Chemical Composition of Flowers of Gossypium hirsutum

Chemistry of Natural Compounds -     

可控表面磷原子修饰提升超细W2C纳米颗粒电解水析氢反应性能

研究高活性和稳定性的非贵金属基析氢催化剂对解决当前能源危机和环境污染问题具有重要意义.碳化钨具有与贵金属Pt类似的d带电子结构,因而成为一类新兴的非贵金属析氢催化剂,受到广泛关注.磷掺杂是提高催化剂析氢活性的有效方法之一,然而目前最常见的构筑磷掺杂方法是使用多金属氧酸盐(POMs,如H3PW12O40),其固定的W/P原子比导致W2C中的掺杂浓度难以调控,并且磷掺杂主要是进入碳载体而不是碳化物本身,从而导致无法明确杂原子对其电催化析氢活性的贡献.本文采用植酸(PA)为磷源设计合成了可控磷掺杂W2C纳米颗粒,并探讨了催化剂组分、杂原子掺杂位置与析氢性能之间的关系.深入研究了磷掺杂碳化钨(WCP)的化学结构和析氢活性.与原始的W2C催化剂相比,WCP具有更高的本征活性、更快的电子转移速率和更多的活性位数量,并且在酸性和碱性条件下均表现出较好的析氢性能.特别是过电位为-200 mV时,WCP催化剂的本征活性在酸性和碱性条件下分别为0.07和0.56 H2 s-1,高出纯W2C(0.01和0.05 H2 S-1)数倍.同时,在电流密度为-10 mA cm-2时,优化后的WCP催化剂在酸性和碱性条件下的析氢过电位分别降低了96和88 mV.XPS及EDS元素分析结果表明,随磷源添加量增加,磷掺杂从碳化钨表面逐渐向内部扩散,进一步说明磷取代位置与析氢活性之间的构效关系,高浓度的表面磷取代可以加速质子捕获过程,从而显著提高其析氢活性,而过量的内部磷取代会破坏W2C结构,降低电子转移速率,从而导致析氢性能下降.利用密度泛函理论计算深入研究了WCP具有较好析氢性能的原因,与内部磷取代相比,表面磷取代会使碳化钨表现出更合适的氢吸附自由能,并且更加有效地降低了氢释放势垒,从而优化了析氢反应动力学.综上,本文为元素掺杂工艺提供了新的思路,同时研究了表面异质原子对析氢活性的关键作用,为该类催化材料的构效关系研究提供了新思路.     

手性1,2-二氢吡啶化合物的合成研究进展

手性1,2-二氢吡啶化合物是重要的手性砌块, 可通过还原或环加成反应来方便构建药物分子中十分重要的手性含氮杂环化合物如哌啶等, 因此其高效合成对于新药研发具有重要的研究意义. 利用手性源和手性辅基诱导的策略需要使用化学计量的手性试剂, 发展不对称催化的方法来合成结构多样性的手性1,2-二氢吡啶化合物无疑十分重要. 自2004年报道首例对活化吡啶的不对称C2位亲核加成反应以来, 该策略被成功用于发展合成C2位芳基、烷基、炔基等取代的手性1,2-二氢吡啶化合物的不对称催化新方法. 最近, 一种新的基于亚胺不对称转化的串联反应策略也被设计开发用于多样性合成这类手性含氮杂环化合物. 本综述概述了相关研究进展, 并介绍了相关研究难点和未来的发展空间.     

双金属团簇Cu12Fe吸附CO和H2的理论研究

基于第一性原理密度泛函理论(DFT)方法研究了Cu₁₂Fe团簇的结构稳定性、热力学稳定性和反应活性.计算得出正二十面体Fe原子核心团簇Ih-core比正二十面体Fe原子壳层团簇Ih-shell的热力学稳定性更强.通过分析吸附能讨论了CO和H₂在Ih-core团簇上的吸附构型.计算结果表明,Ih-core团簇以顶角Corner位吸附CO时吸附能最大,吸附模型最稳定,H₂吸附过程中发生了解离,两个氢原子均形成表面Facet位吸附构型.最后,通过分析前线轨道得到吸附过程的轨道信息.     

Solar Driven Gas Phase Advanced Oxidation Processes for Methane Removal - Challenges and Perspectives

Methane (CH₄) is a potent greenhouse gas and the second highest contributor to global warming. CH₄ emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH₄ emissions by developing large-scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH₄ (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar-driven gas phase advanced oxidation processes for CH₄ removal. And (3) to propose some ideas, which may help to develop solar-driven gas phase advanced oxidation processes and make them deployable at a climate significant scale.     

GEOMETRIC FRAMEWORK AND MINIMAL REALIZATIONS OF NONLINEAR SYSTEMS ON FIBRE BUNDLE

ＧＥＯＭＥＴＲＩＣＦＲＡＭＥＷＯＲＫＡＮＤＭＩＮＩＭＡＬＲＥＡＬＩＺＡＴＩＯＮＳＯＦＮＯＮＬＩＮＥＡＲＳＹＳＴＥＭＳＯＮＦＩＢＲＥＢＵＮＤＬＥＭｕＸｉａｏｗｕ（慕小武）（ＤｅｐａｒｔｍｅｎｔｏｆＭａｔｈｅｍａｔｉｃｓ，ＺｈｅｎｇｚｈｏｕＵｎｉｖｅｒｓ...     

Bitumen/polyethylene blends: using m-LLDPEs to improve stability and viscoelastic properties

The stability and the rheological properties of blends of a 60/70 penetration-grade bitumen with conventional HDPEs and metallocene catalysed LLDPEs (m-LLDPE) are investigated. Considerably better stability results are obtained using m-LLDPEs instead of conventional polyethylenes, allowing one to avoid phase separation of the emulsion-like system during storage at high temperature. Thermodynamical interaction between bitumen and polyethylene is discarded as a cause of the observed difference, because the solubility parameter is practically the same for all the investigated polyethylenes. The result is explained on the basis of the lower melt elasticity of m-LLDPEs (attributed to their narrow molecular weight distribution), which facilitates the drop breakup during mixing process. The modification of bitumen with any of the m-LLDPEs considered in this work gives a new material with considerably improved viscoelastic properties.     

Study on the structure and reactivity of COREX coal

COREX is the primary process in the current smelting reduction method. The process has strict coal quality standards. Combustion processes of coal used in the COREX operating system were analyzed using a synchronous thermogravimetric analyzer combined with a mass spectrometer. The microcosmic structure and macerals were observed by an electronic scanning microscope. The qualitative and quantitative determinations of oxygen functional groups, such as phenolic hydroxyl, carboxyl, carbonyl, and methoxy groups were detected by the Fourier Transform Infrared spectrometer (FT-IR) and through chemical analysis methods. In addition, the evolution of the chemical structure and transformation mechanism of organic oxygen functional groups during COREX coal combustion have been thoroughly investigated. This study proposes a new coal-requirement index system and coal blending method, which will increase the expansion of coal selection and decrease the overall usage of coal during COREX.     

含环糊精链节的拓扑高分子

星形、超支化、树枝状、刷状等具有支化拓扑结构的高分子通常具有不同于直链结构高分子的优异性能。将有客体包合功能的环糊精与其结合构筑环糊精拓扑高分子体系,有望在分子识别、基因传输、药控释放等领域得到应用。本文根据高分子拓扑形态的不同,从星形、超支化、树枝状以及其他拓扑形态环糊精聚合物的合成及自组装构筑等方面进行了总结和评述,并在此基础上展望了基于环糊精的拓扑高分子的研究方向和发展趋势。     

Preparing Greenberger-Horne-Zeilinger States by Lypunov Control

International Journal of Theoretical Physics - A scheme is proposed for preparing Greenberger-Horne-Zeilinger (GHZ) states by Lyapunov control based on quantum Zeno dynamics. The advantage of our...