We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identify...We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identifying and quantifying the oxidation species. Major products, cyclic olefins, and oxygenated products including reactive hydroperoxides and high oxygen compounds were detected. Compared with n-alkanes, a narrow low-temperature window （-80 K） was observed in the low-temperature oxidation of cyclohexane. Besides, a kinetic model for cyclohexane oxidation was developed based on the CNRS model [Combust. Flame 160, 2319 （2013）], which can better capture the experimental results than previous models. Based on the modeling analysis, the 1,5-H shift dominates the crucial isomerization steps of the first and second O2 addition products in the low-temperature chain branching process of cyclohexane. The negative temperature coefficient behavior of cyclohexane oxidation results from the reduced chain branching due to the competition from chain inhibition and propagation reactions, i.e. the reaction between cyclohexyl radical and O2 and the de- composition of cyclohexylperoxy radical, both producing cyclohexene and HO2 radical, as well as the decomposition of cyclohexylhydroperoxy radical producing hex-5-en-l-al and OH radical.展开更多
The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][...The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to 34.8.It was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.展开更多
With the rapid development of smart wearable devices, flexible and biodegradable sensors are in urgent needs. In this study, ‘‘green" electrically conductive Ag nanowire (Ag NW)/cellulose nanofiber (CNF) hybrid...With the rapid development of smart wearable devices, flexible and biodegradable sensors are in urgent needs. In this study, ‘‘green" electrically conductive Ag nanowire (Ag NW)/cellulose nanofiber (CNF) hybrid nanopaper was fabricated to prepare flexible sensors using the facial solution blending and vacuum filtration technique. The amphiphilic property of cellulose is beneficial for the homogeneous dispersion of Ag NW to construct effective electrically conductive networks. Two different types of strain sensors were designed to study their applications in strain sensing. One was the tensile strain sensor where the hybrid nanopaper was sandwiched between two thermoplastic polyurethane (TPU) films through hot compression, and special micro-crack structure was constructed through the pre-strain process to enhance the sensitivity. Interestingly, typical pre-strain dependent strain sensing behavior was observed due to different crack densities constructed under different pre-strains. As a result, it exhibited an ultralow detection limit as low as 0.2%, good reproducibility under different strains and excellent stability and durability during 500 cycles (1% strain, 0.5 mm/min). The other was the bending strain sensor where the hybrid nanopaper was adhered onto TPU film, showing stable and recoverable linearly sensing behavior towards two different bending modes (tension and compression). Importantly, the bending sensor displayed great potential for human motion and physiological signal detection. Furthermore, the hybrid nanopaper also exhibited stable and reproducible negative temperature sensing behavior when it was served as a temperature sensor. This study provides a guideline for fabricating flexible and biodegradable sensors.展开更多
基金supported by the National Natural Science Foundation of China(No.91641205,No.51622605,No.91541201)the Shanghai Science and Technology Committee(No.17XD1402000)
文摘We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identifying and quantifying the oxidation species. Major products, cyclic olefins, and oxygenated products including reactive hydroperoxides and high oxygen compounds were detected. Compared with n-alkanes, a narrow low-temperature window （-80 K） was observed in the low-temperature oxidation of cyclohexane. Besides, a kinetic model for cyclohexane oxidation was developed based on the CNRS model [Combust. Flame 160, 2319 （2013）], which can better capture the experimental results than previous models. Based on the modeling analysis, the 1,5-H shift dominates the crucial isomerization steps of the first and second O2 addition products in the low-temperature chain branching process of cyclohexane. The negative temperature coefficient behavior of cyclohexane oxidation results from the reduced chain branching due to the competition from chain inhibition and propagation reactions, i.e. the reaction between cyclohexyl radical and O2 and the de- composition of cyclohexylperoxy radical, both producing cyclohexene and HO2 radical, as well as the decomposition of cyclohexylhydroperoxy radical producing hex-5-en-l-al and OH radical.
基金Supported by the National Basic Research Program of China(2013CB733501)the National Natural Science Foundation of China(21136004,21176112,21476106,and21428601)+1 种基金Specialized Research Fund for the Doctoral Program of Higher Education(No.20133221110001)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to 34.8.It was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.
基金supported by the National Natural Science Foundation of China(51803191)the China Postdoctoral Science Foundation(2018M642782)the 111 project(D18023)
文摘With the rapid development of smart wearable devices, flexible and biodegradable sensors are in urgent needs. In this study, ‘‘green" electrically conductive Ag nanowire (Ag NW)/cellulose nanofiber (CNF) hybrid nanopaper was fabricated to prepare flexible sensors using the facial solution blending and vacuum filtration technique. The amphiphilic property of cellulose is beneficial for the homogeneous dispersion of Ag NW to construct effective electrically conductive networks. Two different types of strain sensors were designed to study their applications in strain sensing. One was the tensile strain sensor where the hybrid nanopaper was sandwiched between two thermoplastic polyurethane (TPU) films through hot compression, and special micro-crack structure was constructed through the pre-strain process to enhance the sensitivity. Interestingly, typical pre-strain dependent strain sensing behavior was observed due to different crack densities constructed under different pre-strains. As a result, it exhibited an ultralow detection limit as low as 0.2%, good reproducibility under different strains and excellent stability and durability during 500 cycles (1% strain, 0.5 mm/min). The other was the bending strain sensor where the hybrid nanopaper was adhered onto TPU film, showing stable and recoverable linearly sensing behavior towards two different bending modes (tension and compression). Importantly, the bending sensor displayed great potential for human motion and physiological signal detection. Furthermore, the hybrid nanopaper also exhibited stable and reproducible negative temperature sensing behavior when it was served as a temperature sensor. This study provides a guideline for fabricating flexible and biodegradable sensors.
