of Δ~2- to Δ^(15)-isomers and the original double-bond position in these acetates was located unambiguously.

Syntheses and Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)_2Cl]·ClO_4 and [Zn(bipy)_2Cl]·BF_4

Two new transition metal complexes, [Ni（bipy）2Cl]·ClO4 （bipy = 2,2＇-bipyridine） 1 and [Zn（bipy）2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776（1）, b = 12.067（1）, c = 16.146（2）A, β = 93.021（2）o, V = 2031.9（4） A^3, Mr = 505.98, Dc = 1.654 g/cm^3, μ = 1.255 mm^–1, F（000） = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with Ⅰ 〉 2σ（Ⅰ）. For 2, a = 10.758（4）, b = 12.058（4）, c = 16.135（5） A, β = 104.57（1）o, V = 2025.7（12） A^3, Mr = 500.00, Dc = 1.639 g/cm^3, μ = 1.396 mm^–1, F（000） = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen-sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy ···anion···bipy- M hydrogen bonding interactions between the chelating ligands of bipy and anion.

Synthesis and Structural Characterization of a New Cadmium(II) Complex with a Double Betaine

A new flexible double betaine L （L = 1,4-bis（pyridinio-4-carboxylato-N-methyl）benzene, C20H16N2O4） and its cadmium（Ⅱ） complex [Cd（H2O）aL（NO3）]NO3.H2O 1 were synthesized. Complex 1 was obtained by self-assembly reaction of [Cd（NO3）2]-4H2O and L in hot water,and its crystal structure was determined by single-crystal X-ray diffraction analysis. Crystallographic data for complex 1： C20H24CdN4O14.H2O, Mr = 674.85, monoclinic, space group P21/c, a =13.7854（3）, b = 14.2820（3）, c = 14.9188（4） ,A°, β = 116.418（1）°, V = 2630.5（1）A°^3, Z = 4, Dc= 1.704g/cm^3,/J（MoKα） = 0.911 mm^-1, F（000） = 1368, the final R = 0.0315 and wR = 0.0768 for 3637 observed reflections with I 〉 2σ（I）. In complex 1, L acts as a monodentate ligand to link a Cd（Ⅱ） ion in a novel coordination mode of double betaines. The mononuclear [Cd（H2O）aL（NO3）] units are connected through intermolecular hydrogen bonds and π-π stacking reactions to generate a 3D network.

Microstructure of nickel foam/Mg double interpenetrating composites

The magnesium matrix double interpenetrating composites reinforced by nickel foam were fabricated by pressureless infiltration technology.Then the morphology of the nickel reinforcement and the microstructures of composites were characterized by SEM.The results show that not only is the nickel foam reinforcement reticular in three dimensions,but also the struts of foam keep the network structure,which ensures that the Ni foam/Mg composites are double interpenetrating.The interface bonding of composites between magnesium matrix and nickel foam reinforcement is good,without reaction around the interface,which is the indispensable condition that advanced composites should possess.Magnesium matrix distributes in the windows of nickel foam,the triangle center holes and microhole of nickel struts,and the composites have double interpenetrating structure,which makes the composites have unique properties.

基于Multi-stage的double stitch工艺在铜线焊中的应用

作为引线键合工艺中传统的焊接材料,金线在稳定性、导电性及价格等方面存在诸多局限,使得铜线焊技术在IC封装领域得到越来越广泛的应用。同时,由于铜线易氧化、硬度高,焊接能力较低,特别是二焊点容易出现拉力不够、开裂等缺陷,使得铜线焊的应用受到限制。针对传统工艺流程,提出Multi-stage方法,并在此基础上实现二焊点的double stitch工艺方法,通过试验证明该方法能够有效提高二焊点拉力,增强焊接强度。

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.

茂金属聚乙烯薄膜晶点的组成及形成原因

采用凝胶渗透色谱仪(GPC)、差示扫描量热仪(DSC)、偏光显微镜以及红外光谱等分析手段,从原料的分子链结构分析了茂金属聚乙烯薄膜晶点的组成及其形成原因。结果表明,茂金属聚乙烯薄膜晶点的结晶形态与无晶点的正常薄膜的不同,构成晶点的晶体尺寸均匀性远不如无晶点的正常薄膜,这是因为晶点中含有类似于纤维状的晶体,这种晶体先结晶,导致随后形成的晶体在此处生长不均匀。此外,分子链上的端基双键(RCH CH 2)在吹膜过程中引起的分子间交联和分子链中存在的亚甲基序列较长的规整结构,是形成类纤维状晶体的主要因素,而较长亚甲基序列的规整结构是由于共聚单体分布不均匀引起的。

轨道减振器双底模注射硫化成型工艺的研究与应用

对轨道减振器双底模注射硫化成型工艺进行研究,并与传统高压模硫化成型工艺进行对比。结果表明:双底模注射成型工艺缩短了硫化时间,实现了轨道减振器的连续化生产,同时提高了型腔内压,促进了金属与橡胶的有效粘接;双底模注射硫化成型轨道减振器疲劳后垂向静刚度和动静刚度比变化率小,垂向静刚度波动范围在10%以内,产品性能更稳定。

激光二极管端泵方形Tm:YAG复合晶体的热效应

为了有效解决激光二极管端面泵浦激光晶体引起的热效应问题,引入复合晶体的概念,通过两种复合晶体模型(即单端键合和双端键合)来降低激光晶体的热效应。根据激光二极管端面泵浦激光晶体工作特点,建立端面泵浦方形Tm:YAG复合晶体热模型,利用热传导理论,用有限元分析法对复合晶体的温度场、热应力场和形变量进行了数值计算,分析了单端/双端键合方式、未掺杂晶体长度、增益晶体长度对方形复合晶体内部温度场及形变量的影响。结果表明,平衡状态下,激光二极管泵浦功率为30 W、泵浦光斑半径为400μm时,YAG晶体厚度c_(1)为1 mm,增益晶体厚度c_(2)为1.5 mm,方形单端键合和双端键合的Tm:YAG复合晶体内部最大温升分别为81.2、77.9℃;内部最大应力分别为146、104 MPa;热形变量为0.468、0.172μm。可见,复合晶体能有效缓解晶体的温升和热形变,且双端键合的方式降低晶体热效应的效果更好。当增益晶体厚度为2.6 mm以上时,两种键合方式对复合晶体内部最大温升的影响基本保持一致。该研究为方形Tm:YAG复合晶体的增益晶体厚度、未掺杂晶体厚度的选择提供了参考依据,也为实现Tm:YAG激光器高功率输出目标提供了理论指导。

单原子催化剂催化生物质衍生物选择性加氢的研究进展

生物质是以碳源形式存在的可再生资源,其平台化合物及衍生物的升级利用可得到能源和精细化工产品。多相催化剂在生物质资源的转化中起到重要作用,其中不乏纳米催化剂和单原子催化剂的参与。由于木质纤维素的含氧量较高,不能直接作为工业应用原料,因此需要还原反应来降低其含氧量。加氢反应是降低木质纤维素衍生分子中O C比、提高H C比的重要方法。本研究将综合讨论单原子催化剂在呋喃类、α,β-不饱和醛酮和木质素类平台化合物选择性加氢中的应用。

高能量密度氮的研究进展

氮在常压下是非常稳定的元素,以氮气分子形式存在。研究发现,氮在高温高压下能够形成聚合结构,这种结构具有极高的能量密度,而且分解产物为无污染的氮气,从应用角度上看,它能够作为新型环保高能量密度材料。随后,人们对其进行了大量的研究,得到了氮在高压条件下的相图,并且合成出立方偏转氮、层状聚合氮等结构。然而,纯氮聚合结构的合成条件比较严苛,在常压下很难保存。人们又转向分子结构氮和惰性气体氮化物等,希望能够得到常压下稳定的高能量密度氮结构。为此,针对目前高能量密度氮的理论和实验进展进行了简要的介绍,并对未来高能量密度氮的发展方向进行了探讨。

双键型分子光开关的E/Z异构化

适当取代的双键X=Y双键型分子能够在光的作用下发生E型和Z型之间的异构化。目前已报道的分子光开关大多是基于偶氮苯(ABs)、二芳烃乙烯(DAEs)和螺吡喃(SPs)等结构,但新的有趣的结构正在不断被报道。本文将讨论围绕C=C、C=N和N=N双键异构化的各种类型的光开关,重点介绍常用的光开关双键结构和极性质子溶剂等外界因素对其E/Z异构化的影响。

不同光引发剂口腔复合树脂单体的设计合成及性能

背景:目前由树脂基质单体组成的牙科复合树脂充填物,是牙体缺损充填治疗的首选材料,但随着其在口腔环境中使用时间的延长,牙体组织继发龋以及充填材料磨损折断等问题随之而来,造成这些问题的主要原因是充填材料的聚合收缩及其与牙体组织的机械性能不匹配等。目的:通过加入不同组分的引发剂合成牙科新型复合树脂单体,以提升传统体系的双键转化率并进一步提高材料的力学性能。方法:将不同的引发剂加入3,3′,5,5′-四甲基联苯二酚型环氧丙烯酸酯树脂单体中,制备新型复合树脂基质体系:A组加入质量分数1.1%的樟脑醌,B组加入质量分数2.1%的1-苯基-1,2-丙二酮,C组加入质量分数3.1%的樟脑醌与1-苯基-1,2-丙二酮混合物(二者质量比为1∶1)。检测各组样品的双键转化率、聚合收缩率和机械性能。结果与结论:①B、C组双键转化率高于A组(P<0.05);B组聚合收缩率大于A组(P<0.05),C组聚合收缩率小于A组(P<0.05);②B、C组的挠曲强度、弹性模量、压缩强度均大于A组(P<0.05,P<0.01),B组的维氏硬度大于A组(P<0.05),C组的维氏硬度小于A组(P<0.01);③结果显示,1-苯基-1,2-丙二酮是一种性能较理想的引发剂,且1-苯基-1,2-丙二酮与樟脑醌联合应用可有效提高树脂基质体系的双键转化率,从而提高树脂的力学性能。

双辉等离子渗铬界面层对类石墨碳基涂层力学及磨蚀性能的影响

目的 研究渗铬界面层对铬/类石墨碳(Cr/Graphite-Like Carbon,GLC)复合涂层力学性能、结合强度及磨蚀行为的影响,阐明Cr/GLC复合涂层的抗磨蚀机理。方法 以316L不锈钢(316L)为基体,先借助双辉等离子表面合金化(DGPSA)技术制备渗铬界面层,再采用直流磁控溅射(DCMS)技术制备顶层GLC涂层。利用扫描电子显微镜(SEM)、共聚焦显微拉曼光谱仪(Raman)和X射线衍射仪(XRD)表征涂层的微结构与成分,采用纳米压痕仪、划痕仪、摩擦磨损仪和电化学工作站测试复合涂层的力学性能、断裂韧性、结合强度和抗磨蚀性能。结果 渗铬界面层能够促进GLC涂层的石墨化转变,实现硬度分布的梯度变化(基体为3.65 GPa,渗铬界面层为8.97 GPa,表面为13.15 GPa),有效阻碍了裂纹的扩展。与GLC涂层相比,Cr/GLC复合涂层具有较高的断裂韧性和结合强度(≥50 N),在3.5%NaCl溶液中具有更低的摩擦系数(0.055)和更低的磨损率(3.22×10^(-7)mm^(3)/Nm),其抗腐蚀性和化学稳定性也明显更优。结论 通过界面设计,实现了Cr/GLC复合涂层硬度分布的梯度过渡,提高了复合涂层的断裂韧性以及与316L的结合强度,赋予了复合涂层优异的抗磨蚀性能,为其在海洋苛刻环境下的磨蚀防护提供了有益借鉴。