Enhanced Electrocatalytic Performance of Anthraquinonemonosulfonate‐Doped Polypyrrole Composite: Electroanalysis for the Specific Roles of Anthraquinone Derivative and Polypyrrole Layer on Oxygen Reduction Reaction

To analyze the specific roles of anthraquinone‐2‐sulfonate (AQS) and polypyrrole (PPy) layer on oxygen reduction reaction (ORR), the electrocatalytic reduction of oxygen was investigated on the AQS/PPy composite modified graphite electrode. Results show that the enhanced electrocatalytic performance is attributed to the excellent electrocatalytic activity of the immobilized AQS functional groups to mediate two‐electron reduction of O₂ to H₂O₂. The PPy layer may not participate in ORR, but it can further catalyze the two‐electron reduction of H₂O₂ to produce H₂O in the potential range more negative than that the two‐electron reduction of oxygen proceeds efficiently on the AQS sites.     

Asymmetric α-amination of 4-substituted pyrazolones catalyzed by a chiral Gd(OTf)3/N,N'-dioxide complex: highly enantioselective synthesis of 4-amino-5-pyrazolone derivatives

The asymmetric α-amination of 4-substituted pyrazolones with azodicarboxylates was investigated for the first time, employing an N,N'-dioxide gadolinium(III) complex as the catalyst. The novel transformations exhibited high yield, and 4-amino-5-pyrazolone derivatives bearing a chiral quaternary center were obtained in excellent yields (up to 99%) and enantioselectivities (90%-97% ee) for a broad scope of 5-pyrazolones by using 1 mol % or only 0.05 mol % of catalyst.     

一个投影收缩算法的新步长

本文研究了求解单调变分不等式问题的一个投影收缩算法.利用何炳生教授的分析手法,给出了新步长,并且证明了在该步长下算法的全局收敛性.初步的数值试验表明了新步长的实用性.     

Mechanism for degradation of Nafion in PEM fuel cells from quantum mechanics calculations

We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism.     

Electronic structures of Group 9 metallocorroles with axial ammines

The electronic structures of metallocorroles (tpfc)M(NH(3))(2) and (tfc)M(NH(3))(2) (tpfc is the trianion of 5,10,15-(tris)pentafluorophenylcorrole, tfc is the trianion of 5,10,15-trifluorocorrole, and M = Co, Rh, Ir) have been computed using first principles quantum mechanics [B3LYP flavor of Density Functional Theory (DFT) with Poisson-Boltzmann continuum solvation]. The geometry was optimized for both the neutral systems (formal M(III) oxidation state) and the one-electron oxidized systems (formally M(IV)). As expected, the M(III) systems have a closed shell d(6) configuration; for all three metals, the one-electron oxidation was calculated to occur from a ligand-based orbital (highest occupied molecular orbital (HOMO) of B(1) symmetry). The ground state of the formal M(IV) system has M(III)-Cπ character, indicating that the metal remains d(6), with the hole in the corrole π system. As a result the calculated M(IV/III) reduction potentials are quite similar (0.64, 0.67, and 0.56 V vs SCE for M = Ir, Rh and Co, respectively), whereas the differences would have been large for purely metal-based oxidations. Vertically excited states with substantial metal character are well separated from the ground state in one-electron-oxidized cobalt (0.27 eV) and rhodium (0.24 eV) corroles, but become closer in energy in the iridium (0.15 eV) analogues. The exact splittings depend on the chosen functional and basis set combination and vary by ~0.1 eV.     

Microbial transformation of deoxyandrographolide by Alternaria alternata AS 3.4578

Biotransformation of deoxyandrographolide (1) by Alternaria alternata AS 3.4578 gave five derivatives identified by spectral methods including 2D NMR as the known dehydroandrographolide (2) and 9beta-hydroxy-dehydroandrographolide (3) and the new compounds 9beta-hydroxy-deoxyandrographolide (4), 3alpha,17,19-trihydroxy-8,13-ent-labdadien-15,16-olide (5) and 3-oxo-9beta-hydroxy-deoxyandrographolide (6).     

石墨烯及其复合材料吸油性能研究进展

石油化工产品在国民经济生活中占有重要地位,但在石油开采和运输过程中漏油事件频发,对海洋生态环境造成重大污染.物理吸附除油方式以其成本低、污染小、可回收利用、操作简单等优点得到广泛应用.传统吸附材料往往具有双亲性,选择吸附性较差,需要进行表面疏水处理.石墨烯凭借其超大比表面积和亲油疏水的特性引起广泛关注.重点综述了石墨烯...     

Study of the d-f Emission,and f-d Ground-State and Excited-State Absorption of Nd3+ in Crystals Using the Simple Model

The simplified model for 4f-5d transitions is applied to obtain the line strengths for emission, ground-state absorption and excited states absorption involving 4f-5d transitions of Nd³⁺ in crystals. The results are host independent for the usual case where 5d crystal-field interaction can be considered as strong, in the sense that the calculated 5d-4f emission relative line strengths will be the same for Nd³⁺ in any host. Also the calculated 4f-5d absorption line strengths can be grouped by the 5d crystal-field components. For each 5d crystal-field component, the group of absorption line strengths for different 4f²5d transition final states forms a pattern independent of the 5d crystal-field component and the host. For practical cases, due to strong but still limited 5d crystal-field splitting, the transitions to different 5d crystal-field components may overlap each other. The theoretical results are used to interpret available experimental data.     

Nanosecond laser pulse interactions with breakdown plasma in gas medium confined in a microhole

The previous investigations on nanosecond laser pulse interactions with breakdown plasma in a gas medium confined in a microhole have been limited. This kind of plasma has been studied in this paper. Due to the significant measurement difficulty resulted from the very small spatial and temporal scales involved, a physics-based computational model has been employed as the investigation tool. The model is developed by solving gas dynamic equations numerically using the finite difference method based on an essentially non-oscillatory scheme. The gas dynamic equations are coupled with suitable equation of state, where the electron number density for plasma region is calculated through the Saha equation. Using the model, the spatial confinement effects of the microhole sidewall on the plasma evolution under laser radiation have been investigated. It has been found that under the studied conditions the hole sidewall confinement can greatly enhance the plasma temperature, pressure, and thrust (over the same surface area). The enhancement should be due to the sidewall’s restriction on the plasma lateral expansion and the sidewall’s reflection of the pressure wave induced by plasma. This study implies potential advantages of the breakdown plasma confined in a microhole in many relevant applications, such as laser propulsion and laser-induced breakdown spectroscopy. The developed model also provides a useful guiding tool for future fundamental research and practical applications in many areas related to laser interactions with gas breakdown plasma.     

激波冲击R22重气柱所导致的射流与混合研究

基于大涡模拟, 结合五阶加权基本无振荡格式与沉浸边界法对激波自左向右与R22重气柱作用过程进行了数值模拟. 数值结果清晰地显示了激波诱导Richtmyer-Meshkov不稳定性所导致的重气柱变形过程, 并与Haas 和 Sturtevant 的实验结果符合. 另外, 结果还揭示了入射激波在气柱内右侧边界发生聚焦并诱导射流的过程, 以及在Kelvin-Helmhotz 次不稳定性作用下两个主涡滑移层形成次级涡的过程, 并分析了气柱变形过程中与周围空气的混合机理. 最后, 通过改变反射距离对反射激波与不同变形阶段的气柱的再次作用过程进行了研究. 结果表明: 当激波反射距离较长时, 反射激波与充分变形后的气柱作用, 使其在流向方向上进一步被压缩; 而当激波反射距离较短时, 反射激波会在气柱内发生马赫反射, 两个三波点附近产生两个高压区, 当其传播至气柱左侧边界时对气柱边界造成冲击加速, 诱导两道向左传播的反向射流. 关键词： Richtmyer-Meshkov不稳定性 R22重气柱 反射激波 射流