Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

Effects of Rotational Isomerism and Bond Length Alternation on Optical Spectra of FTC Chromophore in Solution

Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.

沉积温度对不同Co含量WC-Co/SiC/Diamond界面结合性能的影响

本文构建了Co质量分数分别为6%、8%、10%和12%的WC-Co/SiC/Diamond金刚石涂层硬质合金界面模型,利用分子动力学方法模拟了不同沉积温度对其界面结合强度的影响,从黏附功及键长分布两个方面进行具体分析。黏附功分析结果表明,与其他三种Co含量界面模型相比,WC-6%Co/SiC/Diamond界面模型在七个沉积温度下所包含的两种界面的黏附功值均为最高值,并且在不同沉积温度下,WC-6%Co/SiC/Diamond界面模型所包含的WC-6%Co/SiC界面、SiC/Diamond界面的黏附功分别在1123、1173 K时最大,为2.468、5.394 J/m^(2)。键长分布概率分析结果表明,与其他三种Co含量界面模型相比,在任一沉积温度下,WC-6%Co/SiC/Diamond界面模型各界面处键长分布范围的最大值较小,且在1123 K时在WC-6%Co基体上沉积SiC中间层,在1173 K时在SiC中间层上沉积Diamond涂层后,该界面模型界面处的键长最短,键能最大,界面结合性能最好。

Ion source effect on the bond length of ^4HeH^＋

The bond length of ^4HeH^＋ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^＋ is 0.094±0.003nm. The bond length of ^4HeH^＋ obtained with our radio frequency （RF） ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory （ANL）, but the bond lengths of H^＋2 and H^＋3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^＋. The main reason why the 4^4HeH^＋ bond lengths obtained by the two different ion sources are different is also discussed.

The Novel Selective Reduction of the C-C Triple Bond

A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)(4) in a base condition and only terminal C-C triple bond is reduced.

Structural and electronic effects boosting Ni-doped Mo_(2)C catalyst toward high-efficiency C-O/C-C bonds cleavage

The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.

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.

A NOVEL SCISSION OF ALKYL-CARBONYL C-C BOND BY ALKYL p-HYDROXYPHENYL KETONES

Methyl, ethyl, n-propyl, and benzyl p-hydroxyphenyl ketones and 6-hydroxy-1-tetralone are shown under the condition of ethylene ketal formation to undergo alkyl-carbonyl C-C bondscission, but not with p-hydroxybenzophenone, p-hydroxyisobutyrophenone, and 5-hydroxy-1-indanone. It is suggested that the scissiou is preceded by an aldol condensation.

A High-Precision Calculation of Bond Length and Spectroscopic Constants of Hg2 Based on the Coupled-Cluster Theory with Spin-Orbit Coupling

Based on the two-component relativistic effective core potential and matched basis sets cc-pwcvnz-pp （n=Q, 5）, combining the completed basis-set extrapolation of electronic correlation energy and the fourth-order polynomial fitting technique, the bond length and spectroscopic constants of Hg2 are studied by the coupled cluster theory with spin-orbit coupling. Spin-orbit coupling is included in the post Hartree-Fock procedure, i.e., in the coupled- cluster iteration, to obtain more reliable theoretical results. The results show that our theoretical values agree with the experimental values very well and will be helpful to understand the spectral character of Hg2.

Flexural Bond Behavior of Rebar in Ultra-High Performance Concrete Beams Considering Lap-Splice Length and Cover Depth

This study intends to find out the correlation between the cover depth and the bond characteristics of UHPC through pull-out tests of UHPC specimens with different cover depths and bond tests of rebar using flexural members. In this experimental study, specimens are fabricated with the lap-splice length as test variable in relation with the calculation of the lap-splice length for 180- MPa UHPC. Moreover, specimens are also fabricated with the cover depth as test variable to evaluate the effect of the cover depth on the UHPC flexural members. The load-displacement curves are analyzed for each of these test variables to compute the lap-splice length proposed in the K-UHPC structural design guideline and to evaluate the influence of the cover depth on the flexural members. As a result, the stability of the structural behavior can be significantly enhanced by increasing slightly the cover depth specification of the current UHPC Structure Design Guideline from the maximum value between 1.5 times of rebar diameter and 20 mm to the maximum value between 1.5 times of rebar diameter and 25 mm.

Further Report on A Novel Scission of Alkyl Carbonyl C-C Bond by Substituted 4-Hydroxyacetophenones

3-Methoxy-, 3, 5-dimethoxy-, and 3-phenyl-4-hydroxyacetophenones suffered alkyl carbonyl C-C bond scission to yield 4-hydroxybenzoate esters and 4-isopropenylphenols under standard conditions of ethylene ketal formation; the latter underwent in situ dimerization, cyclization, and rearrangement to give substituted indanols. The isopropenylphenol derived from 3,5-ditertbutyl-4-hydroxyacetophenone did not dimerize but condensed with its precursor to yield a substituted diphenylpropanone. 3-nitro-, 3,5-dinitro-, and 3,5-dibromo-4-hydroxyacetophenones on the other hand reacted normally to give ethylene ketals in good yields.

Recent Advances of Modern Protocol for C-C Bonds—The Suzuki Cross-Coupling

Over the past 20 years, small molecule solid phase synthesis has become a powerful tool in the discovery of novel molecular materials. In the development of organic chemistry, the carbon-carbon bond formation has always been one of the most useful and fundamental reaction. The current review summarizes recent developments in metal-catalyzed coupling reactions. The following method is discussed in detail—the cross-coupling of aryl halides with aryl boronic acids (the Suzuki coupling), and the others C-C bond formation reactions as the palladium-catalyzed reaction between an aryl and (or) alkyl halide and a vinyl functionality (the Heck reaction);and the palladium-catalyzed cross-coupling reaction of organostannyl reagents with a variety of organic electrophiles (the Stille reaction)—are mentioned.

Calculation of Bond-length, Bond-energy and Force Constant of Hydrogen Molecule by Classical Mechanics

Until recently the hydrogen molecule structural parameters are calculated with the methods of quantum mechanics. To achieve results close to experimental values, the wave function used is complicated and has no clear physical meaning. Because the distribution of the electron probability density is a statistical rule, the macro time has actually been used in the concept on a electron cloud graph. Here are obtained three formulas with a classical mechanics method on the bond length r e , bond energy D e and force constant k of the ground state hydrogen molecule, which have a clear physical meaning but no artificial parameters, and compared with experimental values, the relative errors are respectively less than 1%, 2% and 4%.

锚杆岩体界面载荷传递规律及锚固长度设计

为揭示巷道围岩锚固界面脱粘失效机理,量化锚杆支护设计参数,采用三线性粘结滑移模型进行理论分析,对轴向载荷作用下锚固脱粘失效全过程中,锚固段界面剪应力、锚杆轴力分布演化规律以及界面极限锚固力进行研究,根据锚固段长度不同,得到两种界面剪应力分布演化类型。研究结果表明:当锚固长度较短时,界面剪应力存在全长软化阶段;当锚固长度较长时,界面剪应力存在弹性-软化-滑移三段共存阶段。锚固粘结界面弹性段、软化段、摩擦段内的剪应力分别呈现双曲余弦函数衰减分布、余弦函数上升分布、均匀分布规律,锚杆轴力随界面剪应力分布演化呈现多种形态的衰减分布规律。根据锚固界面模型解析计算获得极限锚固力,当不考虑脱粘摩擦力时,极限锚固力随锚固长度的增加趋近于某一固定值;当考虑脱粘摩擦力时,增加锚固长度能够持续提高锚固界面安全系数。研究成果可为锚固机制分析、锚杆支护参数设计提供理论参考。

考虑锈蚀损伤的黏结滑移本构模型

为合理反映钢筋锈蚀后黏结滑移性能劣化对钢筋混凝土(RC)结构抗震性能的影响,在既有黏结应力分布模式的基础上,推导得到钢筋应力-滑移关系,进而通过分析锈蚀对混凝土与钢筋界面黏结滑移机理的影响,建立考虑钢筋锈蚀损伤的黏结滑移本构模型。基于已有拉拔试验结果,与仅考虑纵筋锈蚀率影响的Cheng模型进行对比,验证所建模型的合理性与准确性。基于OpenSees有限元平台,采用纤维梁柱单元和零长度截面单元串联的方式,将所建钢筋黏结滑移模型嵌套于零长度截面单元的钢筋本构中,建立可考虑黏黏结滑移的锈蚀损伤纤维梁柱模型,并通过6根锈蚀RC柱拟静力试验结果验证模型的准确性,结果发现所提考虑黏结滑移的锈蚀RC纤维梁柱模型计算所得滞回曲线与试验滞回曲线吻合良好,累计耗能最大误差不超过15%。此外,通过参数分析研究影响锈蚀钢筋滑移量的因素,结果表明屈服滑移量与极限滑移量随体积配箍率的增大而明显减小,随混凝土保护层与钢筋直径之比(c/d)增大而变化的幅度较小。

反铁磁材料CrPS_(4)的稳定性及成键分析

根据拓扑学原理,基于密度泛函理论,从能量、能隙差、键级、键级贡献率和键长五个方面对反铁磁材料CrPS_(4)的稳定性与成键情况进行分析。研究表明,团簇的16种稳定构型含二、四重态各8种,其中平面形2种、三角双锥带帽型11种、四角双锥型1种、四棱锥带帽2种。在所有构型中,无论是热力学稳定性还是化学稳定性,构型1^((4))均居于首位,稳定性较好。化学键的键级贡献率因构型不同而异。综合分析发现,化学键强度大小依次为:Cr—S>S—P>S—S,S—S键最不稳定,甚至在有些构型中不易形成,即使形成,也极易断裂,而Cr—P键就很稳定,但与其他三种化学键的强度关系不易确定。

Regioselective C-C bond cleavage/aminocarbonylation cascade under copper catalysis

A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.

Selective activation of C-C bonds in lignin model compounds and lignin for production of value-added chemicals

Lignin is a rich renewable aromatic resource that can produce high-value-added chemicals. Lignin is regarded as one of the three major components of lignocellulosic biomass, which is composed of phenylpropane units connected by C-O bond and C-C bond. The cleavage of two chemical bonds is the main catalytic pathway in the production of chemicals and fuels from lignin. Although the cleavage of C-O converts lignin into valuable aromatic compounds and renewable carbon sources, selective depolymerization for C-C bonds is an important method to increase the yield of aromatic monomers. Therefore, in this review, we summarized the latest research trends on C-C bond selective cleavage in lignin and lignin model compounds, focusing on various catalytic systems, including hydrogenolysis, oxidate, photocatalysis, and electrocatalysis. By analyzing the current status of C-C bond breakage, the core issues and challenges related to this process and the expectations for future research were emphasized.

HRB400钢筋与UHPC锚固可靠度分析及锚固设计研究

为给桥梁工程中HRB400钢筋与超高性能混凝土(Ultra-High Performance Concrete,UHPC)锚固设计提供依据,对两者间的粘结性能及锚固长度进行研究。根据中心拔出试验中54个不同参数HRB400钢筋与UHPC锚固试件的粘结强度结果,回归得到粘结强度计算公式;在此基础上利用中心点法进行锚固可靠度分析与基本锚固长度计算,并与国内外规范基本锚固长度计算结果进行对比。结果表明:《混凝土结构设计规范》(GB 50010-2010)和CEB-FIB Model Code 2010计算的基本锚固长度接近,与中心点法相比偏大、偏安全;基于锚固长度计算结果,给出不同保护层厚度下基本锚固长度和钢筋断裂最小锚固长度建议值;提出UHPC相对保护层厚度为0.5时,可采用《混凝土结构设计规范》计算HRB400钢筋与UHPC基本锚固长度和钢筋断裂最小锚固长度;UHPC相对保护层厚度为1.0、1.5、2.0时,可通过修正《混凝土结构设计规范》计算结果取值,基本锚固长度修正系数分别可取0.8、0.65、0.55,钢筋断裂最小锚固长度修正系数分别可取0.85、0.7、0.6。