Rates of diffusion controlled reactions for one-dimensionally-moving species in 3D space

ABSTRACT

The asymmetry in diffusion dimensionality between self-interstitial atom (SIA) clusters and vacancies is a fundamental feature of irradiation damage in crystals, leading to a defect buildup imbalance that manifests itself as measurable dimensional and mechanical property changes. It is well known that, while vacancies and mobile vacancy clusters diffuse in a three-dimensional (3D) fashion, SIA clusters perform one-dimensional motion along mostly rectilinear trajectories. Despite this, a complete set of kinetic coefficients, including coagulation reaction rates and sink strengths, does not exist for 1D-moving objects. In this paper, we derive analytical expressions for these coefficients from continuum diffusion theory particularised to 1D motion. Moreover, we carry out kinetic Monte Carlo simulations of numerical replicas of the geometry of diffusing particles and sinks to validate the proposed solutions. Our simulations, which are conducted entirely independently from the analytical derivations, reveal excellent agreement with the proposed expressions, adding confidence to their validity. We compare the 1D and 3D cases and discuss their relevance for kinetic codes for damage accumulation calculations.     

一个反应扩散方程的门槛结果

本文讨论反应扩散方程Ｃａｕｃｈｙ问题解的整体存在性，渐近性质和Ｂｌｏｗｕｐ问题．其中或者１＜ｑ＜ｐ＜＋∞，ｎ＝２．得到门槛结果．     

一步法直接合成碳酸二甲酯催化剂

采用浸渍法以MgO、海泡石（Sep）。γ-Al2O3为载体,制备了一系列金属盐Lewis酸-无机碱双组分负载型催化剂,以环氧丙烷（PO）一步合成碳酸二甲酯（DMC）反应为探针。考察了催化剂的不同载体活性组分和反应条件对合成DMC的产率及选择性的影响。结果表明,催化剂的活性次序为：NaOH—LiCl／MgO）NaOH—LiCl／Sep）NaOH—LiCl／γ-Al2O3;选择性的次序为：NaOH—LiCl／Sep）NaOH—LiCl／MgO）NaOH—LiCl／γ-Al2O3。NaOH—LiCl／SeP催化剂具有较高的活性和选择性;其最佳反应条件为：反应温度160℃。反应时间5h,甲醇与PO的量之比为1：1。在最佳条件下。PO转化率为82．6％,DMC的产率达到7．68％。     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Edge-enriched graphene with boron and nitrogen co-doping for enhanced oxygen reduction reaction

Carbon-based electrocatalysts for oxygen reduction reaction (ORR), especially in anion exchange membrane fuel cells (AEMFCs), have received a lot of attention because they exhibit excellent stability and are comparable to commercial Pt/C catalysts. Currently, to maximize the catalytic activity of carbon-based electrocatalysts, there are two major strategies: heteroatom doping or exposing active edge sites. However, the approach of increasing heteroatomic dopants of active edge sites has been rarely addressed. In this study, we present a simple strategy to prepare edge-enriched graphene catalysts with an increased ratio of heteroatomic dopants suitable for ORR of AEMFCs. The catalysts were prepared under harsh oxidation conditions, followed by a simple co-doping process with boron and nitrogen. The ORR activity of the catalysts was observed to be related to an increase of edge sites with heteroatomic dopants. We believe that the edge-enriched structure leads to accelerated electron transfer with enhanced oxygen adsorption.     

Global optical model potential describing 12C-nucleus elastic scattering

We construct a new global optical model potential to describe the elastic scattering of ¹²C. The experimental data of elastic-scattering angular distributions and total reaction cross sections for targets from ²⁴Mg to ²⁰⁹Bi are considered below 200 MeV within the framework of the optical model. The results calculated using the derived global optical potential are then compared with the existing experimental data. The reliability of the global optical potential is further tested by predicting the elastic scattering data out of the mass and energy ranges, within which the global potential parameters are determined, and reasonable results are also obtained.     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

Calculus of variations as a basic tool for modelling of reaction paths and localisation of stationary points on potential energy surfaces

ABSTRACT

The theory of calculus of variations is a mathematical tool which is widely used in different scientific areas in particular in physics and chemistry. This theory is strongly related with optimisation. In fact the former seeks to optimise an integral related with some physical magnitude over some space to an extremum by varying a function of the coordinates. On the other hand, reaction paths and potential energy surfaces, in particular their stationary points, are the basis of many chemical theories, in particular reactions rate theories. We present a review where it is gathered together the variational nature of many types of reaction paths: steepest descent, Newton trajectories, artificial force induced reaction (AFIR) paths, gradient extremals, and gentlest ascent dynamics (GAD) curves. The variational basis permits to select the best optimisation technique in order to locate important theoretical objects on a potential energy surface.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.