Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymer...Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.展开更多
Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed...Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.展开更多
Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),...Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g.molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65 ℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.展开更多
Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been construc...Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.展开更多
A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu2(L)(CN)2]n(1, L =1,1′-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of...A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu2(L)(CN)2]n(1, L =1,1′-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of acetonitrile under hydrothermal conditions. CP 1 was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, Pccn space group, with a = 10.314(3), b = 20.966(7), c =9.432(3)?, V = 2039.5(11)?3, Z = 4, C21 H20 Cu2 N6, Mr = 483.51, Dc = 1.575 g×cm^-3,μ= 2.105 mm-1 and F(000)= 984, the final R = 0.0608 and wR = 0.1942 for 1226 observed reflections with Ⅰ> 2s(Ⅰ)for the CP 1. The CP 1 possesses a 2D {63} layer structure which is composed of Cu(Ⅰ) centers bridged by L and CN– ligands. The thermal stability and luminescence properties of CP 1 are discussed in detail. The complex also displays a remarkable activity for the degradation of methyl orange by hydrogen peroxide in a Fenton-like process.展开更多
Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free r...Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free radial emulsion polymerization was employed for synthesis of p（NIPAAm-HEMA-AAc） polymer microgels. Silver nanoparticles were introduced within the microgels sphere by in situ reduction method. Microgels and hybrid microgels were characterized by Fourier transform infrared spectroscopy, ultra violet-visible spectroscopy,transmission electron microscopy and dynamic light scattering measurements. Catalytic activity of Ag-p（NIPAAm-HEMA-AAc） hybrid microgels was studied using catalytic reduction of 4-nitrophenol（4-NP） as a model reaction in aqueous media. The influence of sodium borohydride（Na BH4） concentration, catalyst dose and 4-NP concentration on catalytic reduction of 4-NP was investigated. A linear relationship was found between catalyst dose and apparent rate constant（kapp）. The mechanism of catalysis by hybrid microgels was explored for further development in this area. The deep analysis of catalytic process reveals that the unique combination of NIPAAm, HEMA and AAc does not only stabilize silver nanoparticles in polymer network but it also enhances the mass transport of hydrophilic substrate like 4-NP from outside to inside the polymer network.展开更多
Various pretreatments of poly (N-vinyl-2-pyrrolidone) (PVP) protected palladium-cobalt system result in different catalytic activities in the hydrodechlorination of chlorobenzene.
A simple and facile synthetic methodology for fabricating the regenerated silk fibroin （RSF）-based hydrogel which consisted of the in situ generated magnetic ferriferous oxide （Fe304） was developed. Using the co-p...A simple and facile synthetic methodology for fabricating the regenerated silk fibroin （RSF）-based hydrogel which consisted of the in situ generated magnetic ferriferous oxide （Fe304） was developed. Using the co-precipitation of Fe2＋ and Fe3＋ within the RSF-based hydrogel with 90% RSF and 10% HPMC （hydroxypropyl methyl cellulose）, the as-prepared RSF/Fe304 hydrogel not only showed high strength of saturation magnetization, but also exhibited excellent catalytic activities. For example, with the assistant of 3,3＇,5,5＇-tetramethylbenzidine （TMB）, the RSF/Fe304 hydrogel could detect H202 at a concentration as low as 1 x 10-6 mol.L-1 In addition, the catalytic activities were able to be maintained for a long term under various conditions. These findings suggest that the RSF-based materials can be endowed with interesting properties, and have great potential for the applications in the fields of biotechnology and environmental chemistry.展开更多
Perovskite-type oxides La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structu...Perovskite-type oxides La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.展开更多
A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling mode...A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.展开更多
This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis（phenoxyimine） ligands. Six phenoxy-imine Ti（IV） complexes {6-R^1-2-[CH=N（2,6-difluoro-3,5-diR^2-4-R^3Ph）]C6H30}2...This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis（phenoxyimine） ligands. Six phenoxy-imine Ti（IV） complexes {6-R^1-2-[CH=N（2,6-difluoro-3,5-diR^2-4-R^3Ph）]C6H30}2TiCl2 （1： R^1 = H, R^2 = H, R^3 = H; 2： R^1 = H, R^2 = H, R%3 = 4-vinylphenyl; 3： R^1 = CH3, R^2 = H, R^3 = H; 4： R^1 = CH3, R^2 = H, R^3 = 4-vinylphenyl; 5： R^1 = CH3, R^2 = F, R^3 = H; 6： R^1 = CH3, R^2 = F, R^3 = 4-vinylphenyl） have been synthesized and evaluated for ethylene polymerization using dried MAO （simplified as DMAO） as cocatalyst. An obvious catalytic heterogeneity of Cat 2 （Complex 2/DMAO） towards ethylene polymerization was observed, which was illustrated by decreased activity, multi- modal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits ＂living＂ characteristics in the process under certain conditions （25 ~C, less than 20 min）. Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/（mol Ti＇h） and high molecular weight （Mw = 105-106） of polyethylene can be obtained by changing the skeleton structure of these complexes.展开更多
Propionamide complexes of rare earth chlorides were synthesized. Formula of the complexes is LnCl 3·3PA. The ligand is shown to behave as a normal amide donor with the oxygen of the carbonyl group coordinated to...Propionamide complexes of rare earth chlorides were synthesized. Formula of the complexes is LnCl 3·3PA. The ligand is shown to behave as a normal amide donor with the oxygen of the carbonyl group coordinated to the metal ions. Binary system composed of propionamide and aluminum alkyl shows higher activity and stereospecificity for butadiene polymerization. The cis 1,4 content of polybutadiene is more than 98%.展开更多
An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene poly...An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.展开更多
Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural ...Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.展开更多
Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based o...Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.展开更多
Divalent organosamarium and organoytterbium complexes as a kind of strong reducing agent not only can react with electron rich agents such as halides, aldehyde, ketone, unsaturated hydrocarbon and the compounds contai...Divalent organosamarium and organoytterbium complexes as a kind of strong reducing agent not only can react with electron rich agents such as halides, aldehyde, ketone, unsaturated hydrocarbon and the compounds containing active hydrogen but also can catalyze hydrogenation of alkyne, ethylene polymerization and methyl methacrylate polymerization. More and more interests and attention have been given to the synthesis, structure and catalytic activity of divalent organolanthanide complexes in recent years,展开更多
(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the ...(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.展开更多
Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of...Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of vip molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.展开更多
In order to study the influence of substituents on imino-aryl rings of mono(imino)pyrrole-transition metal complexes to their ethylene polymerization performance,a series of mono(imine)pyrroles(L1-L3)were synthesized ...In order to study the influence of substituents on imino-aryl rings of mono(imino)pyrrole-transition metal complexes to their ethylene polymerization performance,a series of mono(imine)pyrroles(L1-L3)were synthesized by microwave irradiation from 2-acetylpyrrole and a series of 2,6-position disubstituted anilines(substituent:H,Me,Et).A simplified synthetic method was introduced to prepare the corresponding nickel complexes NiL2(1~3)with direct condensation of mono(imine)pyrrole ligands and nickel dichloride.All the compounds were fully characterized by 1 H NMR,IR,EA,MS,and X-ray crystal diffraction.Ligand L3(C16H20N2,Mr=240.34)belongs to the triclinic system,space group P1,with a=7.9606(19),b=9.028(2),c=11.205(3)?,the final R=0.0606 and wR=0.1875.Complex 3(C32H38N4Ni,Mr=537.37)belongs to the monoclinic system,space group C2/c with a=19.811(3),b=11.262(2),c=26.004(4)?,the final R=0.0388 and wR=0.1020.The crystal structures indicated that all the NiⅡcomplexes have similar tetra-coordinated geometries,in which the ligand chelated to the center nickel with a 2:1 molar ratio.Catalytic properties of the NiⅡcomplexes for ethylene polymerization were systematically investigated,and the results showed a regular increase of catalytic activities with steric hindrance of the substituents on the imino-aryl ring of NiⅡcomplexes.展开更多
he polymers containing different ligand groups of atoms(mainly O,N,and S)and their rare earth complexes were prepared,characterized and classified based on the type of metal-ligand bonding. The catalytic activities of...he polymers containing different ligand groups of atoms(mainly O,N,and S)and their rare earth complexes were prepared,characterized and classified based on the type of metal-ligand bonding. The catalytic activities of the complexes are briefly discussed.The polymer- supported rare earth complexes shwed much greater activities than the correspond- ing complexes with a low molecular weight.展开更多
文摘Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.
文摘Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.
基金Supported by the National Natural Science Foundation of China (21036009,21176268)the Higher-level Talent Project for Guangdong Provincial Universities+1 种基金the Fundamental Research Funds for the Central UniversitiesGuangdong Province 211 Project
文摘Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g.molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65 ℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.
文摘Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.
基金Supported by the National Natural Science Foundation of China(No.51474086)
文摘A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu2(L)(CN)2]n(1, L =1,1′-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of acetonitrile under hydrothermal conditions. CP 1 was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, Pccn space group, with a = 10.314(3), b = 20.966(7), c =9.432(3)?, V = 2039.5(11)?3, Z = 4, C21 H20 Cu2 N6, Mr = 483.51, Dc = 1.575 g×cm^-3,μ= 2.105 mm-1 and F(000)= 984, the final R = 0.0608 and wR = 0.1942 for 1226 observed reflections with Ⅰ> 2s(Ⅰ)for the CP 1. The CP 1 possesses a 2D {63} layer structure which is composed of Cu(Ⅰ) centers bridged by L and CN– ligands. The thermal stability and luminescence properties of CP 1 are discussed in detail. The complex also displays a remarkable activity for the degradation of methyl orange by hydrogen peroxide in a Fenton-like process.
基金financial support for research from Higher Education Commission Pakistan under National Research Program for Universities(NRPU)(No.20-3995/WRPU/R&D/HEC/14/1212)Research Centre for Advanced Materials Science - King Khalid University, Saudi Arabia for support
文摘Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free radial emulsion polymerization was employed for synthesis of p（NIPAAm-HEMA-AAc） polymer microgels. Silver nanoparticles were introduced within the microgels sphere by in situ reduction method. Microgels and hybrid microgels were characterized by Fourier transform infrared spectroscopy, ultra violet-visible spectroscopy,transmission electron microscopy and dynamic light scattering measurements. Catalytic activity of Ag-p（NIPAAm-HEMA-AAc） hybrid microgels was studied using catalytic reduction of 4-nitrophenol（4-NP） as a model reaction in aqueous media. The influence of sodium borohydride（Na BH4） concentration, catalyst dose and 4-NP concentration on catalytic reduction of 4-NP was investigated. A linear relationship was found between catalyst dose and apparent rate constant（kapp）. The mechanism of catalysis by hybrid microgels was explored for further development in this area. The deep analysis of catalytic process reveals that the unique combination of NIPAAm, HEMA and AAc does not only stabilize silver nanoparticles in polymer network but it also enhances the mass transport of hydrophilic substrate like 4-NP from outside to inside the polymer network.
文摘Various pretreatments of poly (N-vinyl-2-pyrrolidone) (PVP) protected palladium-cobalt system result in different catalytic activities in the hydrodechlorination of chlorobenzene.
基金financially supported by the National Natural Science Foundation of China(No.21574024)
文摘A simple and facile synthetic methodology for fabricating the regenerated silk fibroin （RSF）-based hydrogel which consisted of the in situ generated magnetic ferriferous oxide （Fe304） was developed. Using the co-precipitation of Fe2＋ and Fe3＋ within the RSF-based hydrogel with 90% RSF and 10% HPMC （hydroxypropyl methyl cellulose）, the as-prepared RSF/Fe304 hydrogel not only showed high strength of saturation magnetization, but also exhibited excellent catalytic activities. For example, with the assistant of 3,3＇,5,5＇-tetramethylbenzidine （TMB）, the RSF/Fe304 hydrogel could detect H202 at a concentration as low as 1 x 10-6 mol.L-1 In addition, the catalytic activities were able to be maintained for a long term under various conditions. These findings suggest that the RSF-based materials can be endowed with interesting properties, and have great potential for the applications in the fields of biotechnology and environmental chemistry.
基金Project supported by Ordinary University Major Project of Guangdong Province,China,(2017KZDXM057)Ordinary University Characteristic Innovation Project of Guangdong Province,China,(2016KTSCX091)
文摘Perovskite-type oxides La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.
基金financially supported by the National Natural Science Foundation of China(Nos.U1862206 and 21801236)。
文摘A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.
基金financially supported by the National Natural Science Foundation of China(Nos.20936006 and 20976152)National Basic Research Program of China(2011CB606001)+1 种基金Doctoral Program of Higher Education of China(No.20100101110041)Program for Changjiang Scholars and Innovative Research Team in Zhejiang University
文摘This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis（phenoxyimine） ligands. Six phenoxy-imine Ti（IV） complexes {6-R^1-2-[CH=N（2,6-difluoro-3,5-diR^2-4-R^3Ph）]C6H30}2TiCl2 （1： R^1 = H, R^2 = H, R^3 = H; 2： R^1 = H, R^2 = H, R%3 = 4-vinylphenyl; 3： R^1 = CH3, R^2 = H, R^3 = H; 4： R^1 = CH3, R^2 = H, R^3 = 4-vinylphenyl; 5： R^1 = CH3, R^2 = F, R^3 = H; 6： R^1 = CH3, R^2 = F, R^3 = 4-vinylphenyl） have been synthesized and evaluated for ethylene polymerization using dried MAO （simplified as DMAO） as cocatalyst. An obvious catalytic heterogeneity of Cat 2 （Complex 2/DMAO） towards ethylene polymerization was observed, which was illustrated by decreased activity, multi- modal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits ＂living＂ characteristics in the process under certain conditions （25 ~C, less than 20 min）. Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/（mol Ti＇h） and high molecular weight （Mw = 105-106） of polyethylene can be obtained by changing the skeleton structure of these complexes.
文摘Propionamide complexes of rare earth chlorides were synthesized. Formula of the complexes is LnCl 3·3PA. The ligand is shown to behave as a normal amide donor with the oxygen of the carbonyl group coordinated to the metal ions. Binary system composed of propionamide and aluminum alkyl shows higher activity and stereospecificity for butadiene polymerization. The cis 1,4 content of polybutadiene is more than 98%.
基金This work was financially supported by the National Natural Science Foundation of China (No. 29734141, 50103012) Core Research for Engineering Innovation KGCX2-203, the Foundation of "One Hundred Talents" program for W-H Sun, Chinese Academy of Sciences
文摘An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.
基金Supported by the National Basic Research Program of China("973"Program,2014CB260408)Tianjin Natural Science Foundation(No.13JCYBJC19300)
文摘Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.
基金supported by the Key Research and Development Program of Ningxia Autonomous Region (No.2023BFE01001)Tianjin Science and Technology Program (Nos.22ZYJDSS00060+2 种基金22YDTPJC00920)Program for Tianjin Innovative Research Team in Universities (No.TD13-5031)Tianjin 131 Research Team of Innovative Talents。
文摘Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.
基金Project supported by the National Natural Science Foundation of China Academia Sinica and Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Academia Sinica.
文摘Divalent organosamarium and organoytterbium complexes as a kind of strong reducing agent not only can react with electron rich agents such as halides, aldehyde, ketone, unsaturated hydrocarbon and the compounds containing active hydrogen but also can catalyze hydrogenation of alkyne, ethylene polymerization and methyl methacrylate polymerization. More and more interests and attention have been given to the synthesis, structure and catalytic activity of divalent organolanthanide complexes in recent years,
文摘(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.
基金This study was financially supported by the National Nature Science Foundation of China(nos.21771177 and 51603206)the Strategic Priority Research Program of CAS(no.XDB20000000)the Key Research Program of Frontier Sciences,CAS(no.QYZDB-SSW-SLH019).
文摘Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of vip molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.
基金supported by the National Natural Science Foundation of China (No. 51674200)the Science and Technology Research Program of Shaanxi Province (2019JM-421,2018JM2035)。
文摘In order to study the influence of substituents on imino-aryl rings of mono(imino)pyrrole-transition metal complexes to their ethylene polymerization performance,a series of mono(imine)pyrroles(L1-L3)were synthesized by microwave irradiation from 2-acetylpyrrole and a series of 2,6-position disubstituted anilines(substituent:H,Me,Et).A simplified synthetic method was introduced to prepare the corresponding nickel complexes NiL2(1~3)with direct condensation of mono(imine)pyrrole ligands and nickel dichloride.All the compounds were fully characterized by 1 H NMR,IR,EA,MS,and X-ray crystal diffraction.Ligand L3(C16H20N2,Mr=240.34)belongs to the triclinic system,space group P1,with a=7.9606(19),b=9.028(2),c=11.205(3)?,the final R=0.0606 and wR=0.1875.Complex 3(C32H38N4Ni,Mr=537.37)belongs to the monoclinic system,space group C2/c with a=19.811(3),b=11.262(2),c=26.004(4)?,the final R=0.0388 and wR=0.1020.The crystal structures indicated that all the NiⅡcomplexes have similar tetra-coordinated geometries,in which the ligand chelated to the center nickel with a 2:1 molar ratio.Catalytic properties of the NiⅡcomplexes for ethylene polymerization were systematically investigated,and the results showed a regular increase of catalytic activities with steric hindrance of the substituents on the imino-aryl ring of NiⅡcomplexes.
文摘he polymers containing different ligand groups of atoms(mainly O,N,and S)and their rare earth complexes were prepared,characterized and classified based on the type of metal-ligand bonding. The catalytic activities of the complexes are briefly discussed.The polymer- supported rare earth complexes shwed much greater activities than the correspond- ing complexes with a low molecular weight.
