Organic Proton‐Buffer Electrode to Separate Hydrogen and Oxygen Evolution in Acid Water Electrolysis

Hydrogen production from water via electrolysis in acid is attracting extensive attention as an attractive alternative approach to replacing fossil fuels. However, the simultaneous evolution of H₂ and O₂ requires a fluorine‐containing proton exchange membrane to prevent the gases from mixing while using the same space to concentrate the gases, which significantly increases the cost and reduces the flexibility of this approach. Here, a battery electrode based on the highly reversible enolization reaction of pyrene‐4,5,9,10‐tetraone is first introduced as a solid‐state proton buffer to separate the O₂ and H₂ evolution of acidic water electrolysis in space and time, through which the gas mixing issue can be avoided without using any membrane. This process allows us to separately consider H₂ and O₂ production according to the variation in input power (e.g., the renewable energy) and/or the location for H₂ concentration, thus showing high flexibility for H₂ production.     

Unusual Hypochlorous Acid (HClO) Recognition Mechanism Based on Chlorine–Oxygen Bond (Cl−O) Formation

One of the most important endogenous reactive oxygen species, hypochlorous acid (HClO), is involved in numerous pathological and physiological processes. Herein, a near-infrared fluorescence probe (CyHR) was designed and synthesized for ultrafast (within 0.2 s), sensitive (limit of detection=39.44 nm ), and selective response to HClO. The reaction mechanism was systematically analyzed by MS, ¹H NMR spectroscopy, HPLC-MS techniques, and theoretical calculations. The results indicated that HClO can be recognized by CyHR, which is based on chlorine–oxygen (Cl−O) bond formation. To the best of our knowledge, this study is the first to find Cl−O bonds among organic aromatic compounds, given that Cl−O bonds are common among inorganics. Through biological experiments, CyHR was successfully applied to image exogenous and endogenous HClO in macrophage cells (RAW 264.7). Thus, CyHR is a promising tool for HClO-related physiological and pathological studies and may provide a means for designing HClO-specific fluorescence probes.     

Interpretation of the Role of Composition on the Inclusion Efficiency of Monovalent Cations into Cobalt Hexacyanoferrate

Cobalt hexacyanoferrate of various compositions was prepared in flow mode and the role of the vacancy on the structure, thermogravimetric (TG) properties, and the adsorption efficiency was studied. The material, Na_yCo[Fe(CN)₆]_1−x ⋅ z H₂O, with a minimum vacancy of x=0.014 to the highest x=0.47, was obtained. The TG-differential scanning calorimetry (DSC) profile showed a distinct influence of the vacancy on the water release temperature. Materials with x>0.35 showed a smooth release of water at a relatively lower temperature. However, for the materials with x<0.35, water release took place in multiple steps, suggesting the existence of various forms of water. The FTIR profiles supported the existence of free and bonded water molecules. However, the materials with multiple water peaks in the FTIR spectra showed a shift of the major XRD peaks when heated at 285 °C in N₂ atmosphere. Regarding the effect of the vacancy on the adsorption behavior, for NH₄, the adsorption was found to be proportional to the number of Na atoms in the material, confirming the ion-exchange process. On the contrary, the materials with low vacancy and high Na content showed nominal Cs adsorption capacity. Interestingly, the K adsorption capacity was found to be in between that of the other two ions. This means the ionic size decides the rate of placement into the interstitial sites. For larger ions like Cs, the ease of percolation via the vacancy decides the overall adsorption efficiency.     

基于气象卫星云图的红外吸收带火山特征分析

飞行目标在2.7和4.3 μm谱段附近具有较强的红外辐射，因此这两个波段是探测飞行目标的最佳波段, 但是由于这两个波段并非大气窗口，不被大多数遥感器包含。对这两个谱段的典型地物特性开展研究具有重要的价值，但由于缺乏必要的数据获取能力，经常面临数据缺乏的问题。世界范围内频频有各种程度的火山爆发，火山爆发时温度较高的火山口，是否对于天基红外探测系统典型目标探测有影响，其影响程度如何一直缺乏相关的分析和研究。基于大气辐射传输理论，利用多元统计分析得到波段转换模型，使用气象卫星已有波段获得红外吸收谱段数据。将火点像元视为明火和背景的混合像元，采用目标与背景分离的方式描述高温目标像元的热辐射。对高温目标辐射量，在气溶胶模式固定的情况下，选取观测天顶角、大气可降水量、大气廓线为自变量影响因子。对于背景辐射亮度关系，选取观测天顶角、大气可降水量、大气廓线、背景温度为自变量影响因子, 利用多元统计，建立相关模型。利用对地面热状态非常敏感的风云三号可见光红外扫描辐射计第3通道数据的统计特征探测火山口，获取高温目标在特定波段的表观多维特征并定量分析。火山的多维特征分析，主要从时间和空间两个维度展开。时间维度是对同一火山在不同时间的数据进行分析，空间维度上，主要统计火山口的辐射亮度和亮度温度的空间分布特征。一般气象卫星分辨率较低，单纯利用像元个数表示火山面积, 明显夸大了火山的实际面积，所以基于亚像元特性对火山进行分析，将混合像元火点视为明火和背景的组合，运用线性光谱混合模型，通过混合像元的辐射率精确计算火山高温点的面积和温度，提高定量分析精度。分析结果表明： 通过仿真手段结合多元统计分析方法建立高温目标的波段转换模型是一种可行的预研手段。在2.7~2.95 μm谱段，火山口在弱背景环境下可能会对高温目标造成干扰，而在4.2~4.45 μm谱段，火山口能量远高于一般地表类型，是不可忽视的干扰。     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Investigation of active-region doping on InAs/GaSb long wave infrared detectors

The eight-band κ·p model is used to establish the energy band structure model of the type-II InAs/GaSb superlattice detectors with a cut-off wavelength of 10.5μm,and the best composition of M-structure in this type of device is calculated theoretically.In addition,we have also experimented on the devices designed with the best performance to investigate the effect of the active region p-type doping temperature on the quantum efficiency of the device.The results show that the modest active region doping temperature(Be:760℃)can improve the quantum efficiency of the device with the best performance,while excessive doping(Be:>760℃)is not conducive to improving the photo response.With the best designed structure and an appropriate doping concentration,a maximum quantum efficiency of 45% is achieved with a resistance-area product of 688?·cm^2,corresponding to a maximum detectivity of 7.35×10^11cm·Hz^1/2/W.     

四方体MgO的制备及对有机染料的吸附

以六水氯化镁和六次甲基四胺为原料,采用水热法合成四方体MgO,考察其对有机染料甲基橙和亚甲基蓝的吸附行为.通过TGA-DTA、SEM、XRD、N2-sorption和FT-IR等手段表征样品.结果表明,原料浓度、温度和表面活性剂对四方体MgO结构的形成影响较小,而反应时间的延长有助于有序结构的组装.温度170℃、时间24h、MgCl2·6H2O与C6H12N4浓度比为1∶2和表面活性剂PVP是制备四方体MgO的最佳条件.在溶液浓度10mg · L-1的单一吸附实验过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为91.3;和22.3;,吸附过程均为单层吸附且符合Langmuir等温吸附模型和伪二级吸附动力学方程.在溶液浓度40 mg·L-1、甲基橙和亚甲基蓝浓度比3∶1的混合溶液吸附过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为80.1;和97.9;.     

Formation of Azulene-Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction

Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.     

NO分子宏观气体热力学性质的理论研究

采用量子统计系综理论,研究了基态NO分子宏观气体摩尔熵、摩尔内能、摩尔热容等热力学性质.首先应用课题组前期建立的变分代数法(variational algebraic method, VAM)计算获得了基态NO分子的完全振动能级,得到的VAM振动能级作为振动部分,结合欧拉-麦克劳林渐进展开公式的转动贡献,应用于经典的热力学与统计物理公式中,从而计算得到了1000-5000 K温度范围内NO宏观气体的摩尔内能、摩尔熵和摩尔热容.将不同方法计算得到的摩尔热容结果分别与实验值进行比较,结果表明基于VAM完全振动能级获得的结果优于其他方法获得的理论结果.振动部分采用谐振子模型对无限能级求和计算热力学性质的方法有一定的局限性,应当使用有限的完全振动能级进行统计求和.