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1.
The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).  相似文献   
2.
A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties.  相似文献   
3.
Dehydrogenation of an organic compound is the first and the most fundamental elementary reaction in many organic reactions. In ethanol oxidation reaction (EOR) to form CO2, there are a total of 46 pathways in C2HxO (x=1–6) species leading to the removal of all six hydrogen atoms in five C−H bonds and one O−H bond. To investigate the degree of dehydrogenation in EOR under operando conditions, we performed density function theory (DFT) calculations to study 28 dehydrogenation steps of C2HxO on Ir(100). An activation energy surface was then constructed and compared with that of the C−C bond cleavages to understand the importance of the degree of dehydrogenation in EOR. The results show that there are likely 28 dehydrogenations in EOR under fuel cell temperatures and the last two hydrogens in C2H2O are less likely cleaved. On the other hand, deep dehydrogenation including 45 dehydrogenations can occur under ethanol steam reforming conditions.  相似文献   
4.
双电解液锂空气电池因其高理论能量密度受到广泛研究,但电池正极侧氧还原反应(ORR)速率低,其反应速率是限制锂空气电池发展的主要因素之一.本文提出了以钌(Ru)掺杂单层石墨烯作为正极ORR催化剂,采用第一性原理计算nRu (n=1~3)掺杂石墨烯的电子结构和氧气在Ru掺杂石墨烯表面的吸附性能,并以过渡态搜索方法获得ORR反应路径,研究碱性溶液中Ru掺杂单层石墨烯作用下的ORR机理.研究结果表明,经Ru原子掺杂后,石墨烯能够获得稳定的掺杂结构,且电导率显著提升.同原始单层石墨烯相比,Ru掺杂石墨烯增强了对O2的吸附能力.在三Ru(n=3)掺杂石墨烯表面进行的ORR无需克服任何能垒.此外,三Ru掺杂石墨烯表面对OH基团的吸附能最低,有利于ORR的连续进行.研究表明三Ru掺杂石墨烯有望成为一种新型的ORR催化剂以提高双电解液锂空气电池的性能.  相似文献   
5.
延安是中国共产党领导革命的中心和战略总后方,是革命的红色摇篮。延安时期出版了大量具有历史、文化以及教育意义的红色文献,这些红色文献记载了中国共产党波澜壮阔的发展历程,也反映了延安时期不断发展的科技生产水平与独特的制浆造纸工艺,具有重要的研究价值。然而,延安时期出版的红色文献虽距今不到百年时间,但其保存现状不容乐观,普遍存在纸张老化、焦脆易碎等问题,大量文献急需科学检测与修复保护,以延长其保存寿命。目前,针对延安时期红色文献的检测研究仍存在较大空白。考虑到红色文献的珍贵性与特殊性,应当尽可能选择无损检测方法对其分析检测。基于衰减全反射-傅里叶变换红外光谱法(ATR-FTIR),以木素1 510 cm-1处特征峰与纤维素1 030 cm-1处特征峰的强度作为定量依据,建立了造纸原料与红色文献纸张中木素相对含量的无损检测方法。通过检测不同碱强度与碱浓度处理后的构皮、苦竹与杨木的木素含量,考察了制浆过程中碱处理条件对造纸原料脱木素程度的影响,同时体现了红外光谱法测定木素相对含量的普适性。以复旦大学图书馆藏的76册延安时期红色文献为研究对象,分析了红色文献的纸张木素含量与纸张pH值以及纸张氧化度的相互关系。结果表明,木素相对含量高于25%的红色文献,其纸张pH集中在3~4之间且纸张氧化度较高,文献整体保存状况堪忧;而木素相对含量低于25%的红色文献,其纸张氧化度与酸度较低,文献整体保存情况较好。以上结果验证了红外光谱无损检测法用于延安时期红色文献木素含量分析的可行性,并结合纸张氧化度与酸度数据提出了纸张木素含量的合适范围,为制浆造纸中植物原料的脱木素过程提供参考。拓展了红外光谱法在红色文献无损检测中的应用范围,以期为延安时期红色文献的修复与保护研究提供科学依据。  相似文献   
6.
毛赫南  王晓工 《物理化学学报》2022,38(4):2004025-52
氧化石墨烯(GO)片的基面和边缘上存在大量的含氧官能团,能很好地分散在水中,因而具有很好的加工性和广阔的应用前景。在较高浓度范围下,GO水分散液中存在着强烈的竞争性相互作用,从而对流变行为产生较大影响。在本文中,通过稳态、动态等流变实验以及理论分析,研究了pH值、温度和不同的有机溶剂对GO分散液流变行为的影响。结果表明,降低pH值、适当增加温度以及加入吡啶均可促进GO水分散液从粘弹性液体到凝胶态的转变。利用DLVO (Deryagin-Landau-Verwey-Overbeek)理论,探讨了GO片之间的范德华作用力以及双电层排斥作用的相互关系,及其对流变性能的影响。通过群体平衡模型(PBE)分析了GO分散液的屈服应力与体积分数的正相关关系。同时,通过蠕变和松弛实验发现,高浓度的GO分散液中结构变化及流变行为在很多方面与高聚物相似,利用Poyting-Thomson模型能较好地拟合其粘弹性行为。上述研究结果为深入研究复杂的GO分散体系提供理论支撑和实验依据。  相似文献   
7.
建立了氟化氢铵消解地球化学样品,电感耦合等离子体质谱(ICP-MS)法测定样品中钨、锡和钼的方法。方法经过国家土壤和水系沉积物标准参考物质验证,方法的检出限钨为0.048μg/g、锡为0.079μg/g、钼为0.063μg/g,准确度(相对误差)钨为0.64%~6.28%、锡为0.29%~3.74%、钼为2.12%~7.41%,精密度(相对标准偏差)钨为0.13%~0.72%、锡为0.05%~1.2%、钼为0.03%~1.1%,能够满足《地质矿产实验室测试质量管理规范》的质量要求。方法具有操作简便、测试成本低、分析效率高、环境污染小等特点,适合于批量样品的分析测试。  相似文献   
8.
李军  姚道新 《中国物理 B》2022,31(1):17403-017403
This article reviews the basic theoretical aspects of octagraphene, an one-atom-thick allotrope of carbon, with unusual two-dimensional(2 D) Fermi nesting, hoping to contribute to the new family of quantum materials. Octagraphene has an almost strongest sp2hybrid bond similar to graphene, and has the similar electronic band structure as iron-based superconductors, which makes it possible to realize high-temperature superconductivity. We have compared various possible mechanisms of superconductivity, including the unconventional s;superconductivity driven by spin fluctuation and conventional superconductivity based on electron–phonon coupling. Theoretical studies have shown that octagraphene has relatively high structural stability. Although many 2 D carbon materials with C;carbon ring and C;carbon ring structures have been reported, it is still challenging to realize the octagraphene with pure square-octagon structure experimentally.This material holds hope to realize new 2 D high-temperature superconductivity.  相似文献   
9.
Ruppeiner geometry has been successfully applied in the study of the black hole microstructure by combining with the small–large black hole phase transition, and the potential interactions among the molecular-like constituent degrees of freedom are uncovered. In this paper, we will extend the study to the triple point, where three black hole phases coexist acting as a typical feature of black hole systems quite different from the small–large black hole phase transition. For the six-dimensional charged Gauss–Bonnet anti-de Sitter black hole, we thoroughly investigate the swallow tail behaviors of the Gibbs free energy and the equal area laws. After obtaining the black hole triple point in a complete parameter space, we exhibit its phase structures both in the pressure–temperature and temperature–horizon radius diagrams. Quite different from the liquid–vapor phase transition, a double peak behavior is present in the temperature–horizon radius phase diagram. Then we construct the Ruppeiner geometry and calculate the corresponding normalized curvature scalar. Near the triple point, we observe multiple negatively divergent behaviors. Positive curvature scalar is observed for the small black hole with high temperature, which indicates that the repulsive interaction dominates among the microstructure. Furthermore, we consider the variation of the curvature scalar along the coexisting intermediate and large black hole curves. Combining with the observation for different fluids, the result suggests that this black hole system behaves more like the argon or methane. Our study provides a first and preliminary step towards understanding black hole microstructure near the triple point, as well as uncovering the particular properties of the Gauss–Bonnet gravity.  相似文献   
10.
Liang'an Huo 《中国物理 B》2022,31(3):30202-030202
The appearance of rumors intensifies people's panic and affects social stability. How to control the spread of rumors has become an important issue which is worth studying. In order to more accurately reflect the actual situation in the real world, a stochastic model incorporating media coverage and Lévy noise is proposed to describe the dynamic process of rumor propagation. By introducing two control strategies of popular science education and media coverage in an emergency event, an near-optimal control problem that minimizes the influence and control cost of rumor propagation is proposed. Sufficient conditions for near-optimal control of the model are established by using a Hamiltonian function. Then the necessary conditions for near-optimal control are obtained by using the Pontryagin maximum principle. Finally, the effect of popular science education, media coverage and Lévy noise on rumor propagation process control is verified by numerical simulation.  相似文献   
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