镨叶绿素a分子结构的确定

通过合成镨叶绿素a(Pr-Chla)研究了稀土在叶绿素中的结合方式.Pr-Chla的紫外可见光谱(UV-Vis)、红外光谱(FTIR)证实镨离子已配位到叶绿素a的卟啉环上.其磁圆二色谱(MCD)在Soret带具有双层夹心卟啉的特征结构;通过扩展X射线吸收精细结构谱(EXAFS),采用双层夹心结构模型拟合,确定了Pr周围的近邻结构.表明合成镨叶绿素a具有双层夹心结构.Pr(Ⅲ)夹于两个卟啉环之间,与上下卟啉环上共8个N原子配位,Pr-N键平均键长0.242nm.     

V2O5/TiO2催化剂活性组分与载体相互作用研究

制备了一系列负载型V-Ti-O催化剂, 运用现代分析测试手段如BET、TPD、NARP、XRD等进行表征. 研究发现负载于TiO_2上的V_2O_5由于相互作用而使其表面V=O物种选择外露, 载体TiO_2的晶体结构是决定它们之间相互作用的关键因素. 锐铁矿型TiO_2上获得最大V=O暴露的表面V_2O_5浓度显著低于金红石TiO_2载体上获得最大V=O暴露时的表面V_2O_5浓度. 而具有较大比表面及较强酸中心的TiO_2载体导致较强的相互作用. 即可获得较大的表面V=O暴露度.     

白酒中游离有机酸的定量测定

本文介绍了一种简单、准确测定白酒中游离有机酸的方法。酒样经中和、浓缩后,未经衍生直接注入毛细管色谱柱,经气相色谱-质谱鉴定并采用三种内标物定量,可准确测定白酒中C2～C18的二十种游离脂肪酸及三种苯羧酸,结果重现性良好。     

基于金属有机骨架前驱体制备纳米磷化镍催化剂

采用镍基金属有机骨架化合物(Ni-MOF)为前驱体,通过低温碳化获得Ni@C,并通过磷化成功地制备了不同结构的磷化镍纳米颗粒。将所得材料应用于析氢反应(HER)催化剂,在Ni@C与红磷质量比为1∶1及热解温度为500℃时获得的Ni1P1-500表现出优异的电催化性能,在酸性介质中,电流密度为10 mA·cm-2时,过电位为178 mV,并展现了良好的循环性能。较小的Tafel斜率(62 mV·dec-1)揭示了析氢反应的机理为Desorption-Heyrovsky机制。优异的电催化性能可归因于磷化镍催化剂表面存在的质子受体(P位点)和氢化物受体(Ni位点)活性中心。     

用于超级电容器的层状Co3O4/Ti纳米片柔性电极及其低电荷转移电阻

采用水热合成法,在Ti网上原位生长多孔层状Co_3O_4纳米片,并优化了电荷转移电阻。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对产物的结构、形貌进行表征,及对电极的电化学性能进行测试。结果表明,材料是由排列良好的微米矩形二维薄片组成,且具有均匀的孔隙分布。这种独特的微纳米结构的超级电容器电极材料降低了电极的电荷转移电阻,增强了活性物质的结构稳定性,从而提高了电极的电化学性能,在电流密度为100 mA·g-1时,电极循环1 000次后,电容保持率为91.8%,电荷转移电阻(Rct)为0.29Ω。这些显著的超电容性能归因于合理的二维层状结构在柔性基底钛网上的生长及柔性Co_3O_4/Ti电极活性材料的高利用率。     

General π‐Electron‐Assisted Strategy for Ir,Pt, Ru,Pd, Fe,Ni Single‐Atom Electrocatalysts with Bifunctional Active Sites for Highly Efficient Water Splitting

Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm^?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC₃ sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.     

Synthesis and Infrared Multi‐band Absorption Properties of Core‐shell NaYF4:Yb3+, Er3+@SiO2 Nanoparticles

Due to the unique size effects, nanomaterials in infrared absorption have attracted much attention for their strong absorption in the infrared region. To achieve the infrared multi‐band absorption, we propose to synthesize a core‐shell structure nanomaterial consisting of NaYF₄:Yb³⁺, Er³⁺ core and a layer of SiO₂ as shell. A series of NaYF₄:Yb³⁺, Er³⁺ nanocrystals were synthesized through hydrothermal method by adjusting the ratio of citric acid(CA)‐to‐NaOH, and the effects of CA concentration, and NaOH concentration were studied in detail. NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were synthesized by sol‐gel method using TEOS as silica source. The results show that the core‐shell NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were successfully synthesized. Up‐conversion spectra of these nanoparticles were recorded with 980 nm laser excitation under room temperature. There are no changes of the emission centers of nanoparticles before or after silica coating, but the emission intensities of nanoparticles after silica coating are weakened. Furthermore, the property of infrared multi‐band absorption was tested through ultraviolet‐visible‐near infrared spectrophotometer and infrared absorption spectra. The results illustrate that the multi‐band infrared absorption nanomaterial was successfully synthesized.     

炭材料负载金属催化剂催化硅氢加成反应进展

炭材料具有比表面积大、孔径可调、取材广泛等优点,以其为载体负载金属活性组分制备硅氢加成催化剂极具发展前景.我们详细总结了近20年不同炭材料如活性炭、石墨与石墨烯、碳纳米管、富勒烯、卡宾等在硅氢加成反应中负载金属催化剂的制备方法、催化性能以及可能的催化机理,并对有望应用到该反应的新型炭材料载体进行了对比与展望.认为未来硅氢加成炭负载型催化剂的研究可聚焦于(1)探寻新型双金属活性组分以进一步提高催化活性;(2)研发更具优势的金属配体,明晰配体与载体、配体与金属之间的相互作用关系以提高催化选择性与稳定性;(3)结合科学可靠的催化机理研究,以期研发出更符合可持续发展要求的炭负载型硅氢加成金属催化剂,可使硅氢加成反应基本实现原子经济性.     

A novel intumescent flame retardant imparts high flame retardancy to epoxy resin

Intumescent flame retardant (IFR) has received the considerable attention ascribed to the inherent advantages including non‐halogen, low toxicity, low smoke release and environmentally friendly. In this work, a novel charring agent poly (piperazine phenylaminophosphamide) named as PPTA was successfully synthesized and characterized by Fourier transform infrared spectra (FTIR) and X‐ray photoelectron spectroscopy (XPS). Then, a series of flame‐retardant EP samples were prepared by blending with ammonium polyphosphate (APP) and PPTA. Combustion tests include oxygen Index (LOI), vertical Burning Test (UL‐94) and cone calorimeter testing,these test results showed that PPTA greatly enhances the flame retardancy of EP/APP. According to detailed results, EP containing 10 wt% APP had a LOI value of 30.2%,but had no enhancement on UL‐94 rating. However, after both 7.5 wt% APP and 2.5 wt% PPTA were added, EP‐7 passed UL‐94 V‐0 rating with a LOI value of 33.0%. Moreover, the peak heat release rate (PHRR) and peak of smoke product rate (PSPR) of EP‐7 were greatly decreased. Meanwhile, the flame‐retardant mechanism of EP‐7 was investigated by scanning electron microscopy (SEM), thermogravimetric analysis/infrared spectrometry (TG‐IR) and X‐ray photoelectron spectroscopy (XPS). The corresponding results presented PPTA significantly increased the density of char layer, resulting in the good flame retardancy.     

Direct Dynamic Evidence of Charge Separation in a Dye‐Sensitized Solar Cell Obtained under Operando Conditions by Raman Spectroscopy

Interfaces play an important role in enhancing the energy conversion performance of dye‐sensitized solar cells (DSCs). The interface effects have been studied by many techniques, but most of the studies only focused on one part of a DSC, rather than on a complete solar cell. Hence, monitoring the interface evolution of a DSC is still very challenging. Here, in situ/operando resonance Raman (RR) spectroscopic analyses were carried out to monitor the dynamics of the photovoltaic conversion processes in a DSC. We observed the creation of new species (i.e., polyiodide and iodine aggregates) in the photosensitization process. We also obtained molecular‐scale dynamic evidence that the bands from the C=C and C=N bonds of 2,2′‐bipyridyl (bpy), the S=C=N bonds of the NCS ligand, and photochemical products undergo reasonably strong intensity and frequency changes, which clearly demonstrates that they are involved in charge separation. Furthermore, RR spectroscopy can also be used to quickly evaluate the performance of DSCs.