常压连续反应性萃取法由预处理生物质制备乙酰丙酸

采用双相联系流反应性萃取技术实现常压下小麦秸秆向乙酰丙酸的转化,其中生物质在水相中完成降解,形成乙酰丙酸,而后比水密度大的有机相作为乙酰丙酸的萃取相,把生成的乙酰丙酸萃取到有机相,并经过虹吸到收集瓶中,有机相经蒸馏可反复使用,实现了预处理生物质到乙酰丙酸的高效转化,乙酰丙酸最大的产率为30.66%.     

Stable Operation of Aqueous Organic Redox Flow Batteries in Air Atmosphere

As a green route for large-scale energy storage, aqueous organic redox flow batteries (AORFBs) are attracting extensive attention. However, most of the reported AORFBs were operated in an inert atmosphere. Herein, we clarify this issue by using the reported AORFB (i.e., 3, 3′-(9,10-anthraquinone-diyl)bis(3-methylbutanoicacid) (DPivOHAQ)||Ferrocyanide) as an example. We demonstrate that the dissolved O₂ can oxidize the discharged DPivOHAQ in anolyte, leading to capacity-imbalance between anolyte and catholyte. Therefore, this cell shows continuous capacity fading when operated in an air atmosphere. We propose a simple strategy for this challenge, in which the oxygen evolution reaction (OER) in catholyte is employed to balance oxygen reduction reaction (ORR) in anolyte. When using the Ni(OH)₂-modifed carbon felt (CF) as a current collector for catholyte, this cell shows an excellent stability in air atmosphere because the Ni(OH)₂-induced OER capacity in catholyte exactly balances the ORR capacity in anolyte. Such O₂-balance strategy facilitates AORFBs’ practical application.     

Study of the Thermal Stability Properties of Pyridoxine Using Thermogravimetric Analysis

The thermal decomposition behavior and kinetics of pyridoxine in nitrogen-only and air atmospheres were studied using thermogravimetry analysis (TGA). Kinetic interpretation of thermal analysis data for pyridoxine decomposition was carried out using Ozawa and ASTM E698 isoconversional methods. The activation energy of the decomposition process varied with the degree of decomposition and was different in the nitrogen and air atmospheres. At a 5% decomposition level, the activation energy and the pre-exponential factor were found to be 28.3 kcal mol^?1 and 1.2 × 10¹⁴ min^?1, respectively, in the nitrogen-only atmosphere. Thermal stability was determined by calculating the time for 5% of the pyridoxine vitamer to decompose at 25°C. The calculated shelf life for the pyridoxine vitamer obtained via TGA was surprisingly smaller in nitrogen (0.9 years) than in air (1.5 years). This is speculated to be the result of a more complex decomposition mechanism in air, involving thermo-oxidative decomposition in the presence of oxygen.     

The rotational spectrum of chlorine nitrate (ClONO2) in the four lowest nν9 polyads

The analysis of the recently recorded 78-378 GHz broadband spectrum of ClONO₂ has been extended to cover rotational transitions in all 14 excited vibrational states up to 650 cm⁻¹ above the ground state. We report new measurements and analysis of the 2ν₉ and 3ν₉ dyads, and first assignment and analysis for the 4ν₉ and 5ν₉ triads. The polyad fits encompass a total of over 20 000 newly measured transition frequencies and spectroscopic constants are reported for 10 vibrationally excited states in each of ³⁵ClONO₂ and ³⁷ClONO₂. All polyads were fitted with a new coupling scheme between the perturbing states combining c-axis Coriolis and Fermi interactions. The scheme is validated by multiple tests of the physical significance of the derived parameters and it results in improved deviations of fits and significant reduction in the number of adjustable parameters.     

Polarization characteristics of aberrated partially coherent flat-topped beam propagating through turbulent atmosphere

The effects of turbulent atmosphere on the spectral degree of polarization (SDP) of aberrated partially coherent flat-topped beam were studied. Analytical formula for the SDP was derived. Detailed analyses of the SDP demonstrate that it is strongly affected by astigmatic aberration when propagating through turbulent atmosphere. The effect of source parameters such as correlation length and order of flatness as well as the strength of the atmospheric turbulence effect () on the SDP were analysed. The analyses are illustrated by numerical examples.     

获取大气颗粒物消光系数的差分吸收光谱法研究

针对雾霾天气日益增多,大气污染气体向颗粒物的转化在加快,研究了一种大范围对其监测的差分吸收光谱方法。差分吸收光谱法可以实时、在线、准确同时获取颗粒物光学特性和大气痕量气体浓度。论文首先分析了双光路差分吸收光学遥感系统获取颗粒物绝对光强的原理,然后研究了基于单光路测量大气吸收谱,在干净天气状况下测量参考光谱,利用能见度数据,在550 nm波段处实现系统校准,计算校准参数,从而获得大气绝对吸收光强,然后解析出大气总的消光系数。再从总的大气消光系数中,去除瑞利散射以及大气痕量气体吸收对消光系数影响后,精确解析出颗粒物消光系数。同时基于差分思想获取大气痕量气体的浓度。最后把该方法应用于外场实验,获取大气颗粒物在350～700 nm波段范围内消光系数和大气中NO₂的浓度。研究结果表明颗粒物消光系数的随着波长的增加而减少,符合Angstrom公式。该研究为分析大气气相/粒子非均相化学反应提供有力的技术支持。     

少量氧气对大气压氩氧混合气体放电特性的影响

基于一维流体模型,采用数值模拟的方法研究了大气压氩氧混合气体放电中少量氧气含量对放电特性的影响。根据模型方程进行了数值模拟分析,计算结果表明：随着氧气含量由0.1%增加到0.6%,电子密度减小,O^-离子密度增加,总的负粒子密度增加,鞘层区电子温度增加。随着放电时间的增加,O^-离子密度增加,电子密度的变化分为三个阶段：电子密度快速增长阶段、电子密度下降阶段和电子密度稳定阶段。当氧气含量小于1%时,电子密度随着氧气含量的增加迅速减小,氧原子密度快速增加;氧气含量大于1%小于4%时,电子密度随氧气含量的增加而缓慢减少,氧原子密度缓慢增加直至不变。     

氯原子引发的甲基过氧化氢大气光化学反应

有机过氧化物在大气化学过程中起着重要作用 ,并对城市大气质量有着重要影响 ,然而 ,目前对它们大气化学行为的了解还非常不够 ,尤其缺少定量的研究。文章利用长光路傅里叶变换红外光谱 (长光路FTIR)仪原位跟踪反应进程 ,进行实验室模拟研究大气中非常重要的一种有机过氧化物 ,即甲基过氧化氢(CH3OOH ,MHP)的大气光化学反应。反应在内配有红外光多次反射镜 (White镜 )的 2 8 5L静态石英反应池中进行 ,采用氯原子 (Cl)引发反应 ,温度为 (2 92± 2 )K ,压力为 9 3× 10 4 Pa(2 0 %O2 80 %N2 )。FTIR光谱表明反应产物中主要包括甲醛 (HCHO)、甲酸 (HCOOH)、一氧化碳 (CO)和二氧化碳 (CO2 ) ,此外还有少量的甲醇 (CH3OH)生成。测定了前三种主要产物在反应 6 0min内的产率 :HCOOH和CO产率分别为 2 4 %和 6 % ;而HCHO浓度先增后减 ,浓度达到峰值时产率为 5 0 %。根据实验结果探讨了可能的反应机理 ,指出MHP是大气中HOx 自由基的储库分子 ,对整个大气光化学反应的进程有重要作用     

化学发光分析方法在大气环境监测中的应用与进展

本文评述了近年来国内外化学发光分析在大气环境检测中的应用与进展，内容包括无机气体和有机气体污染物，单一组分和多种组分同时检测。引用文献50篇。     

60-GHz oxygen band: Precise experimental profiles and extended absorption modeling in a wide temperature range

The 60-GHz band of atmospheric oxygen was studied in the temperature range of −28° to +60 °C at atmospheric pressure by means of a resonator spectrometer with absorption-variation sensitivity of 0.002 dB/km. The experimental data obtained have sufficient signal-to-noise ratio to take second-order mixing into account, increasing the accuracy of the millimeter-wave propagation model (MPM). A refined set of mixing coefficients for the model is derived from the new data and presented. The fidelity of the new model to the spectrometer data is generally better than 2% between 54 and 65 GHz.