采用半经验的Austin Model 1(AM1)方法,计算了齐分子Poly(Thienylene Vinylene)(PTV)的中性态和掺杂态的几何结构特性。与中性态相比,带电态下齐分子PTV的几何结构表现在C-C键键长发生显著的变化,单电荷掺杂导致极化子元激发;双电荷掺...采用半经验的Austin Model 1(AM1)方法,计算了齐分子Poly(Thienylene Vinylene)(PTV)的中性态和掺杂态的几何结构特性。与中性态相比,带电态下齐分子PTV的几何结构表现在C-C键键长发生显著的变化,单电荷掺杂导致极化子元激发;双电荷掺杂产生双极化子元激发,即使增加链长,仍在链中产生双极化子而不是两个分立的单极化子;掺杂4个电荷时,在齐分子PTV链中产生两个分立的双极化子。展开更多
A simulated gasoline consisting of model sulfur compounds of thiophene （C4H4S） and 3-methythiophene （3-MC4H4S） dissolved in n-heptane was tested for the oxidative desulfurization in the hydrogen peroxide （H202） ...A simulated gasoline consisting of model sulfur compounds of thiophene （C4H4S） and 3-methythiophene （3-MC4H4S） dissolved in n-heptane was tested for the oxidative desulfurization in the hydrogen peroxide （H202） and formic acid oxidative system over metal oxide-loaded molecular sieve. The effects of the oxidative system, loaded metal oxides, phase transfer catalyst, the addition of olefin and aromatics on sulfur removal were investigated in details. The results showed that the sulfur removal rate of simulated gasoline in the H202/formic acid system was higher than in other oxidative systems. The cerium oxide-loaded molecular sieve was found very active catalyst for oxidation of simulated gasoline in this system. The sulfur removal rates of C4H4S and 3-MC4H4S were enhanced when phase transfer catalyst （PTC） was added. However, the sulfur removal rate of simulated gasoline was reduced with the addition of olefin and aromatics.展开更多
The adsorption behavior of thiophene and benzene on NiY zeolite has been investigated by the frequency response(FR) method.The FR spectra of thiophene and benzene on NiY zeolite were recorded at 302-335 K in a pressur...The adsorption behavior of thiophene and benzene on NiY zeolite has been investigated by the frequency response(FR) method.The FR spectra of thiophene and benzene on NiY zeolite were recorded at 302-335 K in a pressure range of 26.6-266 Pa.The results showed that adsorption was found to be the rate-controlling process for the thiophene/NiY zeolite system,and there were two different adsorption processes.Two kinds of adsorption models have been proposed,namely:the S-M interaction(low frequency adsorption) and the π-complexation(high frequency adsorption).High frequency adsorption obeyed the Langmuir model.By combining the FR method and Langmuir model,the adsorption site of high frequency adsorption process at 302 K and 335 K was 3.172 mmol/g and 2.974 mmol/g,respectively,and on the combined adsorption isotherms,the adsorption site of the low frequency adsorption process at 302 K and 335 K was 0.308 mmol/gand 0.436 mmol/g,respectively.The low frequency adsorption process(S-M interaction) was the main adsorption process.The diffusion process was the rate-controlling process for the benzene-NiY zeolite system.展开更多
This article refers to the study on the performance of mesoporous silica used as the catalyst for oxidative desulfurization reactions. The test results revealed that under mild reaction conditions using tert-butyl hyd...This article refers to the study on the performance of mesoporous silica used as the catalyst for oxidative desulfurization reactions. The test results revealed that under mild reaction conditions using tert-butyl hydroperoxide as the oxidizing agent the content of dibenzothiophene(DBT) contained in oil samples could be reduced from 5000 ppm to less than 5 ppm. Furthermore,the mesoporous silica material can be easily regenerated and recycled.展开更多
FT-IR spectrometry, TPD and adsorption isotherms of thiophene on NaY/NiY zeolites were carried out and the diffusion coefficient was obtained by means of its real-time dynamic curves. The loading of thiophene adsorbed...FT-IR spectrometry, TPD and adsorption isotherms of thiophene on NaY/NiY zeolites were carried out and the diffusion coefficient was obtained by means of its real-time dynamic curves. The loading of thiophene adsorbed on the NaY zeolite decreased with an increasing temperature, which was ascribed to the patterns of physical adsorption. Both physical and chemical adsorption phenomena were detected on the NiY zeolite, with the 0 complexation and S-M interaction existing during the chemical adsorption. The loading of thiophene adsorbed on the NiY zeolite at 302 K and 335 K was equal, but it decreased at 373 K. The diffusion coefficient of thiophene on the NaY zeolite decreased when the loading increased to more than 0.02 mmol/g, and on the contrary that of thiophene on the NiY zeolite did not change obviously with the loading adsorbed.展开更多
This paper reports a new donor-acceptor copolymer semiconductor, PTBTh, comprising bithiophene and bithiazole where the regular coplanar structure and the intramolecular charge transfer are expected to increase the op...This paper reports a new donor-acceptor copolymer semiconductor, PTBTh, comprising bithiophene and bithiazole where the regular coplanar structure and the intramolecular charge transfer are expected to increase the opportunity for --- stacking and charge transport. The AFM image shows lamellar stacking of the polymer on the surface. The field-effect transistor (FET) properties of PTBTh have been evaluated by a bottom-contact/bottom-gate TFT configuration. The device showed a high hole mobility of 1.14×10-2 cm2 V-1 s-1 and a current on/off ratio of 3×105 with the polymer thin film annealed at a mild temperature of 120 ℃ when measured under ambient conditions.展开更多
A new star-shaped donor-acceptor molecule has been synthesized for application as the donor material in solution-processed bulk-heterojunction organic solar cells (OSCs). The molecule consists of a triphenylamine (TPA...A new star-shaped donor-acceptor molecule has been synthesized for application as the donor material in solution-processed bulk-heterojunction organic solar cells (OSCs). The molecule consists of a triphenylamine (TPA) unit as the core and a donor unit with three arms containing benzo[1,2,5]thiadiazole (BT) acceptor units and 5,5''-dihexyl-2,2′:3′,2″-terthiophene (tTh) end groups. The molecule, denoted S(TPA-BT-tTh), exhibits a broad absorption band in the wavelength range 300-650 nm and high hole mobility of 1.1×10 -4 cm2 V -1 s 1 . An OSC device based on S(TPA-BT-tTh) as donor and [6,6]-phenyl C71 -butyric acid methyl ester (PC 70 BM) as the acceptor (1:3, w/w) exhibited a power conversion efficiency of 2.28% with a short circuit current density of 6.39 mA/cm2 under illumination of AM.1.5, 100 mW/cm2 .展开更多
Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influence...Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influences on photophysical,electrochemical as well as photovoltaic properties in nanocrystalline TiO_2-based dye sensitized solar cells(DSSCs).The insertion of vinyl bond into the conjugation bridge leads to the molecular planar configuration,and the conjugation bridge of 3,4-ethylenedioxythiophene(EDOT)is prone to positively shift its highest occupied molecular orbital(HOMO).The electrochemical impedance spectroscopy(EIS)results indicate that the grafted long alkyl chain onto thiophene is favorable to suppress dye aggregation when adsorbed onto TiO_2film and modification on interface of TiO_2/dye/electrolyte,resulting in a relatively high open-circuit voltage(V_(oc)).Under optimized conditions,dye LS-4 bearing hexylthiophene as the conjugation bridge shows a relatively high overall conversion efficiency of5.45%,with a photocurrent of 11.61 mA cm^(-2),V_(oc)of 744 mV.展开更多
Thieno[3,2-b]thiophene(TT)monomers end-capped with 3,4-ethylenedioxythiophene(EDOT)moieties are electropolymerized to formπ-conjugated polymers with distinct electrochromic(EC)properties.Steric and electronic factors...Thieno[3,2-b]thiophene(TT)monomers end-capped with 3,4-ethylenedioxythiophene(EDOT)moieties are electropolymerized to formπ-conjugated polymers with distinct electrochromic(EC)properties.Steric and electronic factors(electron donor and acceptor substituents)in the side groups of the TT core,as well as the structure of the polymer backbone strongly affect the electrochemical and optical properties of the polymers and their electrochromic characteristics.The studied polymers show low oxidation potentials,tunable from-0.78 to+0.30 V(vs.Fc/Fc^+)and the band gaps from 1.46 to 1.92 eV and demonstrate wide variety of color palettes in polymer films in different states,finely tunable by structural variations in the polymer backbone and the side chains.EC materials of different colors in their doped/dedoped states have been developed(violet,deep blue,light blue,green,brown,purple-red,pinkish-red,orange-red,light gray,cyan and colorless transparent).High optical contrast(up to 79%),short response time(0.57-0.80 s),good cycling stability(up to 91%at 2000 cycles)and high coloration efficiency(up to 234.6 cm2C^(-1))have been demonstrated and the influence of different factors on the above parameters of EC polymers have been discussed.展开更多
文摘采用半经验的Austin Model 1(AM1)方法,计算了齐分子Poly(Thienylene Vinylene)(PTV)的中性态和掺杂态的几何结构特性。与中性态相比,带电态下齐分子PTV的几何结构表现在C-C键键长发生显著的变化,单电荷掺杂导致极化子元激发;双电荷掺杂产生双极化子元激发,即使增加链长,仍在链中产生双极化子而不是两个分立的单极化子;掺杂4个电荷时,在齐分子PTV链中产生两个分立的双极化子。
基金Supported by the National Natural Science Foundation of China （No.20276015） and the Natural Science Foundation of Hebei Province （No.203364）.
文摘A simulated gasoline consisting of model sulfur compounds of thiophene （C4H4S） and 3-methythiophene （3-MC4H4S） dissolved in n-heptane was tested for the oxidative desulfurization in the hydrogen peroxide （H202） and formic acid oxidative system over metal oxide-loaded molecular sieve. The effects of the oxidative system, loaded metal oxides, phase transfer catalyst, the addition of olefin and aromatics on sulfur removal were investigated in details. The results showed that the sulfur removal rate of simulated gasoline in the H202/formic acid system was higher than in other oxidative systems. The cerium oxide-loaded molecular sieve was found very active catalyst for oxidation of simulated gasoline in this system. The sulfur removal rates of C4H4S and 3-MC4H4S were enhanced when phase transfer catalyst （PTC） was added. However, the sulfur removal rate of simulated gasoline was reduced with the addition of olefin and aromatics.
基金the National Natural Science Foundation of China(NSFC.Contract No.20546003 and No.20776064)
文摘The adsorption behavior of thiophene and benzene on NiY zeolite has been investigated by the frequency response(FR) method.The FR spectra of thiophene and benzene on NiY zeolite were recorded at 302-335 K in a pressure range of 26.6-266 Pa.The results showed that adsorption was found to be the rate-controlling process for the thiophene/NiY zeolite system,and there were two different adsorption processes.Two kinds of adsorption models have been proposed,namely:the S-M interaction(low frequency adsorption) and the π-complexation(high frequency adsorption).High frequency adsorption obeyed the Langmuir model.By combining the FR method and Langmuir model,the adsorption site of high frequency adsorption process at 302 K and 335 K was 3.172 mmol/g and 2.974 mmol/g,respectively,and on the combined adsorption isotherms,the adsorption site of the low frequency adsorption process at 302 K and 335 K was 0.308 mmol/gand 0.436 mmol/g,respectively.The low frequency adsorption process(S-M interaction) was the main adsorption process.The diffusion process was the rate-controlling process for the benzene-NiY zeolite system.
文摘This article refers to the study on the performance of mesoporous silica used as the catalyst for oxidative desulfurization reactions. The test results revealed that under mild reaction conditions using tert-butyl hydroperoxide as the oxidizing agent the content of dibenzothiophene(DBT) contained in oil samples could be reduced from 5000 ppm to less than 5 ppm. Furthermore,the mesoporous silica material can be easily regenerated and recycled.
文摘FT-IR spectrometry, TPD and adsorption isotherms of thiophene on NaY/NiY zeolites were carried out and the diffusion coefficient was obtained by means of its real-time dynamic curves. The loading of thiophene adsorbed on the NaY zeolite decreased with an increasing temperature, which was ascribed to the patterns of physical adsorption. Both physical and chemical adsorption phenomena were detected on the NiY zeolite, with the 0 complexation and S-M interaction existing during the chemical adsorption. The loading of thiophene adsorbed on the NiY zeolite at 302 K and 335 K was equal, but it decreased at 373 K. The diffusion coefficient of thiophene on the NaY zeolite decreased when the loading increased to more than 0.02 mmol/g, and on the contrary that of thiophene on the NiY zeolite did not change obviously with the loading adsorbed.
基金supported by the National Natural Science Foundation of China (20772094)
文摘This paper reports a new donor-acceptor copolymer semiconductor, PTBTh, comprising bithiophene and bithiazole where the regular coplanar structure and the intramolecular charge transfer are expected to increase the opportunity for --- stacking and charge transport. The AFM image shows lamellar stacking of the polymer on the surface. The field-effect transistor (FET) properties of PTBTh have been evaluated by a bottom-contact/bottom-gate TFT configuration. The device showed a high hole mobility of 1.14×10-2 cm2 V-1 s-1 and a current on/off ratio of 3×105 with the polymer thin film annealed at a mild temperature of 120 ℃ when measured under ambient conditions.
基金supported by the National Natural Science Foundation of China (50933003 and 21021091)the support from MOE, Jiangsu Province, and SEU (NCET-09-0294, 20100092120037,XNY-48-037 and Seujq201103)
文摘A new star-shaped donor-acceptor molecule has been synthesized for application as the donor material in solution-processed bulk-heterojunction organic solar cells (OSCs). The molecule consists of a triphenylamine (TPA) unit as the core and a donor unit with three arms containing benzo[1,2,5]thiadiazole (BT) acceptor units and 5,5''-dihexyl-2,2′:3′,2″-terthiophene (tTh) end groups. The molecule, denoted S(TPA-BT-tTh), exhibits a broad absorption band in the wavelength range 300-650 nm and high hole mobility of 1.1×10 -4 cm2 V -1 s 1 . An OSC device based on S(TPA-BT-tTh) as donor and [6,6]-phenyl C71 -butyric acid methyl ester (PC 70 BM) as the acceptor (1:3, w/w) exhibited a power conversion efficiency of 2.28% with a short circuit current density of 6.39 mA/cm2 under illumination of AM.1.5, 100 mW/cm2 .
基金supported by the Science Fund for Creative Research Groups(21421004)Distinguished Young Scholars, the National Natural Science Foundation of China(21325625)+4 种基金Oriental Scholarship,Programme of Introducing Talents of Discipline to UniversitiesScience and Technology Commission of Shanghai Municipality (14YF1410500 and 15XD1501400)Shanghai Young Teacher Supporting Foundation(ZZEGD14011)School Funding of Shanghai Second Polytechnic University(EGD14XQD08)"Shu Guang" project(13SG55)
文摘Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influences on photophysical,electrochemical as well as photovoltaic properties in nanocrystalline TiO_2-based dye sensitized solar cells(DSSCs).The insertion of vinyl bond into the conjugation bridge leads to the molecular planar configuration,and the conjugation bridge of 3,4-ethylenedioxythiophene(EDOT)is prone to positively shift its highest occupied molecular orbital(HOMO).The electrochemical impedance spectroscopy(EIS)results indicate that the grafted long alkyl chain onto thiophene is favorable to suppress dye aggregation when adsorbed onto TiO_2film and modification on interface of TiO_2/dye/electrolyte,resulting in a relatively high open-circuit voltage(V_(oc)).Under optimized conditions,dye LS-4 bearing hexylthiophene as the conjugation bridge shows a relatively high overall conversion efficiency of5.45%,with a photocurrent of 11.61 mA cm^(-2),V_(oc)of 744 mV.
基金Shenzhen Key Laboratory of Organic Optoelectromagnetic Functional Materials of Shenzhen Science and Technology Plan(ZDSYS20140509094114164)the Shenzhen Peacock Program(KQTD2014062714543296)+6 种基金Shenzhen Science and Technology Research Grant(JCYJ20140509093817690)Nanshan Innovation Agency Grant(KC2015ZDYF0016A)Guangdong Key Research Project(2014B090914003,2015B090914002)Guangdong Talents Project, the National Basic Research Program of China(2015CB856505)the National Natural Science Foundation of China(51373075)Guangdong Academician Workstation(2013B090400016)the Natural Science Foundation of Guangdong Province(2014A030313800)
文摘Thieno[3,2-b]thiophene(TT)monomers end-capped with 3,4-ethylenedioxythiophene(EDOT)moieties are electropolymerized to formπ-conjugated polymers with distinct electrochromic(EC)properties.Steric and electronic factors(electron donor and acceptor substituents)in the side groups of the TT core,as well as the structure of the polymer backbone strongly affect the electrochemical and optical properties of the polymers and their electrochromic characteristics.The studied polymers show low oxidation potentials,tunable from-0.78 to+0.30 V(vs.Fc/Fc^+)and the band gaps from 1.46 to 1.92 eV and demonstrate wide variety of color palettes in polymer films in different states,finely tunable by structural variations in the polymer backbone and the side chains.EC materials of different colors in their doped/dedoped states have been developed(violet,deep blue,light blue,green,brown,purple-red,pinkish-red,orange-red,light gray,cyan and colorless transparent).High optical contrast(up to 79%),short response time(0.57-0.80 s),good cycling stability(up to 91%at 2000 cycles)and high coloration efficiency(up to 234.6 cm2C^(-1))have been demonstrated and the influence of different factors on the above parameters of EC polymers have been discussed.
