Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herei...Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herein,N-(bromophenyl)carbazoles are cyclized to lock up phenyl-carbazol internal rotation in advance and the fused nitrogen hetero-cyclic compounds are doped into poly(methyl methacrylate)(PMMA).The results show that locking up the molecular internal rotation can achieve ultra-long RTP polymers with lifetimes over 2 s,in contrast,the unlocked molecules hardly emit RTP in PMMA.The high-lying triplet excitons can transfer the energy to low-lying organic fluorescent dyes,and the persistent multicolor afterglows including white emission can be readily modulated.This work discloses an effective and extendable dopant molecular strategy for developing high-performance ultra-long organic RTP polymers.展开更多
The interaction of phenosafranine （PSF） with a glycosaminoglycans of heparin （Hep） in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robins...The interaction of phenosafranine （PSF） with a glycosaminoglycans of heparin （Hep） in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robinson （B-R） buffer solution. The addition of Hep caused decrease of the absorbance of PSF at 532 nm and the redox peak current of PSF. The study showed that an supramolecular complex of PSF-Hep was formed because of the electrostatic attraction of negatively charged Hep with the positively charged PSF, which resulted in the decrease of the equilibrium concentration of PSF in solutions, and the decrease of the absorbance or the peak current of PSF. The stoichiometry of the Hep/PSF complex was further calculated by voltammetric data with the result of 1：1 complex.展开更多
Near infrared （NIR） light induced photothermal effect for Fe304 nanoparticles, contained in Pluronic F127 micelles, has been studied and it exhibits high photothermal converting efficiency. Heat is found to be rapid...Near infrared （NIR） light induced photothermal effect for Fe304 nanoparticles, contained in Pluronic F127 micelles, has been studied and it exhibits high photothermal converting efficiency. Heat is found to be rapidly generated in micelles containing Fe304 nanoparticles by NIR laser irradiation. Upon irradiation at 808 nm light and with mass concentration of Pe304 nanoparticles in 4 g/L, the micelle temperature increase is higher than 34 ℃ for 10 min irradiation. The maximum temperature of micelles containing Fe304 nanoparticles in 4 g/L reaches 62 ℃.展开更多
Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-sca...Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.展开更多
Wearable self-powered piezoelectric pressure sensors are attracting tremendous interest.However,fabricating a high-sensitive elastic piezoelectric sensor for a broad response range remains challenging.Here,we assemble...Wearable self-powered piezoelectric pressure sensors are attracting tremendous interest.However,fabricating a high-sensitive elastic piezoelectric sensor for a broad response range remains challenging.Here,we assemble polar poly(vinylidene fluoride)(PVDF)microsphere-elastomer composites,achieving high-sensitive and wide-responsive pressure sensing.The polar PVDF microspheres are produced cost-effectively through phase separation,enabling scalability.The piezoelectric composite(PC)film demonstrates low Young's modulus,and excellent anti-fatigue performance.Further,the PC-based piezoelectric sensor exhibits a rather high sensitivity of 540 m V N^(-1) in a wide sensing range(5–40 N),240 times greater than the PVDF film-based sensor and comparable to the inorganic piezoelectric sensor.Such excellent performance is attributed to the highest average stress concentration on the spherical PVDF coupled with the remarkable deformation of dipoles of spherical PVDF in the flexible matrix.Based on excellent performance,this piezoelectric sensor achieves precise recognition of motions and sound visualization.This high-sensitive flexible piezoelectric sensor enabling large area production with ultralow price exerts great potential in smart monitoring and intelligent robots.展开更多
Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartw...Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it＇s obvious that they show high glass transition temperatures （Tg〉200 ℃）, good thermal stability with high decomposition temperatures （TD〉500℃） and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers.展开更多
Using the industrial technologies of rubber latex irradiation,preparation of nanoscale silica(SiO2) slurry,mixing irradiated rubber latex with SiO2 slurry,and the spray drying,we have prepared the ultrafine fully-vulc...Using the industrial technologies of rubber latex irradiation,preparation of nanoscale silica(SiO2) slurry,mixing irradiated rubber latex with SiO2 slurry,and the spray drying,we have prepared the ultrafine fully-vulcanized powder carboxyl styrene-butadiene rubber(UFPCSBR)/SiO2 nanocompound powder,in which the SiO2 particles and UFPCSBR particles are isolated and stuck each other.When the UFPCSBR/SiO2 nanocompound powder is mixed with crude rubber,the UFPCSBR particles are dispersed well in rubber matrix because of their good compatibility,then the SiO2 particles are also dispersed well in rubber matrix because of the carrier nature of the UFPCSBR particles during the mixing procedure,and the novel rubber/UFPCSBR/SiO2 nanocomposites are fabricated.Compared with the rubber composites prepared by mixing the crude rubber with the UFPCSBR powder and SiO2 powder one after the other,the novel UFPCSBR/SiO2 nanocompound modified rubber/UFPCSBR/SiO2 nanocomposites have better abrasion resistance,higher tensile strength and tear strength,and lower heat build-up data.Noteworthily,the tanδ-temperature curve of the novel rubber/UFPCSBR/SiO2 nanocomposites has the second tanδ peak due to the newly generated boundary layer surrounding the SiO2 particles,increasing the tanδ values in the temperature range of 0-20℃,which is very important to the research of green tyre tread.展开更多
Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hin...Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hinge to achieve excellent solar conversion efficiency.In this work,tubular Ni_(1−x)Co_(x)S_(2)-CdS heterostructures with reinforced Z-scheme charge transmission were constructed through an In-metal-organic framework(MOF)templated strategy.The Z-scheme charge transfer mechanism was sufficiently confirmed by combining density functional theory(DFT)calculation,X-ray photoelectron spectroscopy(XPS),surface photovoltage spectroscopy(SPV),and radical testing results.Crucially,the use of sodium citrate complexant contributes to the formation of intimate heterointerface,and the Fermi level gap between CdS and NiS_(2)is enlarged through Co doping into NiS_(2),which enhances the built-in electric field and photo-carriers transmission driving force for Ni_(1−x)Co_(x)S_(2)-CdS heterojunction,resulting in an evidently promoted activity toward H2 evolution reaction(HER).Under visible-light(λ>400 nm)irradiation,the Ni_(1−x)Co_(x)S_(2)-CdS composite with 10 mol%Co doping and 80 wt.%CdS(NC_(0.10)S-80%CdS)achieved an outstanding HER rate up to 35.94 mmol·g^(−1)·h^(−1)(corresponding to the apparent quantum efficiency of 34.7%at 420 nm),approximately 76.4 times that of 3 wt.%Pt-loaded CdS and it is much superior to that of most CdS-based photocatalysts ever reported.Moreover,the good photocatalytic durability of Ni_(1−x)Co_(x)S_(2)-CdS heterostructures was validated by cycling and long-term HER tests.This work could inspire the development of high-performance Z-scheme heterojunction via optimizing the morphology and interfacial charge transmission.展开更多
Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneousl...Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneously. Nevertheless, it is still challenging to exploit low-cost and stable Zscheme photocatalysts with highly-efficient H2 evolution from solar water-splitting so far. Herein, we report a novel all-solidstate Z-scheme photocatalyst Cd1-xZnxS@WO3-x consisting of Cd1-xZnxS nanorods coated with oxygen-deficient WO3-x amorphous layers. The Cd1-xZnxS@WO3-x exhibits an outstanding H2 evolution reaction(HER) activity as compared with Pt-loaded Cd1-xZnxS and most WO3- and Cd S-based photocatalysts, due to the generation of stronger reducing electrons through the appropriate Zn-doping in Cd1-xZnxS and the enhanced charge transfer by introducing oxygen vacancies(W^5+/OVs) into the ultrathin WO3-x amorphous coatings. The optimal HER rate of Cd1-xZnxS@WO3- xis determined to be 21.68 mmol h^-1 g^-1, which is further raised up to 28.25 mmol h^-1 g^-1(about 12 times more than that of Pt/Cd1-xZnxS) when Cd1-xZnxS@WO3-x is hybridized by Co Ox and Ni Oxdual cocatalysts(Cd1-xZnxS@WO3-x/CoOx/NiOx)through in-situ photo-deposition. Moreover, the corresponding apparent quantum yield(AQY) at 420 nm is significantly increased from 34.6% for Cd1-xZnxS@WO3-x to 60.8% for Cd1-xZnxS@WO3-x/CoOx/NiOx. In addition, both Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx demonstrate good stability towards HER. The results displayed in this work will inspire the rational design and synthesis of high-performance nanostructures for photocatalytic applications.展开更多
With TiCl4/MgCl2(Ti)and Al(i-Bu)3(Al)as catalysts,the thermoplastic copolymer of 1-butene(Bt)and 1-hexene(He)was synthesized successfully.The effects of Bt/He,Ti/(He+Bt),Al/Ti,temperature and reaction time on conversi...With TiCl4/MgCl2(Ti)and Al(i-Bu)3(Al)as catalysts,the thermoplastic copolymer of 1-butene(Bt)and 1-hexene(He)was synthesized successfully.The effects of Bt/He,Ti/(He+Bt),Al/Ti,temperature and reaction time on conversion,catalyst efficiency(CE),intrinsic viscosity([g])and insoluble content were studied.The copolymer was analyzed with Fourier transform-infrared(FTIR)and nuclear magnetic resonance(1H-NMR).Results showed that the optimal polymerization conditions were:He/Bt=0.25,temperature 40℃–50℃,Al/Ti=400–500,Ti/(Bt+He)=3x10-5-4x10-5,time 4 h.Intrinsic viscosity was found to increase with increasing Ti/(Bt+He)and decreasing Al/Ti and polymerization temperature.When the molar content of He,Al/Ti and polymerization temperature increased,the insoluble content in CH2Cl2 of copolymers decreased.When Ti/(Bt+He)and reaction time increased,the insoluble con-tent in CH2Cl2 of copolymers also increased.The crystal-lization and stereoregularity of poly(1-butene)decreased with the addition of He.展开更多
We prepared and utilized a novel ultrafine fully-vulcanized powder nitrile butadiene rubber (UFPNBR)/ sodium montmorillonite (Na-MMT) nanocompound powder, in which nanoscale UFPNBR particles and nanoscale platelets of...We prepared and utilized a novel ultrafine fully-vulcanized powder nitrile butadiene rubber (UFPNBR)/ sodium montmorillonite (Na-MMT) nanocompound powder, in which nanoscale UFPNBR particles and nanoscale platelets of Na-MMT were isolated and stuck each other. When the UFPNBR/Na-MMT nano-compoud powder was mixed with crude nitrile butadiene rubber (NBR), UFPNBR particles could be easily dispersed in NBR matrix because of good compatibility, and nanoscale Na-MMT was also dis-persed well in NBR matrix due to the carrier aidance of UFPNBR particle, thus the NBR/UFPNBR/Na- MMT ternary nanocomposites adapting to industry was fabricated. X-ray diffraction test and scanning electron microscopy (SEM) observation indicated that nanoscale Na-MMT was dispersed well in NBR matrix. Compared with NBR/Na-MMT binary composites, NBR/UFPNBR/Na-MMT ternary nanocompo-sites have shorter vulcanization time and higher flame retardancy due to the exfoliated Na-MMT in NBR matrix.展开更多
Photocatalytic water splitting for hydrogen(H_(2))production is a green sustainable technology,in which highly-efficient steady photocatalysts are fundamentally required.In this work,unique CdS/Cd_(0.5)Zn_(0.5)S-M0_(1...Photocatalytic water splitting for hydrogen(H_(2))production is a green sustainable technology,in which highly-efficient steady photocatalysts are fundamentally required.In this work,unique CdS/Cd_(0.5)Zn_(0.5)S-M0_(1-x)W_(x)S_(2) photocatalyst constructed by CdS hollow nano-spheres with successively surface-modified Cd_(0.5)Zn_(0.5)S shell and defect-rich MO_(1-x)W_(x)S_(2) ultrathin nanosheets was reported for the first time.Interestingly,the Cd_(0.5)Zn_(0.5)S shell could greatly enhance the photo-stability and reduce the carrier recombination of CdS.Meanwhile,enriching active sites and accelerating charge transfer could be achieved via anchoring defect-rich Mo_(1-x)W_(x)S_(2) onto CdS/Cd_(0.5)Zn_(0.5)S hollow heterostructures.Specifically,the optimized CdS/Cd_(0.5)Zn_(0.5)S-Mo_(1-x)W_(x)Sa(6 h Cd_(0.5)Zn_(0.5)S-coating,7 wt.%Mo_(1-x)W_(x)S_(2),x=0.5)hybrid delivered an exceptional H_(2) generation rate of 215.99 mmol·g^(-1)·h^(-1),which is approximately 502,134,and 23 times that of pure CdS,CdS/Cd_(0.5)Zn_(0.5)S,and 3 wt.%Pt-loaded CdS/Cd_(0.5)Zn_(0.5)S,respectively.Remarkably,a high H_(2) evolution reaction(HER)apparent quantum yield(AQY)of 64.81%was obtained under 420-nm irradiation.In addition,the CdS/Cd_(0.5)Zn_(0.5)S-Mo_(1-x)W_(x)S_(2) was also durable for H2 production under long-term irradiation.This work provides valuable inspirations to rational design and synthesis of efficient and stable hybrid photocatalysts for solar energy conversion.展开更多
文摘Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herein,N-(bromophenyl)carbazoles are cyclized to lock up phenyl-carbazol internal rotation in advance and the fused nitrogen hetero-cyclic compounds are doped into poly(methyl methacrylate)(PMMA).The results show that locking up the molecular internal rotation can achieve ultra-long RTP polymers with lifetimes over 2 s,in contrast,the unlocked molecules hardly emit RTP in PMMA.The high-lying triplet excitons can transfer the energy to low-lying organic fluorescent dyes,and the persistent multicolor afterglows including white emission can be readily modulated.This work discloses an effective and extendable dopant molecular strategy for developing high-performance ultra-long organic RTP polymers.
基金supported form the National Natural Science Foundation of China(20405008,20375020)the Natural Science Foundation of Qingdao City(04-2-JZ-114)the Doctoral Foundation of Qingdao University of Science and Technology(0022125).
文摘The interaction of phenosafranine （PSF） with a glycosaminoglycans of heparin （Hep） in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robinson （B-R） buffer solution. The addition of Hep caused decrease of the absorbance of PSF at 532 nm and the redox peak current of PSF. The study showed that an supramolecular complex of PSF-Hep was formed because of the electrostatic attraction of negatively charged Hep with the positively charged PSF, which resulted in the decrease of the equilibrium concentration of PSF in solutions, and the decrease of the absorbance or the peak current of PSF. The stoichiometry of the Hep/PSF complex was further calculated by voltammetric data with the result of 1：1 complex.
基金the National Natural Science Foundation of China(No.51073121)
文摘Near infrared （NIR） light induced photothermal effect for Fe304 nanoparticles, contained in Pluronic F127 micelles, has been studied and it exhibits high photothermal converting efficiency. Heat is found to be rapidly generated in micelles containing Fe304 nanoparticles by NIR laser irradiation. Upon irradiation at 808 nm light and with mass concentration of Pe304 nanoparticles in 4 g/L, the micelle temperature increase is higher than 34 ℃ for 10 min irradiation. The maximum temperature of micelles containing Fe304 nanoparticles in 4 g/L reaches 62 ℃.
基金Supported by National Key Research and Development Program of China(2022 YFB 3704700(2022 YFB 3704702))Major Scientific and Technological Innovation Project of Shandong Province(2021 CXGC 010901)Taishan Scholar Program。
文摘Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.
基金supported by the National Natural Science Foundation of China(22022501,22073006)。
文摘Wearable self-powered piezoelectric pressure sensors are attracting tremendous interest.However,fabricating a high-sensitive elastic piezoelectric sensor for a broad response range remains challenging.Here,we assemble polar poly(vinylidene fluoride)(PVDF)microsphere-elastomer composites,achieving high-sensitive and wide-responsive pressure sensing.The polar PVDF microspheres are produced cost-effectively through phase separation,enabling scalability.The piezoelectric composite(PC)film demonstrates low Young's modulus,and excellent anti-fatigue performance.Further,the PC-based piezoelectric sensor exhibits a rather high sensitivity of 540 m V N^(-1) in a wide sensing range(5–40 N),240 times greater than the PVDF film-based sensor and comparable to the inorganic piezoelectric sensor.Such excellent performance is attributed to the highest average stress concentration on the spherical PVDF coupled with the remarkable deformation of dipoles of spherical PVDF in the flexible matrix.Based on excellent performance,this piezoelectric sensor achieves precise recognition of motions and sound visualization.This high-sensitive flexible piezoelectric sensor enabling large area production with ultralow price exerts great potential in smart monitoring and intelligent robots.
基金Project supported by the National Natural Science Foundation of China （No. 10576017）.
文摘Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it＇s obvious that they show high glass transition temperatures （Tg〉200 ℃）, good thermal stability with high decomposition temperatures （TD〉500℃） and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers.
基金supported by the National Natural Science Foundation of China (Grant No. 50873049)National High Technology Research and Development Program of China ("863" Program) (Grant No. 2009AA-03Z338)+1 种基金Shandong Young Scientists Encouragement Foundation (Grant No. 2007BS04038)the Scientific Research Foundation of Shandong Education Department (Grant No. J07YA12)
文摘Using the industrial technologies of rubber latex irradiation,preparation of nanoscale silica(SiO2) slurry,mixing irradiated rubber latex with SiO2 slurry,and the spray drying,we have prepared the ultrafine fully-vulcanized powder carboxyl styrene-butadiene rubber(UFPCSBR)/SiO2 nanocompound powder,in which the SiO2 particles and UFPCSBR particles are isolated and stuck each other.When the UFPCSBR/SiO2 nanocompound powder is mixed with crude rubber,the UFPCSBR particles are dispersed well in rubber matrix because of their good compatibility,then the SiO2 particles are also dispersed well in rubber matrix because of the carrier nature of the UFPCSBR particles during the mixing procedure,and the novel rubber/UFPCSBR/SiO2 nanocomposites are fabricated.Compared with the rubber composites prepared by mixing the crude rubber with the UFPCSBR powder and SiO2 powder one after the other,the novel UFPCSBR/SiO2 nanocompound modified rubber/UFPCSBR/SiO2 nanocomposites have better abrasion resistance,higher tensile strength and tear strength,and lower heat build-up data.Noteworthily,the tanδ-temperature curve of the novel rubber/UFPCSBR/SiO2 nanocomposites has the second tanδ peak due to the newly generated boundary layer surrounding the SiO2 particles,increasing the tanδ values in the temperature range of 0-20℃,which is very important to the research of green tyre tread.
基金supported by the National Natural Science Foundation of China(Nos.22179068,52272222,52072197,and 52171140)the 111 Project of China(No.D20017)+5 种基金the Natural Science Foundation of Shandong Province(No.ZR2019JQ14)the Major Scientific and Technological Innovation Project of Shandong Province(No.2019JZZY020405)the Key Research and Development Program of Jiangsu Province(No.BE2021070)the Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(No.2022TSGC1257)the Shandong Province“Double-Hundred Talent Plan”(Nos.WST2019011,WST2020003,and WST2021021)the Major Research Program of Jining City(No.2020ZDZP024).
文摘Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hinge to achieve excellent solar conversion efficiency.In this work,tubular Ni_(1−x)Co_(x)S_(2)-CdS heterostructures with reinforced Z-scheme charge transmission were constructed through an In-metal-organic framework(MOF)templated strategy.The Z-scheme charge transfer mechanism was sufficiently confirmed by combining density functional theory(DFT)calculation,X-ray photoelectron spectroscopy(XPS),surface photovoltage spectroscopy(SPV),and radical testing results.Crucially,the use of sodium citrate complexant contributes to the formation of intimate heterointerface,and the Fermi level gap between CdS and NiS_(2)is enlarged through Co doping into NiS_(2),which enhances the built-in electric field and photo-carriers transmission driving force for Ni_(1−x)Co_(x)S_(2)-CdS heterojunction,resulting in an evidently promoted activity toward H2 evolution reaction(HER).Under visible-light(λ>400 nm)irradiation,the Ni_(1−x)Co_(x)S_(2)-CdS composite with 10 mol%Co doping and 80 wt.%CdS(NC_(0.10)S-80%CdS)achieved an outstanding HER rate up to 35.94 mmol·g^(−1)·h^(−1)(corresponding to the apparent quantum efficiency of 34.7%at 420 nm),approximately 76.4 times that of 3 wt.%Pt-loaded CdS and it is much superior to that of most CdS-based photocatalysts ever reported.Moreover,the good photocatalytic durability of Ni_(1−x)Co_(x)S_(2)-CdS heterostructures was validated by cycling and long-term HER tests.This work could inspire the development of high-performance Z-scheme heterojunction via optimizing the morphology and interfacial charge transmission.
基金financially supported by the National Natural Science Foundation of China (51572136, 51772162, 21571112, 51802170 and 21801150)the Natural Science Foundation of Shandong Province (ZR2018BEM014, ZR2018LB008 andZR2019MB001)+2 种基金Taishan Scholar Foundation of Shandong Province (H. W., ts201712047)the Special Fund Project to Guide Development of Local Science and Technology by Central Government (H.W.)Taishan Scholar Program of Advantage and Characteristic Discipline Team of Eco Chemical Process and Technology
文摘Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneously. Nevertheless, it is still challenging to exploit low-cost and stable Zscheme photocatalysts with highly-efficient H2 evolution from solar water-splitting so far. Herein, we report a novel all-solidstate Z-scheme photocatalyst Cd1-xZnxS@WO3-x consisting of Cd1-xZnxS nanorods coated with oxygen-deficient WO3-x amorphous layers. The Cd1-xZnxS@WO3-x exhibits an outstanding H2 evolution reaction(HER) activity as compared with Pt-loaded Cd1-xZnxS and most WO3- and Cd S-based photocatalysts, due to the generation of stronger reducing electrons through the appropriate Zn-doping in Cd1-xZnxS and the enhanced charge transfer by introducing oxygen vacancies(W^5+/OVs) into the ultrathin WO3-x amorphous coatings. The optimal HER rate of Cd1-xZnxS@WO3- xis determined to be 21.68 mmol h^-1 g^-1, which is further raised up to 28.25 mmol h^-1 g^-1(about 12 times more than that of Pt/Cd1-xZnxS) when Cd1-xZnxS@WO3-x is hybridized by Co Ox and Ni Oxdual cocatalysts(Cd1-xZnxS@WO3-x/CoOx/NiOx)through in-situ photo-deposition. Moreover, the corresponding apparent quantum yield(AQY) at 420 nm is significantly increased from 34.6% for Cd1-xZnxS@WO3-x to 60.8% for Cd1-xZnxS@WO3-x/CoOx/NiOx. In addition, both Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx demonstrate good stability towards HER. The results displayed in this work will inspire the rational design and synthesis of high-performance nanostructures for photocatalytic applications.
基金supported by the National High-Tech Research and Development Program of China(863 Program)(Grant No.2006AA03Z546).
文摘With TiCl4/MgCl2(Ti)and Al(i-Bu)3(Al)as catalysts,the thermoplastic copolymer of 1-butene(Bt)and 1-hexene(He)was synthesized successfully.The effects of Bt/He,Ti/(He+Bt),Al/Ti,temperature and reaction time on conversion,catalyst efficiency(CE),intrinsic viscosity([g])and insoluble content were studied.The copolymer was analyzed with Fourier transform-infrared(FTIR)and nuclear magnetic resonance(1H-NMR).Results showed that the optimal polymerization conditions were:He/Bt=0.25,temperature 40℃–50℃,Al/Ti=400–500,Ti/(Bt+He)=3x10-5-4x10-5,time 4 h.Intrinsic viscosity was found to increase with increasing Ti/(Bt+He)and decreasing Al/Ti and polymerization temperature.When the molar content of He,Al/Ti and polymerization temperature increased,the insoluble content in CH2Cl2 of copolymers decreased.When Ti/(Bt+He)and reaction time increased,the insoluble con-tent in CH2Cl2 of copolymers also increased.The crystal-lization and stereoregularity of poly(1-butene)decreased with the addition of He.
基金Supported by National Natural Science Foundation of China (Grant No. 50873049)Shandong Young Scientists Encouragement Foundation (Grant No. 2007BS04038)+1 种基金Scientific Research Foundation of Shandong Education Department (Grant No. J07YA12)the Special Funds for Major State Basic Research Projects of China (Grant No. 2005CB623805)
文摘We prepared and utilized a novel ultrafine fully-vulcanized powder nitrile butadiene rubber (UFPNBR)/ sodium montmorillonite (Na-MMT) nanocompound powder, in which nanoscale UFPNBR particles and nanoscale platelets of Na-MMT were isolated and stuck each other. When the UFPNBR/Na-MMT nano-compoud powder was mixed with crude nitrile butadiene rubber (NBR), UFPNBR particles could be easily dispersed in NBR matrix because of good compatibility, and nanoscale Na-MMT was also dis-persed well in NBR matrix due to the carrier aidance of UFPNBR particle, thus the NBR/UFPNBR/Na- MMT ternary nanocomposites adapting to industry was fabricated. X-ray diffraction test and scanning electron microscopy (SEM) observation indicated that nanoscale Na-MMT was dispersed well in NBR matrix. Compared with NBR/Na-MMT binary composites, NBR/UFPNBR/Na-MMT ternary nanocompo-sites have shorter vulcanization time and higher flame retardancy due to the exfoliated Na-MMT in NBR matrix.
基金support from the National Natural Science Foundation of China(Nos.51802170,51772162,and 21801150)the Natural Science Foundation of Shandong Province(Nos.ZR2019MB001,ZR2018BEM014,and ZR2019JQ14)+3 种基金the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)the Taishan Scholar Project of Shandong Province(No.ts201712047)the Special Fund Project to Guide Development of Local Science and Technology by Central Government,the Open Research Fund of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University(No.2019-22)the Taishan Scholar Program of Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology.
文摘Photocatalytic water splitting for hydrogen(H_(2))production is a green sustainable technology,in which highly-efficient steady photocatalysts are fundamentally required.In this work,unique CdS/Cd_(0.5)Zn_(0.5)S-M0_(1-x)W_(x)S_(2) photocatalyst constructed by CdS hollow nano-spheres with successively surface-modified Cd_(0.5)Zn_(0.5)S shell and defect-rich MO_(1-x)W_(x)S_(2) ultrathin nanosheets was reported for the first time.Interestingly,the Cd_(0.5)Zn_(0.5)S shell could greatly enhance the photo-stability and reduce the carrier recombination of CdS.Meanwhile,enriching active sites and accelerating charge transfer could be achieved via anchoring defect-rich Mo_(1-x)W_(x)S_(2) onto CdS/Cd_(0.5)Zn_(0.5)S hollow heterostructures.Specifically,the optimized CdS/Cd_(0.5)Zn_(0.5)S-Mo_(1-x)W_(x)Sa(6 h Cd_(0.5)Zn_(0.5)S-coating,7 wt.%Mo_(1-x)W_(x)S_(2),x=0.5)hybrid delivered an exceptional H_(2) generation rate of 215.99 mmol·g^(-1)·h^(-1),which is approximately 502,134,and 23 times that of pure CdS,CdS/Cd_(0.5)Zn_(0.5)S,and 3 wt.%Pt-loaded CdS/Cd_(0.5)Zn_(0.5)S,respectively.Remarkably,a high H_(2) evolution reaction(HER)apparent quantum yield(AQY)of 64.81%was obtained under 420-nm irradiation.In addition,the CdS/Cd_(0.5)Zn_(0.5)S-Mo_(1-x)W_(x)S_(2) was also durable for H2 production under long-term irradiation.This work provides valuable inspirations to rational design and synthesis of efficient and stable hybrid photocatalysts for solar energy conversion.
