Two distinct copper coordination polymers, namely [Cu^Ⅱ2(2,5-pydc)2(bpp)2]·H2O(1) and Cu2^ⅠCu^Ⅱ(2,5-pydc)2(bpp)2(2)(2,5-pydc = pyridine-2,5-dicarboxylic acid, bpp = 1,3-bi(4-pyridyl)propane), h...Two distinct copper coordination polymers, namely [Cu^Ⅱ2(2,5-pydc)2(bpp)2]·H2O(1) and Cu2^ⅠCu^Ⅱ(2,5-pydc)2(bpp)2(2)(2,5-pydc = pyridine-2,5-dicarboxylic acid, bpp = 1,3-bi(4-pyridyl)propane), have been successfully synthesized through hydrothermal conditions under different temperatures. Single-crystal X-ray structural analysis revealed that both complexes 1 and 2 are 3D frameworks. Complex 1 is an 8-connected 2-fold interpenetrating network based on [Cu(2,5-pydc)]4 molecular building block(MBB), and also can be simplified as a 4-connected net if the Cu(Ⅱ) ion is regarded as an independent node, whereas 2 shows a(4,4)-connected non-interpenetrated framework which contains mixed valence Cu(Ⅰ/Ⅱ) centers. The results demonstrate that temperature plays a significant role in the final structures of the complexes.展开更多
Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated here...Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.展开更多
Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperat...Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs).However,they still face the critical issue of insufficient activity in phosphoric acid.Herein,we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method.X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N_(4) site through C atoms.The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V(vs.reversible hydrogen electrode(RHE),0.1 M H_(3)PO_(4)),which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts,respectively.More importantly,the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm^(−2)in a high temperature fuel cell(160℃),exceeding the non-noble-metal catalysts ever reported.The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N_(4) caused by neighboring P.This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs,but also provides a feasible P-doping method for regulating the structure of single atom site.展开更多
Efficient polymeric room-temperature phosphorescence(PRTP)with excellent processability and flexibility is highly desirable but still faces formidable challenge.Herein,a general strategy is developed for efficient PRT...Efficient polymeric room-temperature phosphorescence(PRTP)with excellent processability and flexibility is highly desirable but still faces formidable challenge.Herein,a general strategy is developed for efficient PRTP through photo-polymerization of phosphor monomers and N-isopropylacrylamide(NIPAM)spontaneously without a crosslinker.Remarkably ultralong lifetime of 3.54 s with afterglow duration time of 25 s and decent phosphorescent quantum efficiency of 13%are achieved.This efficient PRTP has been demonstrated to be derived from the synergistic effect of the covalent and hydrogen bonds networks formed through photo-polymerization of NIPAM.The electron paramagnetic resonance(EPR)spectra confirmed that methyl radicals are generated under the irradiation of ultraviolet light and promote the formation of covalent cross-linking networks.This strategy has also been proved to be generalizable to several other phosphor monomers.Interestingly,the polymer films display ultrahigh temperature resistance with long afterglows even at 140℃ and unexampled ultralong lifetime of 2.45 s in aqueous solutions.This work provides a simple and feasible avenue to obtain efficient PRTP.展开更多
Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete t...Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete time system, a design scheme of model-free adaptive (MFA) controller is given. Then, particle swarm optimization (PSO) algorithm is applied to optimizing and setting the key parameters for controller tuning. After that, the MFA controller is used to control the system of polymerizing temperature. Finally, simulation results are given to show that the MAC strategy based on PSO obtains a good controlling performance index.展开更多
The characteristics of a two-layer structure on the basis of the layers of varistor ceramics and polymeric PPTC nanocomposite being in thermal contact for the purpose of using it as a limiter of constant voltage and l...The characteristics of a two-layer structure on the basis of the layers of varistor ceramics and polymeric PPTC nanocomposite being in thermal contact for the purpose of using it as a limiter of constant voltage and long-term varying electrical overvoltages are analyzed.A theoretical model of such a structure has been developed,and its main electrical characteristics are simulated.It is shown that the provision of the required output voltage limitation is performed by selecting the classification voltage of the varistor layer.The maximum current of the varistor layer required for heating the structure is determined by the intensity of heat transfer to the environment.It has established a satisfactory agreement between the theoretical and experimental electrical characteristics for the structure based on the layers used in commercial varistors and PPTC fuses.展开更多
基金supported by the application basis research key project of Yunnan Province science and technology department(201401CB00299)the major project of Qujing Normal University(2012ZD002)
文摘Two distinct copper coordination polymers, namely [Cu^Ⅱ2(2,5-pydc)2(bpp)2]·H2O(1) and Cu2^ⅠCu^Ⅱ(2,5-pydc)2(bpp)2(2)(2,5-pydc = pyridine-2,5-dicarboxylic acid, bpp = 1,3-bi(4-pyridyl)propane), have been successfully synthesized through hydrothermal conditions under different temperatures. Single-crystal X-ray structural analysis revealed that both complexes 1 and 2 are 3D frameworks. Complex 1 is an 8-connected 2-fold interpenetrating network based on [Cu(2,5-pydc)]4 molecular building block(MBB), and also can be simplified as a 4-connected net if the Cu(Ⅱ) ion is regarded as an independent node, whereas 2 shows a(4,4)-connected non-interpenetrated framework which contains mixed valence Cu(Ⅰ/Ⅱ) centers. The results demonstrate that temperature plays a significant role in the final structures of the complexes.
基金financially supported by the National Science Foundation of China, China (22179130, 91834301)the Foundation of the Key Laboratory of Chinese Academy of Sciences (CXJJ21S024)Dalian Institute of Chemical Physics, China (DICPI202023)。
文摘Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.
基金the National Key Research and Development Program of China(No.2018YFA0702002)the Beijing Natural Science Foundation(No.Z210016)the National Natural Science Foundation of China(No.21935001)。
文摘Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs).However,they still face the critical issue of insufficient activity in phosphoric acid.Herein,we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method.X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N_(4) site through C atoms.The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V(vs.reversible hydrogen electrode(RHE),0.1 M H_(3)PO_(4)),which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts,respectively.More importantly,the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm^(−2)in a high temperature fuel cell(160℃),exceeding the non-noble-metal catalysts ever reported.The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N_(4) caused by neighboring P.This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs,but also provides a feasible P-doping method for regulating the structure of single atom site.
基金supported by the National Natural Science Foundation of China(22175149,21975215)the Natural Science Foundation of Hunan Province(2021JJ30661)the Scientific Research Foundation of Hunan Provincial Education Department(19A486)。
文摘Efficient polymeric room-temperature phosphorescence(PRTP)with excellent processability and flexibility is highly desirable but still faces formidable challenge.Herein,a general strategy is developed for efficient PRTP through photo-polymerization of phosphor monomers and N-isopropylacrylamide(NIPAM)spontaneously without a crosslinker.Remarkably ultralong lifetime of 3.54 s with afterglow duration time of 25 s and decent phosphorescent quantum efficiency of 13%are achieved.This efficient PRTP has been demonstrated to be derived from the synergistic effect of the covalent and hydrogen bonds networks formed through photo-polymerization of NIPAM.The electron paramagnetic resonance(EPR)spectra confirmed that methyl radicals are generated under the irradiation of ultraviolet light and promote the formation of covalent cross-linking networks.This strategy has also been proved to be generalizable to several other phosphor monomers.Interestingly,the polymer films display ultrahigh temperature resistance with long afterglows even at 140℃ and unexampled ultralong lifetime of 2.45 s in aqueous solutions.This work provides a simple and feasible avenue to obtain efficient PRTP.
基金supported by University of Science and Technology Liaoning,National Financial Security and System Equipment Engineering Research Center(No.USTLKFGJ201502)
文摘Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete time system, a design scheme of model-free adaptive (MFA) controller is given. Then, particle swarm optimization (PSO) algorithm is applied to optimizing and setting the key parameters for controller tuning. After that, the MFA controller is used to control the system of polymerizing temperature. Finally, simulation results are given to show that the MAC strategy based on PSO obtains a good controlling performance index.
文摘The characteristics of a two-layer structure on the basis of the layers of varistor ceramics and polymeric PPTC nanocomposite being in thermal contact for the purpose of using it as a limiter of constant voltage and long-term varying electrical overvoltages are analyzed.A theoretical model of such a structure has been developed,and its main electrical characteristics are simulated.It is shown that the provision of the required output voltage limitation is performed by selecting the classification voltage of the varistor layer.The maximum current of the varistor layer required for heating the structure is determined by the intensity of heat transfer to the environment.It has established a satisfactory agreement between the theoretical and experimental electrical characteristics for the structure based on the layers used in commercial varistors and PPTC fuses.