Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices

Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost‐effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10‐anthraquinone‐2,7‐disulfonic acid (AQDS)/1,2‐benzoquinone‐3,5‐disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L^?1 and a solar‐to‐output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.     

Template–Framework Interactions in Tetraethylammonium‐Directed Zeolite Synthesis

Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost‐prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA⁺) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA⁺ in solution, a heteroatom‐dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host–guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore‐filling.     

Peculiar All‐Metal σ‐Aromaticity of the [Au2Sb16]4− Anion in the Solid State

Gas‐phase clusters are deemed to be σ‐aromatic when they satisfy the 4n+2 rule of aromaticity for delocalized σ electrons and fulfill other requirements known for aromatic systems. While the range of n values was shown to be quite broad when applied to short‐lived clusters found in molecular‐beam experiments, stability of all‐metal cluster‐like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n=0). In this work, the applicability of this concept is extended towards solid‐state compounds by demonstrating a unique example of a storable compound, which was isolated as a stable [K([2.2.2]crypt)]⁺ salt, featuring a [Au₂Sb₁₆]^4? cluster core possessing two all‐metal aromatic AuSb₄ fragments with six delocalized σ electrons each (n=1). This discovery pushes the boundaries of the original idea of Kekulé and firmly establishes the usefulness of the σ‐aromaticity concept as a general idea for both small clusters and solid‐state compounds.     

Tuning of Supramolecular Architectures of l‐Valine‐Containing Dicyanoplatinum(II) 2,2′‐Bipyridine Complexes by Metal–Metal, π–π Stacking,and Hydrogen‐Bonding Interactions

A series of newly synthesized dicyanoplatinum(II) 2,2′‐bipyridine complexes exhibits self‐assembly properties in solution after the incorporation of the l ‐valine amino units appended with various hydrophobic motifs. These l ‐valine‐derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature‐dependent studies. On the other hand, systematic transformation from less uniform aggregates to well‐defined fibrous and rod‐like structures via Pt???Pt and π–π stacking interactions has also been observed in the mixed‐solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.     

高效液相色谱法测定镇咳药中左旋羟基苯哌嗪含量

建立了高效液相色谱法(HPLC)测定镇咳药中左旋羟基苯哌嗪含量的方法,运用二极管阵列检测器(PAD),C18反相柱,以甲醇∶水(冰醋酸HAc调节pH值为6.5)∶三乙胺(TEA)(30∶70∶0.5,V/V/V),为流动相测定了3批镇咳药(利咳净糖浆)中左旋羟基苯哌嗪的含量分别为5772.65、809.25、833.2μg/mL,变异系数小于2%,回收率为99.1%~100.2%.该方法快速,精密度及准确度在允许范围内,可作为镇咳药中左旋羟基苯哌嗪的测定方法.     

CHIRALCEL OD手性柱直接拆分萘普生对映体

以CHIRALCELOD为固定相,建立了在正相条件下直接拆分萘普生对映体的HPLC方法。考察了流动相组成、流速、进样量和温度等因素对对映体分离的影响。优化后的色谱条件为:CHIRACELOD色谱柱(250mm×4.6mm,10μm);流动相:正己烷-异丙醇-冰醋酸(97∶3∶1,V/V);流速:1.0mL/min;紫外检测波长:254nm;柱温:35℃。在此条件下,萘普生对映体可得到基线分离。此方法可用于S-萘普生制备时酶膜反应器中萘普生甲酯动态拆分过程的跟踪分析。     

某些酚类的高温液相色谱行为

建立了高温液相色谱系统,在高温条件下,采用甲醇-水作为流动相,在Polymerx RP-1聚合物(PSDVB)色谱柱上考察了6种酚类样品的色谱行为.实验条件:温度40～160 ℃,流速0.2～5.5 mL/min,流动相中甲醇浓度范围40%～80%.考察了温度、流速和流动相组成对酚类样品的保留、分辨、柱效和系统压力的影响,探讨了酚类样品在聚合物柱上的热力学行为.温度升高2.35℃大约相当于流动相中甲醇浓度增加1%,可以通过改变色谱柱温度调节样品保留和改变选择性.柱温升高,降低了流动相的粘度,允许在高温条件下使用较高的流速实现快速分离.在160℃、V(甲醇):V(水)=40:60,为流动相和3 mL/min流速条件下,可于2.5 min内实现6种酚类的完全分离.     

Selective oxidation of methanol to dimethoxymethane under mild conditions over V2O5/TiO2 with enhanced surface acidity

Dimethoxymethane was synthesized from the direct oxidation of methanol with high conversion and selectivity over specially designed bifunctional V(2)O(5)/TiO2 catalysts with redox and enhanced acidic character, in which the surface acidity played an essential role for inhibiting the formation of formaldehyde through the enhanced condensation reaction of formaldehyde with methanol to produce dimethoxymethane.     

Colloid chemical reaction route to the preparation of nearly monodispersed perylene nanoparticles: size-tunable synthesis and three-dimensional self-organization

By employing a colloid chemical reaction method we demonstrate the preparation of organic nanoparticles composed of perylene molecules (PeNPs) based on the reduction of perylene perchlorate by Br- anions in the presence of cetyl trimethyl ammonium bromide (CTA+Br-) in acetonitrile. A discrete nucleation event, followed by a slower controlled growth on the existing particles, is identified during formation of PeNPs. By changing the growth parameters, such as the monomer concentration and the method of injection, quasi-spherical PeNPs with controllable sizes from 25 to 90 nm could be obtained. The homogeneous solution phase of this method makes it capable of large-scale synthesis of PeNPs with a size distribution (<10%) that is improved by formation of a protective layer of CTA+ around the PeNPs. The three-dimensional, hierarchical self-organization of 25-nm PeNPs building blocks is observed to form nanobelts and square nanorods, possibly templated by the CTA+ lamellar micelle structures in acetonitrile. Spectroscopic results reveal two kinds of trends in the development of the optical properties of perylene as they evolve from the molecular to the bulk phase in the nanometer range. The so-called size dependence is evidenced by a switch from Y-type to E-type excimers as the size of the PeNPs increased from 25 to 90 nm. As the 25-nm PeNPs organize into nanobelts or square nanorods the oscillator strength of the Y-type excimers is relatively enhanced. That is, collective phenomena develop as the proximal particles interact in the glassy solids. Our very recent results indicate that this colloid chemical reaction method can also be applied to other organic compounds.     

Development of a new method for analysis of Sudan dyes by pressurized CEC with amperometric detection

A new analytical method, pressurized CEC (pCEC) with amperometric detection (AD) using 1.5 microm RP nonporous silica packed columns has been developed for the rapid separation and determination of four Sudan dyes in hot chilli. The influence of several experimental parameters on the retention behavior has been investigated. The electrochemical oxidation of Sudans I-IV separated by pCEC can be reliably monitored with a carbon electrode at +0.95 V (vs. Ag/AgCl). Fast and efficient separation of the analytes was achieved within 7 min by pCEC under the optimum conditions with an ACN/water (95:5%) mobile phase containing formic acid (pH 4.3), 5% acetone and 0.002% triethylamine using a separation voltage of 12 kV. The detection limits for four Sudan dyes ranged from 8.0 x 10(-7) to 1.2 x 10(-6) mol/L. To evaluate the feasibility and reliability of this method, the proposed pCEC-AD method was further demonstrated with hot chilli samples spiked with Sudan dyes.