Adsorption enthalpy and desorption enthalpy during displacement of adsorbate to solvent in a liquid-solid system

The adsorption heat of the stoichiometric displacement process for the adsorption of a solute in a liquid-solid system was investigated. On the basis of the SDM-A and the rule of the additivity of energy, an expression which describes the dependence of the adsorption enthalpy on the nature and concentration of the solute, and on the solvent and adsorbent, was derived. The adsorption heat determined for the solute with the traditional method can be divided into two independent fractions, relating to the adsorption of the solute and to the desorption of the solvent. Experimental data on both isotherms from the literatures and precise calorimetry were used to test the adsorption heat and its fractions computed quantitatively via the equations presented in this study, and a satisfactory degree of conformity between them was obtained. Supported by the Natural Science Foundation of Shaanxi Province in China.     

Isolation and purification of honokiol and magnolol from cortex Magnoliae officinalis by high-speed counter-current chromatography

High-speed counter-current chromatography was used to isolate and purify honokiol and magnolol from cortex Magnoliae Officinalis (Magnolia officinalis Rehd. et Wils.), a plant used in the traditional Chinese medicine. A crude sample, 150 mg, was successfully separated with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:0.4:1:0.4, v/v), and the fractions were analyzed by high-performance liquid chromatography. The separation produced 80 and 45 mg of honokiol and magnolol with purities of 99.2 and 98.2%, respectively, in 2.5 h.     

Atomic radical—molecule reactions F + CH<Subscript>3</Subscript>C≡CH: mechanistic study

The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions, i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical F attacking on the C≡C triple bond in propyne (CH₃C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H₂CCCHF + H via transition state TS₅/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons. This material is available from author via E-mail.     

Single Atoms of Iron on MoS2 Nanosheets for N2 Electroreduction into Ammonia

Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH₃). Reported herein is a novel Fe-MoS₂ catalyst with Fe atomically dispersed onto MoS₂ nanosheets, imitating natural nitrogenase, to boost N₂ electroreduction into NH₃ at room temperature. The Fe-MoS₂ nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg_cat.⁻¹ h⁻¹ for NH₃ at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N₂ was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS₂ with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N₂ into NH₃. This work provides new ideas for the design of catalysts for N₂ electroreduction and strengthens the understanding about N₂ activation over Mo-based catalysts.     

Synthesis of high purity single-walled carbon nanotubes in high yield

A simple method for the synthesis of high purity single wall carbon nanotubes has been developed by using nickel formate as a precursor for the formation of nearly mono-dispersed nickel seed-nanoparticles as catalysts in the CVD growth process.     

MLIMC: Machine Learning-Based Implicit-Solvent Monte Carlo

Monte Carlo (MC) methods are important computational tools for molecular structure optimizations and predictions. When solvent effects are explicitly considered, MC methods become very expensive due to the large degree of freedom associated with the water molecules and mobile ions. Alternatively implicit-solvent MC can largely reduce the computational cost by applying a mean field approximation to solvent effects and meanwhile maintains the atomic detail of the target molecule. The two most popular implicit-solvent models are the Poisson-Boltzmann (PB) model and the Generalized Born (GB) model in a way such that the GB model is an approximation to the PB model but is much faster in simulation time. In this work, we develop a machine learning-based implicit-solvent Monte Carlo (MLIMC) method by combining the advantages of both implicit solvent models in accuracy and efficiency. Specifically, the MLIMC method uses a fast and accurate PB-based machine learning (PBML) scheme to compute the electrostatic solvation free energy at each step. We validate our MLIMC method by using a benzene-water system and a protein-water system. We show that the proposed MLIMC method has great advantages in speed and accuracy for molecular structure optimization and prediction.     

离散式任意充磁角度Halbach永磁电机解析模型研究

Halbach电机因其自身优势在新型船舶推进、海洋洋流发电等方面受到广泛关注. 本文在假设铁磁材料线性和定子内表面光滑的条件下, 通过将任意充磁角度Halbach阵列等效为两组90° Halbach(或180° Halbach)阵列的矢量合成, 提出了一种分析离散式任意充磁角度Halbach永磁电机气隙磁场的解析方法; 通过对电机中磁标量势的傅里叶级数进行计算, 推导出了最简单的90° Halbach永磁电机在极坐标系下的气隙磁密表达式, 并在此基础上, 给出了任意充磁角度Halbach电机永磁体磁化强度在一个极下的表达式, 进而得出任意充磁角度Halbach电机气隙磁密的分布, 并分析了气隙磁密与电机极对数、永磁体厚度和充磁角度间的关系. 最后通过有限元和试验结果验证了本文方法的正确性. 关键词： 离散式Halbach电机 任意充磁角度 矢量等效 解析模型     

Coherent beam combination of adaptive fiber laser array with tilt-tip and phase-locking control

We present an experimental study on tilt-tip(TT) and phase-locking(PL) control in a coherent beam combination(CBC) system of adaptive fiber laser array.The TT control is performed using the adaptive fiber-optics collimator(AFOC),and the PL control is realized by the phase modulator(PM).Cascaded and simultaneous controls of TT and PL using stochastic parallel gradient descent(SPGD) algorithm are investigated in this paper.Two-fiber-laser-,four-fiber-laser-,and six-fiber-laser-arrays are employed to study the TT and PL control.In the cascaded control system,only one high-speed CMOS camera is used to collect beam data and a computer is used as the controller.In a simultaneous control system one high-speed CMOS camera and one photonic detector(PD) are employed,and a computer and a control circuit based on field programmable gate array(FPGA) are used as the controllers.Experimental results reveal that both cascaded and simultaneous controls of TT using AFOC and PL using PM in fiber laser array are feasible and effective.Cascaded control is more effective in static control situation and simultaneous control can be applied to the dynamic control system directly.The control signals of simultaneous PL and TT disturb each other obviously and TT and PL control may compete with each other,so the control effect is limited.