Durable and efficient bi-functional catalyst,that is capable of both oxygen evolution reaction and hydrogen evolution reaction under acidic condition,are highly desired for the commercialization of proton exchange mem...Durable and efficient bi-functional catalyst,that is capable of both oxygen evolution reaction and hydrogen evolution reaction under acidic condition,are highly desired for the commercialization of proton exchange membrane water electrolysis.Herein,we report a robust L-Ru/HfO_(2)heterostructure constructed via confining crystalline Ru nanodomains by HfO_(2)matrix.When assembled with a proton exchange membrane,the bi-functional L-Ru/HfO_(2)catalyst-based electrolyzer presents a voltage of 1.57 and 1.67 V to reach 100 and 300 mA cm^(-2)current density,prevailing most of previously reported Ru-based materials as well as commercial Pt/C||RuO_(2)electrolyzer.It is revealed that the synergistic effect of HfO_(2)modification and small crystalline domain formation significantly alleviates the over-oxidation of Ru.More importantly,this synergistic effect facilitates a dual-site oxide path during the oxygen evolution procedure via optimization of the binding configurations of oxygenated adsorbates.As a result,the Ru active sites maintain the metallic state along with reduced energy barrier for the rate-determining step(^(*)O→^(*)OOH).Both of water adsorption and dissociation(Volmer step)are strengthened,while a moderate hydrogen binding is achieved to accelerate the hydrogen desorption procedure(Tafel step).Consequently,the activity and stability of acidic overall water splitting are simultaneously enhanced.展开更多
Orthorhombic YFeO_3 thin film was prepared on La_(0.67)Sr_(0.33)MnO_3/LaAlO_3 substrate by a sol-gel spin-coating method. The structures of the YFeO_3/La_(0.67)Sr_(0.33)MnO_3/LaAlO_3(YFO/LSMO/LAO) sample were detected...Orthorhombic YFeO_3 thin film was prepared on La_(0.67)Sr_(0.33)MnO_3/LaAlO_3 substrate by a sol-gel spin-coating method. The structures of the YFeO_3/La_(0.67)Sr_(0.33)MnO_3/LaAlO_3(YFO/LSMO/LAO) sample were detected by x-ray diffraction pattern, Raman spectrometer, scanning electron microscopy, and atomic force microscope. The local ferroelectric polarization switching properties of the orthorhombic YFO film were confirmed by piezoresponse force microscopy(PFM) for the first time. The results show that the YFO film deposited on LSMO/LAO possesses orthorhombic structure,with ultra-fine crystal grains and flat surface. The leakage current of the YFO film is 8.39 × 10^(-4) A·cm^(-2) at 2 V,with its leakage mechanism found to be an ohmic behavior. PFM measurements indicate that the YFO film reveals weak ferroelectricity at room temperature and the local switching behavior of ferroelectric domains has been identified. By local poling experiment, polarization reversal in the orthorhombic YFO film at room temperature was further observed.展开更多
The La0.85Sr0.015MnO3/Fe heterostructure deposited on Si （100） substrate was prepared by the magnetron sputtering. The laser-induced voltage in the sample and the difference in the voltage signals between the curre...The La0.85Sr0.015MnO3/Fe heterostructure deposited on Si （100） substrate was prepared by the magnetron sputtering. The laser-induced voltage in the sample and the difference in the voltage signals between the current-in-plane geometry and current-perpendicular-to-plane geometry at 77 K were investigated. This difference can be attributed to the different transport mechanisms.展开更多
The transport properties in the La2/3（Ca（1-x）Sr（x））1/3MnO3 （x=0.1/3, 2/3） films prepared using the RF magnetron sputtering method were investigated, The effect of the Ca, Sr double-doping at the A position in ...The transport properties in the La2/3（Ca（1-x）Sr（x））1/3MnO3 （x=0.1/3, 2/3） films prepared using the RF magnetron sputtering method were investigated, The effect of the Ca, Sr double-doping at the A position in the La（2/3）A（1/3）MnO3 on the structure of the targets and transport of the films has been studied. With the increase of x, the structures of the targets transform from the rhombohedral phase to the cubic phase; the metal-insulator phase transition temperature （Tp） of the films increases; and the corresponding peak resistivity decreases. All the phenomena can be qualitatively explained by the lattice effect.展开更多
The magneto-electric effect in magnetic materials has been widely investigated, but obtaining an enhanced magnetoelectric effect is challenging. In this study, tricolor superlattices composed of manganese oxides-Pr（...The magneto-electric effect in magnetic materials has been widely investigated, but obtaining an enhanced magnetoelectric effect is challenging. In this study, tricolor superlattices composed of manganese oxides-Pr（0.9）Ca（0.1）MnO3,La（0.9）Sr（0.1）MnO3, and La（0.9）Sb（0.1）MnO3-on（001）-oriented Nb：SrTiO3 substrates with broken space-inversion and timereversal symmetries are designed. Regarding the electric polarization in the hysteresis loops of the superlattices at different external magnetic fields, both coercive electric field Ec and remnant polarization intensity Pr clearly show strong magneticfield dependences. At low temperatures（〈 120 K）, a considerable magneto-electric effect in the well-defined tricolor superlattice is observed that is absent in the single compounds. Both maxima of the magneto-electric coupling coefficients ？Ec and ？Pr appear at 30 K. The magnetic dependence of the dielectric constant further supports the magneto-electric effect. Moreover, a dependence of the magneto-electric effect on the periodicity of the superlattices with various structures is observed, which indicates the importance of interfaces. Our experimental results verify previous theoretical results regarding magneto-electric interactions, thereby paving the way for the design and development of novel magneto-electric devices based on manganite ferromagnets.展开更多
Objective: To study the effect of practicing Jianshenqigong-wuqinxi on subhealth problems including depression, anxiety, and memory loss. Methods: 1) 80 cases with subhealth problem were randomly divided into two grou...Objective: To study the effect of practicing Jianshenqigong-wuqinxi on subhealth problems including depression, anxiety, and memory loss. Methods: 1) 80 cases with subhealth problem were randomly divided into two groups. 40 cases practicing Jianshenqigong-wuqinxi were used as test group, and the other 40 unpracticing cases were used as control group. 2) The test group was practising Jianshenqigong-wuqinxi one hour in the morning five times per week for three months. 3) Scores of subhealth status such as depression and anxiety were evaluated once every two weeks, while the memory test was performed once a month. 4) Data analysis: SPSS11.0 software was used for statistical analyses. Data were shown in mean ± SEM. Difference was considered significant if the t-test P value is less than 0.05. Results: 1) Scores of subhealth state and depression were significantly lower in test group than those of control group. The beneficial effects of practicing Jianshenqigong-wuqinxi were more obvious for the subjects in the test group who had practiced Jianshenqigong-wuqinxi for two to twelve weeks (P < 0.05). 2) Scores of anxiety test were significantly lower in test group than those of control group after practicing Jianshenqigong-wuqinxi for six to twelve weeks (P < 0.05). 3) Scores of memory were significantly higher in test group than those of control group (P < 0.05). Conclusions: 1) Practicing Jianshenqigong-wuqinxi could promote health in people who have subhealth mental problems. 2) Practicing Jianshenqigong-wuqinxi could relieve depression, anxiety while enhance memory.展开更多
Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After dec...Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.展开更多
The development of degradable and recyclable polymers is an attractive strategy to tackle the post-consumption pollution issue of commercial plastics.Cyclic-acyclic monomers metathesis polymerization(CAMMP)has been re...The development of degradable and recyclable polymers is an attractive strategy to tackle the post-consumption pollution issue of commercial plastics.Cyclic-acyclic monomers metathesis polymerization(CAMMP)has been recently reported to produce degradable thermoset,thermoplastic and elastomeric polymers,and their degradability is enabled with addition of various chemicals.In this contribution,we demonstrate that the utilization of diene comonomers containing photodegradable moiety can give access to thermoset and thermoplastic materials bearing photo-degradation capabilities.The copolymerization of a series easily accessible diene comonomers bearing photodegradable ortho-nitrobenzyl moieties with dicyclopentadiene(DCPD)or cyclooctene(COE)leads to the formation of photodegradable p DCPD thermosets and p COE thermoplastic polymers with mechanical properties comparable to their non-degradable counterparts.Most importantly,their photo-degradation properties can be efficiently tuned with the addition of ultraviolet absorber during in-situ polymerization.展开更多
Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of high...Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of highly active phosphino-phenolate nickel catalysts with polymer-insoluble solvent(heptane)to access UHMWPE(Mn up to 8.3×10^(6)g mol^(-1))with good product morphology,free-flowing characteristics,and great mechanical properties.Compared with the academically commonly used aromatic solvent(toluene),the utilization of heptane offers simultaneous enhancement in important parameters including activity,polymer molecular weight,and catalyst thermal stability.This system can also generate polar functionalized UHMWPE with molecular weight of up to 1.6×10^(6)g mol^(-1)in the copolymerization of ethylene with polar comonomers.More importantly,this precipitation polymerization strategy is generally applicable to several representative transition metal catalyst systems,leading to UHMWPE synthesis with good product morphology control.展开更多
For transition metal-based olefin polymerization catalysts, ligand steric and electronic effects can strongly influence important catalytic properties. However, the simultaneous tuning of both steric and electronic ef...For transition metal-based olefin polymerization catalysts, ligand steric and electronic effects can strongly influence important catalytic properties. However, the simultaneous tuning of both steric and electronic effects has not been explored in most of the previous studies. In this contribution, a strategy to tune the ligand electronic and steric effects in a concerted fashion is reported. In such a system, both dibenzhydryl groups and multiple methoxy/fluoro groups were installed in α-diimine ligands. In addition to strongly influencing ligand electronics, the methoxy/fluoro groups can interact with the dibenzhydryl groups and efficiently increase ligand sterics. In ethylene polymerization, this concurrent tuning of electronic and steric effects can lead to simultaneous enhancement of several parameters(activity, stability, polymer molecular weight, melting point, branching density) for both the nickel and palladium catalysts. The effectiveness of this strategy is highly attractive for future studies in other catalytic systems.展开更多
In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization...In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization mechanism for this type of catalysts was discussed. Next, recent advances in ligand design were provided with special focus on the influence of ligand structures on the catalytic polymerization properties. Last, the ethylene homopolymerization and copolymerization with various polar comonomers, especially acrylate and vinyl ethers were summarized.展开更多
The transition-metal-catalyzed copolymerization of olefins with polar comonomers is a direct strategy to access polar-functionalized polyolefins in an economical manner.Due to the intrinsic poisoning effect of polar g...The transition-metal-catalyzed copolymerization of olefins with polar comonomers is a direct strategy to access polar-functionalized polyolefins in an economical manner.Due to the intrinsic poisoning effect of polar groups towards Lewis acidic metal centers and the drastic reactivity differences of polar comonomers versus non-polar olefins,it is challenging to develop catalysts that provide the desired polymer molecular weight,comonomer incorporation,and activity.In this contribution,we tackle this issue from a comonomer perspective using 5,6-disubstituted norbornenes,which are highly versatile,easily accessible,inexpensive,and capable of introducing two functional groups in a single insertion.More importantly,they are only mildly poisoning due to the presence of long spacers between double bonds and polar groups,and are not prone to b-hydride elimination due to their cyclic structures.As strong pdonors,they can competitively bind to metal centers versus olefins.Indeed,phosphine-sulfonate palladium catalysts can catalyze the copolymerization of ethylene with 5,6-disubstituted norbornenes and simultaneously achieve a high polymerization activity,copolymer molecular weight,and comonomer incorporation.The practicality of this system was demonstrated by studying the properties of the resulting polymers,copolymerization in hydrocarbon solvents or in bulk,recovery/utilization of unreacted comonomer,molecular weight modulation,and large-scale synthesis.展开更多
Ziegler and Natta won the Nobel Prize in 1963 due to their contributions in olefin polymerization catalysis.Subsequent studies into related catalysts have led to a multibillion-dollar polyolefin industry.Currently,mor...Ziegler and Natta won the Nobel Prize in 1963 due to their contributions in olefin polymerization catalysis.Subsequent studies into related catalysts have led to a multibillion-dollar polyolefin industry.Currently,more than 178 million tons of polyolefin materials are produced annually,which constitute more than half of global plastics production.Interestingly,the metal nickel was initially recognized as a“poison”for olefin polymerization.Alkyl aluminum species can oligomerize ethylene(degree of polymerization up to 100)at high temperature and pressure;while the addition of nickel salt to the system led to the exclusive formation of 1-butene.This famous“nickel effect”marks the starting point of the era of Ziegler catalysts[1].After decades of research,the situation of nickel has changed dramatically,and a large number of nickelbased catalysts have been shown with the capabilities of producing high-molecular-weight polyethylene.As an exceptional demonstration,some groups have recently developed nickel catalysts that are able to produce ultra-high molecular weight polyethylene(UHMWPE).UHMWPE,with molecular weight of above one-million,is a special class of advanced engineering plastics with superior properties and wide applications.展开更多
In the past few decades,the development of high-performance catalysts has been a key driving force and a center of research efforts in the field of olefin polymerization.However,a major discrepa ncy exists between in ...In the past few decades,the development of high-performance catalysts has been a key driving force and a center of research efforts in the field of olefin polymerization.However,a major discrepa ncy exists between in dustrial researches which utilize aliphatic hydrocarb on solventsz and academic researches which predominantly focus the catalytic properties in aromatic solvents.In this con-tribution,a novel diaryl-methyl aniline bearing eight tert-butyl groups was prepared and subsequently transformed to four different kinds of imine-type ligands.The corresponding nickel complexes as well as their counterparts derived from diphenyl-methyl aniline without the tert-butyl groups were prepared and investigated in ethylene polymerization.展开更多
A series of dibenzhydryl-based iminopyridine-N-oxide ligands bearing a range of electron-donating or-withdrawing substituents(OMe,H;and NO_(2))and corresponding nickel pre-catalysts are prepared and characterized.The ...A series of dibenzhydryl-based iminopyridine-N-oxide ligands bearing a range of electron-donating or-withdrawing substituents(OMe,H;and NO_(2))and corresponding nickel pre-catalysts are prepared and characterized.The substituents are installed at different positions on the ligand structure,including 4-position of the pyridine-N-oxide moiety(position X)and 4-position of the aniline moiety(position Y).These nickel pre-catalysts are highly active in ethylene polymerization with the addition of very little amount of aluminum cocatalysts,leading to the formation of polyethylenes with molecular weights of well above one million.Electron-donating substituents make the catalysts sensitive to polymerization temperature.In contrast,the catalysts bearing electron-withdrawing NO_(2) substituents show relatively steady performances at different temperatures.Most importantly,we demonstrate that different substituents and different positions both play important roles in determining the properties of nickel catalysts.This provides an alternative strategy for the future design of high-performance polymerization catalyst.展开更多
Phosphine-sulfonate based palladium is one of the most extensively studied catalyst systems in olefin polymerization.This type of catalyst features six-membered chelate ring size,and can enable the copolymerizations o...Phosphine-sulfonate based palladium is one of the most extensively studied catalyst systems in olefin polymerization.This type of catalyst features six-membered chelate ring size,and can enable the copolymerizations of ethylene with a wide variety of polar monomers.In this contribution,we decide to investigate the influence of chelate ring size on the properties of phosphinesulfonate palladium catalysts.As such,a series of phosphine-sulfonate ligands and the corresponding seven-membered ring Pd(II)complexes[κ~2-(P,O)-2-(CH_2-PR_1R_2)-4-methylphenyl-sulfonato]Pd(Me)(DMSO)(Pd1,R_1=R_2=Cy,Pd2,R_1=R_2=o-Me O-C_6H_4;Pd3,R_1=Ph,R_2=2-[2,6-(Me O)_2C_6H_3]C_6H_4;DMSO=dimethyl sulfoxide)were designed,prepared and characterized.These palladium complexes are moderately active when they were applied in ethylene polymerization and copolymerizations with methyl acrylate and butyl vinyl ether.However,their properties are greatly reduced from those of the classic six-membered ring phosphine-sulfonate palladium complex Pd2′.The experimental results indicate that the bigger chelate ring size can increase the ligand flexibility and damage the catalytic properties for the phosphine-sulfonate type palladium catalysts.展开更多
Introduction of polar comonomers into polyethylene is highly challenging,paving the way to tuning the copolymers'mechanical properties,adhesion/compatibility,and biodegradability.Polar-group tolerant single-site p...Introduction of polar comonomers into polyethylene is highly challenging,paving the way to tuning the copolymers'mechanical properties,adhesion/compatibility,and biodegradability.Polar-group tolerant single-site palladium and,more tempting,nickel-based catalysts have demon-strated promising reactivities in the ethylene copolymerization with polar comonomers via coordination/insertion mechanism。展开更多
Magnetocaloric and colossal magnetoresistance effects of the layered perovskite La 1.4 Sr 1.6 Mn 2 O 7 compound have been studied.A broad peak of magnetic entropy change （-△S M） is found above the Curie temperature...Magnetocaloric and colossal magnetoresistance effects of the layered perovskite La 1.4 Sr 1.6 Mn 2 O 7 compound have been studied.A broad peak of magnetic entropy change （-△S M） is found above the Curie temperature （T C =120 K）,which can be associated with the existence of two-dimensional short range ferromagnetic order.Additionally,the curvilinear shape of-△S M for layered perovskite is quite different from that of the Ln 1-x A x MnO 3 probably arising from magnetocrystalline anisotropy.At the same time,a wide peak of colossal magnetoresitance effect near T C is found in the layered provskite La 1.4 Sr 1.6 Mn 2 O 7.展开更多
Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of m...Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of metal–metal distance are complicated and time-consuming.In this contribution,a supramolecular chemistry strategy was used to construct multinuclear olefin polymerization catalysts.Urea functional groups were installed into severalα-diimine palladium catalysts to enable hydrogenbonding-induced self-assembly.展开更多
Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized ...Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized polyolefin materials, First, pyridine-diimine cobalt-catalyzed dehydrogenative silylations of various terminal olefins with alkylsilanes lead to the formation of a variety of allylsilanes at high yields, Then, the allylsilanes are copolymerized with ethylene using an α-diimine nickel catalyst, leading to the formation of branched polyolefins with high molecular weight and moderate comonomer incorporation. This subsequent catalytic process is an efficient strategy for the synthesis of silicon-functionalized polyolefins using widely available and inexpensive starting materials.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22279162,22261142664)Natural Science Fund for Colleges and Universities in Anhui Province(2022AH030057)CAS Project for Young Scientists in Basic Research(No.YSBR-094).
文摘Durable and efficient bi-functional catalyst,that is capable of both oxygen evolution reaction and hydrogen evolution reaction under acidic condition,are highly desired for the commercialization of proton exchange membrane water electrolysis.Herein,we report a robust L-Ru/HfO_(2)heterostructure constructed via confining crystalline Ru nanodomains by HfO_(2)matrix.When assembled with a proton exchange membrane,the bi-functional L-Ru/HfO_(2)catalyst-based electrolyzer presents a voltage of 1.57 and 1.67 V to reach 100 and 300 mA cm^(-2)current density,prevailing most of previously reported Ru-based materials as well as commercial Pt/C||RuO_(2)electrolyzer.It is revealed that the synergistic effect of HfO_(2)modification and small crystalline domain formation significantly alleviates the over-oxidation of Ru.More importantly,this synergistic effect facilitates a dual-site oxide path during the oxygen evolution procedure via optimization of the binding configurations of oxygenated adsorbates.As a result,the Ru active sites maintain the metallic state along with reduced energy barrier for the rate-determining step(^(*)O→^(*)OOH).Both of water adsorption and dissociation(Volmer step)are strengthened,while a moderate hydrogen binding is achieved to accelerate the hydrogen desorption procedure(Tafel step).Consequently,the activity and stability of acidic overall water splitting are simultaneously enhanced.
基金supported by the National Natural Science Foundation of China(Grant No.61471301)Natural Science Basic Research Program of Shaanxi,China(Grant No.2017JQ5083)PhD Research Startup Foundation of Xi’an University of Science and Technology,China(Grant No.2017QDJ044)
文摘Orthorhombic YFeO_3 thin film was prepared on La_(0.67)Sr_(0.33)MnO_3/LaAlO_3 substrate by a sol-gel spin-coating method. The structures of the YFeO_3/La_(0.67)Sr_(0.33)MnO_3/LaAlO_3(YFO/LSMO/LAO) sample were detected by x-ray diffraction pattern, Raman spectrometer, scanning electron microscopy, and atomic force microscope. The local ferroelectric polarization switching properties of the orthorhombic YFO film were confirmed by piezoresponse force microscopy(PFM) for the first time. The results show that the YFO film deposited on LSMO/LAO possesses orthorhombic structure,with ultra-fine crystal grains and flat surface. The leakage current of the YFO film is 8.39 × 10^(-4) A·cm^(-2) at 2 V,with its leakage mechanism found to be an ohmic behavior. PFM measurements indicate that the YFO film reveals weak ferroelectricity at room temperature and the local switching behavior of ferroelectric domains has been identified. By local poling experiment, polarization reversal in the orthorhombic YFO film at room temperature was further observed.
基金The authors are thankful to the National Natural Science Foundation of China （Grant No. 50331040）NWPU Doctor Foundation for supporting this work.
文摘The La0.85Sr0.015MnO3/Fe heterostructure deposited on Si （100） substrate was prepared by the magnetron sputtering. The laser-induced voltage in the sample and the difference in the voltage signals between the current-in-plane geometry and current-perpendicular-to-plane geometry at 77 K were investigated. This difference can be attributed to the different transport mechanisms.
基金supported by the National Natural Science Foundation of China(No.50331040)the National Natural Science Foundation of Shaanxi Provice(No.2001C21)NWPU Doctor Foundation(cx200323)
文摘The transport properties in the La2/3（Ca（1-x）Sr（x））1/3MnO3 （x=0.1/3, 2/3） films prepared using the RF magnetron sputtering method were investigated, The effect of the Ca, Sr double-doping at the A position in the La（2/3）A（1/3）MnO3 on the structure of the targets and transport of the films has been studied. With the increase of x, the structures of the targets transform from the rhombohedral phase to the cubic phase; the metal-insulator phase transition temperature （Tp） of the films increases; and the corresponding peak resistivity decreases. All the phenomena can be qualitatively explained by the lattice effect.
基金Project supported by the National Natural Science Foundation of China(Grant No.61471301)
文摘The magneto-electric effect in magnetic materials has been widely investigated, but obtaining an enhanced magnetoelectric effect is challenging. In this study, tricolor superlattices composed of manganese oxides-Pr（0.9）Ca（0.1）MnO3,La（0.9）Sr（0.1）MnO3, and La（0.9）Sb（0.1）MnO3-on（001）-oriented Nb：SrTiO3 substrates with broken space-inversion and timereversal symmetries are designed. Regarding the electric polarization in the hysteresis loops of the superlattices at different external magnetic fields, both coercive electric field Ec and remnant polarization intensity Pr clearly show strong magneticfield dependences. At low temperatures（〈 120 K）, a considerable magneto-electric effect in the well-defined tricolor superlattice is observed that is absent in the single compounds. Both maxima of the magneto-electric coupling coefficients ？Ec and ？Pr appear at 30 K. The magnetic dependence of the dielectric constant further supports the magneto-electric effect. Moreover, a dependence of the magneto-electric effect on the periodicity of the superlattices with various structures is observed, which indicates the importance of interfaces. Our experimental results verify previous theoretical results regarding magneto-electric interactions, thereby paving the way for the design and development of novel magneto-electric devices based on manganite ferromagnets.
文摘Objective: To study the effect of practicing Jianshenqigong-wuqinxi on subhealth problems including depression, anxiety, and memory loss. Methods: 1) 80 cases with subhealth problem were randomly divided into two groups. 40 cases practicing Jianshenqigong-wuqinxi were used as test group, and the other 40 unpracticing cases were used as control group. 2) The test group was practising Jianshenqigong-wuqinxi one hour in the morning five times per week for three months. 3) Scores of subhealth status such as depression and anxiety were evaluated once every two weeks, while the memory test was performed once a month. 4) Data analysis: SPSS11.0 software was used for statistical analyses. Data were shown in mean ± SEM. Difference was considered significant if the t-test P value is less than 0.05. Results: 1) Scores of subhealth state and depression were significantly lower in test group than those of control group. The beneficial effects of practicing Jianshenqigong-wuqinxi were more obvious for the subjects in the test group who had practiced Jianshenqigong-wuqinxi for two to twelve weeks (P < 0.05). 2) Scores of anxiety test were significantly lower in test group than those of control group after practicing Jianshenqigong-wuqinxi for six to twelve weeks (P < 0.05). 3) Scores of memory were significantly higher in test group than those of control group (P < 0.05). Conclusions: 1) Practicing Jianshenqigong-wuqinxi could promote health in people who have subhealth mental problems. 2) Practicing Jianshenqigong-wuqinxi could relieve depression, anxiety while enhance memory.
基金supported by the National Key R&D Program of China(grant no.2021YFA1501700)the National Natural Science Foundation of China(grant nos.52025031,22001004,52373002,U1904212,and 52203016).
文摘Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.
基金supported by the National Key R&D Program of China(2021YFA1501700)the National Natural Science Foundation of China(52025031,22261142664,22301294)+2 种基金China Postdoctoral Science Foundation(BX20230339,2023M743352)the CAS Project for Young Scientists in Basic Research(YSBR-094)Anhui Province Key Research and Development Plan Project(2022j11020004)。
文摘The development of degradable and recyclable polymers is an attractive strategy to tackle the post-consumption pollution issue of commercial plastics.Cyclic-acyclic monomers metathesis polymerization(CAMMP)has been recently reported to produce degradable thermoset,thermoplastic and elastomeric polymers,and their degradability is enabled with addition of various chemicals.In this contribution,we demonstrate that the utilization of diene comonomers containing photodegradable moiety can give access to thermoset and thermoplastic materials bearing photo-degradation capabilities.The copolymerization of a series easily accessible diene comonomers bearing photodegradable ortho-nitrobenzyl moieties with dicyclopentadiene(DCPD)or cyclooctene(COE)leads to the formation of photodegradable p DCPD thermosets and p COE thermoplastic polymers with mechanical properties comparable to their non-degradable counterparts.Most importantly,their photo-degradation properties can be efficiently tuned with the addition of ultraviolet absorber during in-situ polymerization.
基金This work was supported by National Key R&D Program of China(No.2021YFA1501700)National Natural Science Foundation of China(No.52025031,52203016,and 22261142664)USTC Research Funds of the Double First-Class Initiative(YD9990002018).
文摘Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of highly active phosphino-phenolate nickel catalysts with polymer-insoluble solvent(heptane)to access UHMWPE(Mn up to 8.3×10^(6)g mol^(-1))with good product morphology,free-flowing characteristics,and great mechanical properties.Compared with the academically commonly used aromatic solvent(toluene),the utilization of heptane offers simultaneous enhancement in important parameters including activity,polymer molecular weight,and catalyst thermal stability.This system can also generate polar functionalized UHMWPE with molecular weight of up to 1.6×10^(6)g mol^(-1)in the copolymerization of ethylene with polar comonomers.More importantly,this precipitation polymerization strategy is generally applicable to several representative transition metal catalyst systems,leading to UHMWPE synthesis with good product morphology control.
基金supported by the National Natural Science Foundation of China (21690071 and 21871242)the Fundamental Research Funds for the Central Universities.
文摘For transition metal-based olefin polymerization catalysts, ligand steric and electronic effects can strongly influence important catalytic properties. However, the simultaneous tuning of both steric and electronic effects has not been explored in most of the previous studies. In this contribution, a strategy to tune the ligand electronic and steric effects in a concerted fashion is reported. In such a system, both dibenzhydryl groups and multiple methoxy/fluoro groups were installed in α-diimine ligands. In addition to strongly influencing ligand electronics, the methoxy/fluoro groups can interact with the dibenzhydryl groups and efficiently increase ligand sterics. In ethylene polymerization, this concurrent tuning of electronic and steric effects can lead to simultaneous enhancement of several parameters(activity, stability, polymer molecular weight, melting point, branching density) for both the nickel and palladium catalysts. The effectiveness of this strategy is highly attractive for future studies in other catalytic systems.
基金supported by the National Natural Science Foundation of China(21374108,21304054)the Promotive Research Fund for the Young and Middle-aged Scientists of Shandong Province(BS2012CL018)+2 种基金the Foundation of Qufu Normal University(XJ201212)the Fundamental Research Funds for the Central Universities(WK3450000001)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,Donghua University(LK1424)
文摘In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization mechanism for this type of catalysts was discussed. Next, recent advances in ligand design were provided with special focus on the influence of ligand structures on the catalytic polymerization properties. Last, the ethylene homopolymerization and copolymerization with various polar comonomers, especially acrylate and vinyl ethers were summarized.
基金the National Natural Science Foundation of China(52025031,21690071,U19B6001,and U1904212)K.C.Wong Education Foundation。
文摘The transition-metal-catalyzed copolymerization of olefins with polar comonomers is a direct strategy to access polar-functionalized polyolefins in an economical manner.Due to the intrinsic poisoning effect of polar groups towards Lewis acidic metal centers and the drastic reactivity differences of polar comonomers versus non-polar olefins,it is challenging to develop catalysts that provide the desired polymer molecular weight,comonomer incorporation,and activity.In this contribution,we tackle this issue from a comonomer perspective using 5,6-disubstituted norbornenes,which are highly versatile,easily accessible,inexpensive,and capable of introducing two functional groups in a single insertion.More importantly,they are only mildly poisoning due to the presence of long spacers between double bonds and polar groups,and are not prone to b-hydride elimination due to their cyclic structures.As strong pdonors,they can competitively bind to metal centers versus olefins.Indeed,phosphine-sulfonate palladium catalysts can catalyze the copolymerization of ethylene with 5,6-disubstituted norbornenes and simultaneously achieve a high polymerization activity,copolymer molecular weight,and comonomer incorporation.The practicality of this system was demonstrated by studying the properties of the resulting polymers,copolymerization in hydrocarbon solvents or in bulk,recovery/utilization of unreacted comonomer,molecular weight modulation,and large-scale synthesis.
基金This work was supported by the National Natural Science Foundation of China(21690071,U19B6001 and U1904212).
文摘Ziegler and Natta won the Nobel Prize in 1963 due to their contributions in olefin polymerization catalysis.Subsequent studies into related catalysts have led to a multibillion-dollar polyolefin industry.Currently,more than 178 million tons of polyolefin materials are produced annually,which constitute more than half of global plastics production.Interestingly,the metal nickel was initially recognized as a“poison”for olefin polymerization.Alkyl aluminum species can oligomerize ethylene(degree of polymerization up to 100)at high temperature and pressure;while the addition of nickel salt to the system led to the exclusive formation of 1-butene.This famous“nickel effect”marks the starting point of the era of Ziegler catalysts[1].After decades of research,the situation of nickel has changed dramatically,and a large number of nickelbased catalysts have been shown with the capabilities of producing high-molecular-weight polyethylene.As an exceptional demonstration,some groups have recently developed nickel catalysts that are able to produce ultra-high molecular weight polyethylene(UHMWPE).UHMWPE,with molecular weight of above one-million,is a special class of advanced engineering plastics with superior properties and wide applications.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.52025031,21871242,U19B6001 and U1904212)and K.C.Wong Education Foundation.
文摘In the past few decades,the development of high-performance catalysts has been a key driving force and a center of research efforts in the field of olefin polymerization.However,a major discrepa ncy exists between in dustrial researches which utilize aliphatic hydrocarb on solventsz and academic researches which predominantly focus the catalytic properties in aromatic solvents.In this con-tribution,a novel diaryl-methyl aniline bearing eight tert-butyl groups was prepared and subsequently transformed to four different kinds of imine-type ligands.The corresponding nickel complexes as well as their counterparts derived from diphenyl-methyl aniline without the tert-butyl groups were prepared and investigated in ethylene polymerization.
基金the National Natural Science Foundation of China(Grant Nos.52025031,21690071,22001004,U19B6001 and U1904212)K.C.Wong Education Foundation。
文摘A series of dibenzhydryl-based iminopyridine-N-oxide ligands bearing a range of electron-donating or-withdrawing substituents(OMe,H;and NO_(2))and corresponding nickel pre-catalysts are prepared and characterized.The substituents are installed at different positions on the ligand structure,including 4-position of the pyridine-N-oxide moiety(position X)and 4-position of the aniline moiety(position Y).These nickel pre-catalysts are highly active in ethylene polymerization with the addition of very little amount of aluminum cocatalysts,leading to the formation of polyethylenes with molecular weights of well above one million.Electron-donating substituents make the catalysts sensitive to polymerization temperature.In contrast,the catalysts bearing electron-withdrawing NO_(2) substituents show relatively steady performances at different temperatures.Most importantly,we demonstrate that different substituents and different positions both play important roles in determining the properties of nickel catalysts.This provides an alternative strategy for the future design of high-performance polymerization catalyst.
基金supported by the National Natural Science Foundation of China (21690071, 51522306)
文摘Phosphine-sulfonate based palladium is one of the most extensively studied catalyst systems in olefin polymerization.This type of catalyst features six-membered chelate ring size,and can enable the copolymerizations of ethylene with a wide variety of polar monomers.In this contribution,we decide to investigate the influence of chelate ring size on the properties of phosphinesulfonate palladium catalysts.As such,a series of phosphine-sulfonate ligands and the corresponding seven-membered ring Pd(II)complexes[κ~2-(P,O)-2-(CH_2-PR_1R_2)-4-methylphenyl-sulfonato]Pd(Me)(DMSO)(Pd1,R_1=R_2=Cy,Pd2,R_1=R_2=o-Me O-C_6H_4;Pd3,R_1=Ph,R_2=2-[2,6-(Me O)_2C_6H_3]C_6H_4;DMSO=dimethyl sulfoxide)were designed,prepared and characterized.These palladium complexes are moderately active when they were applied in ethylene polymerization and copolymerizations with methyl acrylate and butyl vinyl ether.However,their properties are greatly reduced from those of the classic six-membered ring phosphine-sulfonate palladium complex Pd2′.The experimental results indicate that the bigger chelate ring size can increase the ligand flexibility and damage the catalytic properties for the phosphine-sulfonate type palladium catalysts.
文摘Introduction of polar comonomers into polyethylene is highly challenging,paving the way to tuning the copolymers'mechanical properties,adhesion/compatibility,and biodegradability.Polar-group tolerant single-site palladium and,more tempting,nickel-based catalysts have demon-strated promising reactivities in the ethylene copolymerization with polar comonomers via coordination/insertion mechanism。
基金supported by the National Natural Science Foundation of China (Nos. 50331040 and 60171043)
文摘Magnetocaloric and colossal magnetoresistance effects of the layered perovskite La 1.4 Sr 1.6 Mn 2 O 7 compound have been studied.A broad peak of magnetic entropy change （-△S M） is found above the Curie temperature （T C =120 K）,which can be associated with the existence of two-dimensional short range ferromagnetic order.Additionally,the curvilinear shape of-△S M for layered perovskite is quite different from that of the Ln 1-x A x MnO 3 probably arising from magnetocrystalline anisotropy.At the same time,a wide peak of colossal magnetoresitance effect near T C is found in the layered provskite La 1.4 Sr 1.6 Mn 2 O 7.
基金supported by the National Natural Science Foundation of China(grant nos.21690071,21871242,U19B6001,and U1904212)the K.C.Wong Education Foundation,and the Fundamental Research Funds for the Central Universities.
文摘Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of metal–metal distance are complicated and time-consuming.In this contribution,a supramolecular chemistry strategy was used to construct multinuclear olefin polymerization catalysts.Urea functional groups were installed into severalα-diimine palladium catalysts to enable hydrogenbonding-induced self-assembly.
基金supported by the National Natural Science Foundation of China(21690071 and 51522306)
文摘Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized polyolefin materials, First, pyridine-diimine cobalt-catalyzed dehydrogenative silylations of various terminal olefins with alkylsilanes lead to the formation of a variety of allylsilanes at high yields, Then, the allylsilanes are copolymerized with ethylene using an α-diimine nickel catalyst, leading to the formation of branched polyolefins with high molecular weight and moderate comonomer incorporation. This subsequent catalytic process is an efficient strategy for the synthesis of silicon-functionalized polyolefins using widely available and inexpensive starting materials.
