Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

Sulfur-Modified Oxygen Vacancies in Iron–Cobalt Oxide Nanosheets: Enabling Extremely High Activity of the Oxygen Evolution Reaction to Achieve the Industrial Water Splitting Benchmark

The oxygen vacancies of defective iron–cobalt oxide (FeCoO_x-Vo) nanosheets are modified by the homogeneously distributed sulfur (S) atoms. S atoms can not only effectively stabilize oxygen vacancies (Vo), but also form the Co−S coordination with Co active site in the Vo, which can modulate the electronic structure of the active site, enabling FeCoO_x-Vo-S to exhibit much superior OER activity. FeCoO_x-Vo-S exhibits a mass activity of 2440.0 A g⁻¹ at 1.5 V vs. RHE in 1.0 m KOH, 25.4 times higher than that of RuO₂. The Tafel slope is as low as 21.0 mV dec⁻¹, indicative of its excellent charge transfer rate. When FeCoO_x-Vo-S (anode catalyst) is paired with the defective CoP₃/Ni₂P (cathode catalyst) for overall water splitting, current densities of as high as 249.0 mA cm⁻² and 406.0 mA cm⁻² at a cell voltage of 2.0 V and 2.3 V, respectively, can be achieved.     

BESIII 实验对奇特态 X(3872) 的研究

量子色动力学允许超出夸克模型中重子和介子的奇特态的存在。对奇特态的研究是当前高能物理实验的热门话题之一。X(3872)是第一个被实验上观测到的奇特态候选者。实验和理论上对X(3872)的研究从未间断,这使得X(3872)成为了解最好的奇特态。运行在北京正负电子对撞机(BEPCII)上的北京谱仪(BESIII)实验积累了大量的质心能量从3.87 到 4.70 GeV的正负电子对撞数据样本。利用这些数据样本,得到了很多关于X(3872)的实验结果。本文将回顾BESIII上关于X(3872)所取得一系列成果及最新实验进展。对X(3872)等奇特态的研究,将有利于我们对自然界的基本相互作用的理解,也将促进标准模型理论的完善。     

One-step In-situ Synthesis of Vacancy-rich CoFe2O4@Defective Graphene Hybrids as Bifunctional Oxygen Electrocatalysts for Rechargeable Zn-Air Batteries

Developing efficient catalysts toward both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) is the core task for rechargeable metal-air batteries. Although integration of two active components should be an effective method to produce the bifunctional catalysts in principle, traditional techniques still can not attain fine tunable surface structure during material-hybridization process. Herein, we present a facile short-time in-situ argon(Ar) plasma strategy to fabricate a high-performance bifunctional hybrid catalyst of vacancy-rich CoFe₂O₄ synergized with defective graphene(r-CoFe₂O₄@DG). Reflected by the low voltage gap of 0.79 V in two half-reaction measurements, the striking capability to catalyze ORR/OER endows it excellent and durable performance in rechargeable Zn-air batteries, with a maximum power density of 155.2 mW/cm² and robust stability(up to 60 h). Further experimental and theoretical studies validate its remarkable bifunctional energetics root from plasma-induced surface vacancy defects and interfacial charge polarization between DG and CoFe₂O₄. This work offers more opportunities for reliable clean energy systems by rational interfacial and defect engineering on catalyst design.     

Solution,thermal and optical properties of new poly(pyridinium salt)s derived from conjugated quinoline diamines

Several new poly(pyridinium salt)s with quinoline diamine moieties in their backbones with tosylate and triflimide counterion were prepared by either a ring‐transmutation polymerization reaction with bis(pyrylium tosylate) with a series of isomeric quinoline diamines in dimethyl sulfoxide (DMSO) for 48 h at 130–140 °C or a metathesis reaction of the tosylate polymers with lithium triflimide in DMSO at about 60 °C. Their chemical structures were confirmed by FTIR, ¹H and ¹³C NMR spectroscopy, and elemental analysis. Their number‐average molecular weights (M_n) were in the range of 18,000–58,000, and their polydispersities were in the range of 1.12–1.53 as determined by gel permeation chromatography. They had thermal stability in the temperature range of 353–455 °C and glass‐transition temperatures >240 °C. They had good solubility in common organic solvents and were characterized with polarizing optical microscopy (POM) studies for their lyotropic liquid‐crystalline properties. Their light‐emission properties were examined by spectrofluorometry in both the solution and film states. Their quantum yields were also determined. Additionally, their morphologies in the thin‐film states and melt‐drawn fibers were examined with POM, scanning electron microscopy, and transmission electron microscopy techniques. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

负载铂的缺陷活性炭作为一种在碱性条件下具有优异氧还原反应性能的催化剂

燃料电池因其高的能量转化效率和无污染的特点而被认为是目前最有发展前景的高效清洁发电技术,然而燃料电池迟缓的阴极氧还原反应(ORR)极大地降低了其整体性能.目前,铂碳(Pt/C)仍然是催化ORR最有效的催化剂.但是,由于Pt的价格很高以及其稳定性差等缺点极大地限制了燃料电池的大规模化应用,因此设计与开发廉价高效稳定的ORR电催化剂对实现燃料电池的大规模商业化应用具有重要的意义.在过去的几十年中,研究发现Pt和其他的非贵金属形成合金,如Pt-Fe,Pt-Ni和Pt-Co等不仅可以降低Pt的用量,而且也可以使所得催化剂具有较高的ORR活性.此外,研究发现核-壳结构也可以提高铂基ORR催化剂的活性与稳定性.但是,这些催化剂的制备一般会使用毒性和危险性较高的有机化学试剂并且其制备过程繁杂,因此并不适用于大规模的实际生产.从这个角度来说,开发一种简易的方法来制备高效廉价的ORR催化剂显得尤为重要.之前的研究表明,Pt的载体对提高所得ORR催化剂来说非常关键.可以发现大部分载体都是经过改进的碳材料,如微孔/介孔材料,杂原子掺杂的石墨烯以及缺陷碳等.尤其是我们课题组最近提出的一种缺陷催化机理表明,在碳材料中特定类型的缺陷(如缺陷活性炭(D-AC)和缺陷石墨烯等)可以使纯的碳材料具有很高的电催化活性.尽管D-AC的ORR催化活性在不含金属的催化剂中位居前列,但是其催化性能仍然比商业化的Pt/C差.鉴于此,如果我们可以通过使用具有较高ORR催化活性的D-AC作为Pt的载体而降低Pt的用量,但并不牺牲其催化活性,这将是一个很具有前景的方法来解决昂贵ORR催化剂的问题,进而有可能实现燃料电池的大规模化生产.在本研究中,我们通过一种简易的液相浸渍法以D-AC作为Pt的载体而制备了一种高效的ORR催化剂.具体来说,我们通过调节合成过程中的还原温度实现了控制所得催化剂中Pt颗粒尺寸的目的,同时我们也对催化剂中的Pt含量对其催化性能的影响进行了探讨.研究表明,所得催化剂中Pt的颗粒尺寸以及其结晶性都可能影响其ORR催化活性.更为重要的是,所得样品D-AC@5.0%Pt中含有约5 wt%的Pt,然而其在碱性条件下的ORR催化活性已经超过了商业化的含有20 wt%Pt的Pt/C,例如其起始电位和半波电位都优于商业化的Pt/C,并且其稳定性也比商业化的Pt/C好.除此之外,D-AC@5.0%Pt在催化ORR的过程中表现出了一种一步四电子的反应路径,而且中间产物过氧化氢的产率很低.所得催化剂D-AC@5.0%Pt优异的ORR反应活性表明D-AC中的特殊缺陷以及负载的Pt纳米颗粒都对提高其催化活性具有很大的贡献,同时也说明选择合适的载体对提高电催化剂的活性至关重要.实验结果还表明,D-AC@5.0%Pt在酸性条件下的ORR催化活性也有一定的提高,虽然比商业化的Pt/C要差一些.更进一步减小Pt的颗粒尺寸到亚纳米甚至原子级别可能会明显地提高其在酸性电解液中的ORR催化活性.     

Charge Polarization from Atomic Metals on Adjacent Graphitic Layers for Enhancing the Hydrogen Evolution Reaction

Atomic metal species‐based catalysts (AMCs) show remarkable possibilities in various catalytic reactions. The coordination configuration of the metal atoms has been widely recognized as the determining factor to the electronic structure and the catalytic activity. However, the synergistic effect between the adjacent layers of the multilayered AMCs is always neglected. We reported an atomic Co and Pt co‐trapped carbon catalyst, which exhibits a ultrahigh activity for HER in the wide range of pH (η₁₀=27 and 50 mV in acidic and alkaline media, respectively) with ultralow metal loadings (1.72 and 0.16 wt % for Co and Pt, respectively), which is much superior to the commercial Pt/C. Theoretical analysis reveals that the atomic metals on the inner graphitic layers significantly alter the electronic structure of the outmost layer, thus tailoring the HER activity. This finding arouses a re‐thinking of the intrinsic activity origins of AMCs and suggests a new avenue in the structure design of AMCs.     

First evidence for the formation of technetium oxosulfide complexes: synthesis, structure and characterization

The reaction of tetrabutylammonium pertechnetate with bis(trimethylsilyl) sulfide in solution was studied by UV-Visible spectroscopy and mass spectrometry. Experimental results and density functional calculations provide the first evidence for the formation of a TcO(3)S(-) precursor. Larger scale synthesis afforded a solid that was characterized by EDX and XANES spectroscopy. XANES showed the presence of technetium in tetravalent state. EDX indicated the solid contained technetium, sulfur and oxygen.     

8mm磁控管微波源单次工作实验

８ｍｍ波磁控管（国产１１３Ａ型）微波源是为ＳＧ一１ＦＥＬ放大器研究的，ＦＥＬ要求微波源单次状态下工作。而国产８ｍｍ磁控管正处于研制阶段，尚无单次工作的先例。１１３Ａ型微波源输出功率≥２０ｋＷ，脉冲平顶宽度≥０．３５ｕｓ，频率３４３６ＧＨｚ，满足了ＦＥＬ的要求，在８６一１ＦＥＬ实验中运行良好。