Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

关于Gibbs函数变关系式引出的探讨

本文推荐陈林根编著的《工程化学》对化学热力学基本公式△G=△H-T△S的引出方法,试探基础教学的改革。     

Reconstruction of a discontinuous function from a few fourier coefficients using bayesian estimation

The goal of this paper is the application of spectral methods to the numerical solution of conservation law equations. Spectral methods furnish estimates of the firstn Fourier coefficients of the solution. But since the solutions of conservation law equations can have discontinuities, the estimate of the solution by summing the firstn terms of the Fourier series will haveO(1/n) error, even if the Fourier coefficients are known to high accuracy. But if the solution could be accurately reconstructed from its Fourier coefficients, spectral methods could be used effectively in these problems. A method for doing this is to assume a probability distribution for functions. Functions which are smooth away from the discontinuity are assumed to be likely, and those which are not smooth away from the discontinuity are assumed to be unlikely. Then a reconstruction algorithm is chosen by minimizing the expected error over all algorithms. It is possible to put the smoothness assumptions mentioned earlier into an infinite-dimensional Gaussian probability distribution, and then the minimum-error algorithm is well-known and fairly simple to construct and apply. If the Fourier coefficients of the reconstructed function are known exactly, then this approach gives very good results. But when used with Fourier coefficients obtained from a spectral approximation to Burgers' equation, the results were much less impressive, probably because the coefficients were not known very accurately. It is possible to construct filters that reconstruct a function using Legendre or Chebyshev coefficients for information instead Fourier coefficients. It is found that the performance of these filters is similar to the Fourier case.     

单元系T—p相图的数学结构

作者以化学元素的稳定单质为基准,推演出了任意物质M_i(相态Ω)的热力学生成活度{相态Ω)的函数形式:?D_Ω数值的大小体现着相态Ω的热力学相对稳定性.根据集合论原理沿D(稳定性)座标取极大值的方法把物理性质互不连续的各个异相态连结在一起,建立了单元系在T-p面上的优势分布方程(PSDE):■作者以H_2O为实例,计算了T-p相图,与实验相图基本一致.     

Activity measurement of the constituents in molten Fe–B and Fe–B–C alloys

The distribution ratios of Fe and B between molten Fe–B alloy and molten Ag were measured at temperatures between 1573 and 1923 K. Also, distribution ratios of Fe and B between molten Fe–B–C_satd. alloys and molten Ag were measured at 1873 K. It was found that the excess Gibbs free energy of mixing in molten Fe–B and Fe–B–C alloys can be expressed by utilizing the Redlich–Kister polynomial. The activity curves of the elements in molten Fe–B alloy and Fe–B–C alloy were estimated.     

NdBO_3和 Nd(BO_2)_3的标准生成自由能

用 CaF_2单晶和 ZrO_2(+MgO)为固体电解质分别构成原电池:■和 Pt,B_((s)),NdBO_(3(s)),Nd(BO_2)_(3(s))|ZrO_2|Cr_2O_(3(s)),Cr_((s)),Pt联合测了 NdBO_3和 Nd(BO_2)_3的标准生成自由能:ΔG~0_(NdBO_3)=-1757+3.8×10~(-1)TΔG~0_(Nd)(BO_2)_3=-3435+8.8×10~(-1)T由此求出由氧化物生成 NdBO_3及 Nd((BO_2)_3)的反应的标准生成自由能变化:1/2Nd_2O_(3(s))+1/2B_2O_(3■)=NdBO_(3(s))ΔG~0_(NdBO_3)=-242+1.4×10~(-1)T和 1/2Nd_2O_(3(s))+3/2B_2O_(3(s))=Nd(BO_2)_(3■)ΔG~0′_(NdBO_2)3=-693+4.6×10~(-1)T     

Chemical Composition Determination at the Bottom Region of a Recovery Boiler Furnace by Direct Minimization of Gibbs Free Energy

An optimization strategy has been applied to describe the chemical composition at the furnace bottom in the Kraft recovery boiler of a pulp production process. The concentrations of each involved chemical species were calculated through an optimization approach, minimizing the Gibbs free energy of the system. Various systems were proposed and tested, assuming different chemical species and phases number. Because serious initialization problems were found at this stage for some of the proposed systems, an optimization heuristic method (PSO) was used for the first approach to the problem. Once the appropriate phases number and chemical species in the system were determined, the initialization problems disappeared and the use of a deterministic optimization method (SQP) became viable. The proposed approach has shown to be satisfactory to reproduce industrial data and also data reported in the open scientific literature.     

逐步增加定数截尾下Weibull 分布恒加试验的Bayes估计

基于逐步增加定数截尾样本,对累积失效模型(简称CE模型)下,Weibull分布恒定应力加速寿命试验(简称恒加试验)进行了Bayes统计分析,利用Gibbs抽样给出了该模型的Bayes估计。最后,通过模拟例子表明Bayes估计有效而实用。     

不对称性定量化的三元系热力学模型

本文提出了一个由二元系推算三元系热力学性质的新模型，此模型能自动用热力学准则来检查各二元系的对称性，并根据不对称程度来构筑权重函数，由于不需要事先选择不对称组元，消除了计算过程中的人为干扰。此模型的适用范围有所拓宽。