α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were ...α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.展开更多
Controlled release NPK compound fertilizers were prepared by means of in situ polymerization of monomers on the surface of fertilizer granules at room temperature. Methacrylate, α-methyl acrylic acid, and ethylene di...Controlled release NPK compound fertilizers were prepared by means of in situ polymerization of monomers on the surface of fertilizer granules at room temperature. Methacrylate, α-methyl acrylic acid, and ethylene dimethylacrylate were used as monomers, Dibenzoyl peroxide as initiator, and cobalt naphthenate, and triethyl amine as promoters. The structures of coating materials were characterized by IR spectra. The thermogravimetric analysis result indicated that the coating materials were of good thermal stability. The mean thickness of single coating measured with screw gauge was ca. 140 μm. The morphologies of uncoated and coated fertilizer granules analyzed by using scanning electron microscopy were changed from porosities and gullies to hills and plain. The release rate of coated compound fertilizers in water could be controlled by the hydrophicity and thickness of coating. The increase in coating hydrophicity caused the increase in release rate of fertilizer. The increase in thickness of coating slowed the release rate.展开更多
Poly （methyl methacrylate） （PMMA） brushes were synthesized from silicon wafers via surface initiated atom transfer radical polymerization （SI-ATRP）. Energy disperse spectroscopy （EDS） and atomic force microsco...Poly （methyl methacrylate） （PMMA） brushes were synthesized from silicon wafers via surface initiated atom transfer radical polymerization （SI-ATRP）. Energy disperse spectroscopy （EDS） and atomic force microscopy （AFM） confirmed that PMMA brushes were successfully prepared on the silicon wafers, and the surface became more hydrophobic according to the contact angle of 69~. It is found that CuCI/1, 1, 4, 7, 10, 10-hexamethyl triethylenetetramine （HMTETA） system is more suitable than CuBr/N, N, N′, N″, N′″-pentamethyl diethylenetriamine （PMDETA） system to control the free radical polymerization of MMA in solution. Nevertheless, better control on the thickness of PMMA brushes was achieved in CuBr/PMDETA than in CuC1/HMTETA due to higher activity and better reversibility of the former system.展开更多
Polyesters,such as polylactide(PLA),are a class of biodegra-dable and biocompatible polymers that have received increasing attention in biomedicine,agriculture,and commodity thermoplastics[1-2].However,the lack of pen...Polyesters,such as polylactide(PLA),are a class of biodegra-dable and biocompatible polymers that have received increasing attention in biomedicine,agriculture,and commodity thermoplastics[1-2].However,the lack of pendant functionality of conventional polyesters makes it difficult to modify and modulate the physicochemical properties in subsequent applications[3-4].Since 2006[5],the ring-opening polymerization(ROP)of O-carbox-yanhydrides(OCAs),which can be readily synthesized from amino acid or hydroxyl acid precursors,has been recognized as a promising route to functionalized polyesters[3-4].However,due to the increased methine C-H acidity,significant racemization of the stereogenic center and decreased stereoregularity have been identified for most OCAs,for instance,ManOCA[6](OCA from mandelic acid)and SerOCA[7](OCA from serine),when using typical 4-(dimethylamino)pyridine(DMAP)as catalyst.To minimize epimerization,some classical metal-based catalysts of coordination polymerization have been introduced to mediate ROP of OCAs,furnishing isotactic polyesters[8].展开更多
The redox initiation system for polyacrylate sodium of high molecular mass was designed and its effect with varying component dosage on the degree of polymerization was investigated. The results show that the proper t...The redox initiation system for polyacrylate sodium of high molecular mass was designed and its effect with varying component dosage on the degree of polymerization was investigated. The results show that the proper type and amount of inorganic salt, as well as amine initiator, are conductive to the increase of degree of polymerization. The fine ingredient of the initiation system is as follows:the dosages of amine, persulphate and inorganic salt are 0.75%, 0.10% and 1.00% by mass based on acryl acid respectively, the molar ratio of sulphite to the persulphate is 1:1. Under such conditions the degree of polyacrylate can reach 7.43×107 with a acceptable polymerization time for industrial production.展开更多
The emulsion polymerization of aniline in three phase system of xylene functionalized protonic acid water was carried out using (NH 4) 2S 2O 4 as oxidant. The influences of water phase concentration on the viscosity, ...The emulsion polymerization of aniline in three phase system of xylene functionalized protonic acid water was carried out using (NH 4) 2S 2O 4 as oxidant. The influences of water phase concentration on the viscosity, conductivity, transmittance of polyaniline(PAN) latex and its powders were studied. The results show that the properties of PAN prepared through the emulsion polymerization are influenced by the amount of water used in the polymerization. The morphology of PAN varies with the water phase concentration used in the polymerization, which may result in the change of properties of PAN latex and its powders. When the volume fraction of water (φ) is about 20% 30%, the prepared PAN powder has higher conductivity, and the PAN latex has appropriate viscosity and particle size. The consumption of xylene was reduced at high φ value.展开更多
In this work,by combining the specific selectivity of molecularly imprinted polymer(MIP)with a simple and sensitive electrochemiluminescence(ECL)detection method,a molecularly imprinted ECL sensor for kanamycin(KA)was...In this work,by combining the specific selectivity of molecularly imprinted polymer(MIP)with a simple and sensitive electrochemiluminescence(ECL)detection method,a molecularly imprinted ECL sensor for kanamycin(KA)was developed.The MIP film was synthesized on the surface of gold electrode via electrochemical polymerization,using pyrrole(PY)as the functional monomer and KA as the template molecule.The commonly used luminescent reagent Ru(bpy)32+was employed as the ECL probe,and its co-reagent tripropylamine(TPA)was added to enhance the detection sensitivity of the sensor.Quantitative analysis of KA was performed by evaluating the difference in ECL responses between MIP film electrodes after KA removal and KA rebinding.The sensor exhibited high selectivity,good reproducibility,and stability toward KA,with a linear range of 5.00×10^(-8) to 1.00×10^(-5) mol·L^(-1) and a limit of detection of 1.67×10^(-8) mol·L^(-1)(S/N=3).This work would provide a new idea for the development of simple and sensitive molecularly imprinted ECL sensors.展开更多
Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubri...Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubricant additives,their macromolecular analogs have been rarely considered yet to develop environmentally friendly lubricant additives.In this work,a series of boron-containing copolymers have been synthesized by free-radical copolymerization of stearyl methacrylate and isopropenyl boronic acid pinacol ester with different feeding ratios(S_(n)-r-B_(m),n=1,m=1/3,1,2,3,5,9).The resulting copolymers of S_(n)-r-B_(m)(n=1,m=1/3,1,2,3,5)are readily dispersed in the PAO-10 base oil and form micelle-like aggregates with hydrodynamic diameters ranging from 9.7 to 52 nm.SRV-IV oscillating reciprocating tribological tests on ball-on-flat steel pairs show that compared with the base oil of PAO-10,the friction coefficients and wear volumes of the base oil solutions of S_(n)-r-B_(m)decrease considerably up to 62%and 97%,respectively.Moreover,the base oil solution of S_(1)-r-B_(1)exhibits an excellent load-bearing capacity of(850±100)N.These superior lubricating properties are due to the formation of protective tribofilms comprising S_(n)-r-B_(m),boron oxide,and iron oxide compounds on the lubricated steel surface.Therefore,the boron-containing copolymers can be regarded as a novel class of environmentally friendly lubricating oil macroadditives for efficient friction and wear reduction without sulfur and phosphorus elements.展开更多
Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic...Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),campho...We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.展开更多
Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous s...Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.展开更多
A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been d...A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been designed and synthesized through solvothermal reaction.Structural analysis shows that Cd(Ⅱ)is connected by H4L and 1,4-bimb to form a 2D network,and 1,4-bimb further expands the 2D network into a 3D framework.CP 1 can be used as an excellent fluorescence sensor for Fe^(3+)and 4-nitrophenol(4-NP),with low detection limits and good anti-interference.The detection limits of Fe^(3+)and 4-NP were 0.034 and 0.031μmol·L^(-1),respectively.In addition,the fluorescence quenching mechanism was studied.1 was successfully applied to determine Fe^(3+)and 4-NP content in the Yanhe River water sample.CCDC:2351092.展开更多
Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal me...This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal method,demonstrating a significant improvement in photocatalytic NO removal under visible light irradiation.For high-flux simulated flue gas,the composite with 10%SnS_(2)(denoted as SNCN-10)showed exceptional NO removal efficiency,reaching up to 66.8%,along with excellent reusability over five consecutive cycles.Detailed band structure and density of states(DOS)calculations confirmed the formation of a characteristic heterojunction.Spin-trapping ESR spectroscopy identified·O_(2)^(-)−as the key reactive species driving NO oxidation.Additionally,in situ DRIFT spectroscopy revealed that SNCN-10 facilitated the conversion of NO to nitrate through intermediate species,including bridging nitrite and cis-nitrite(N_(2)O_(2)^(2-)).Kinetic studies further indicated that NO oxidation followed the Langmuir-Hinshelwood(L-H)mechanism.Based on density functional theory(DFT)calculations of free energy changes,a comprehensive reaction pathway for NO oxidation was proposed.These findings provide valuable insights for the development of efficient photocatalytic strategies for NO removal.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_...A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.展开更多
Recently,foamed polymers have been widely used in the repair of underground engineering disasters by grouting(trenchless technology)due to controllable gelation time and self-expansion.However,the grouting process bec...Recently,foamed polymers have been widely used in the repair of underground engineering disasters by grouting(trenchless technology)due to controllable gelation time and self-expansion.However,the grouting process becomes more complicated due to the complex geological conditions and the self-expansion of slurry.Therefore,this paper adopts a self-made visual experimental device with peripheral pressure and water plugging rate(WPR)monitoring functions to study the influence of main influencing parameters(particle size distribution,grouting amount and dynamic water pump pressure(DWPP))on the spatiotemporal distribution of slurry WPR and diffusion dynamic response(peripheral pressure).The results show that:When grouting amount is 563 g and DWPP is 0.013 MPa,the expansion force of the slurry in the diffusion process is dominant and can significantly change the local sand and gravel skeleton structure.When grouting amount is 563 g,DWPP is 0.013 MPa,and particle size distribution type isⅢ,the flow time of the polymer is shortened,the pores of the gravel are rapidly blocked.Then,the peripheral pressure decreases rapidly with the increase of the distance,and the time to reach the inflection point WPR is shortened.The instantaneous blockage of the pores leads to the delayed transmission of flow field blockage information.展开更多
This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Appl...This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Applications(CEA),software.ABS was selected as the base fuel due to its thermoplastic nature,which allows for the creation of complex fuel geometries through 3D printing,offering significant flexibility in fuel design.Hybrid rockets,which combine a solid fuel with a liquid oxidiser,offer advantages in terms of operational simplicity and safety.However,conventional polymer fuels often exhibit low regression rates and suboptimal combustion efficiencies.In this research,we evaluated a range of metal additives-aluminium(Al),boron(B),nickel(Ni),copper(Cu),and iron(Fe)-at chamber pressures ranging from 1 to 30 bar and oxidiser-to-fuel(O/F)ratios between 1.1 and 12,resulting in 1800 unique test conditions.The main performance parameters used to assess each formulation were characteristic velocity(C^(*))and adiabatic flame temperature.The results revealed that each test produced a different optimum O/F ratio,with most ratios falling between 4 and 6.The highest performance was achieved at a chamber pressure of 30 bar across all formulations.Among the additives,Al and B demonstrated significant potential for improved combustion performance with increasing metal loadings.In contrast,Fe,Cu,and Ni reached optimal performance at a minimum loading of 1%.Future work includes investigating B-Al metal composites as additives into the ABS base polymer fuel,and doing experimental validation tests where the metallised ABS polymer fuel is 3D printed.展开更多
基金supported by the National Natural Science Foundation of China(52203016)the USTC Research Funds of the Double First-Class Initiative(YD9990002018)+3 种基金the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province(2021LCX022)the Key R&D Projects in Anhui Province(2022i01020012)the Natural Science Foundation of Hefei(2022039)the Excellent Research and Innovation Team Project of Anhui Province(2022AH010001).
文摘α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.
基金Supported by Natural Science Foundation of China(30571086)
文摘Controlled release NPK compound fertilizers were prepared by means of in situ polymerization of monomers on the surface of fertilizer granules at room temperature. Methacrylate, α-methyl acrylic acid, and ethylene dimethylacrylate were used as monomers, Dibenzoyl peroxide as initiator, and cobalt naphthenate, and triethyl amine as promoters. The structures of coating materials were characterized by IR spectra. The thermogravimetric analysis result indicated that the coating materials were of good thermal stability. The mean thickness of single coating measured with screw gauge was ca. 140 μm. The morphologies of uncoated and coated fertilizer granules analyzed by using scanning electron microscopy were changed from porosities and gullies to hills and plain. The release rate of coated compound fertilizers in water could be controlled by the hydrophicity and thickness of coating. The increase in coating hydrophicity caused the increase in release rate of fertilizer. The increase in thickness of coating slowed the release rate.
基金Project(21376271)supported by the National Natural Science Foundation of ChinaProject(2013)supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,China+2 种基金Projects(CL12129,201310533008)supported by the Undergraduates Innovative Training Foundation of Central South University,ChinaProject(Z12060)supported by the Undergraduate Free Exploration Innovation Foundation of Central South University,ChinaProject(CSUZC2013008)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘Poly （methyl methacrylate） （PMMA） brushes were synthesized from silicon wafers via surface initiated atom transfer radical polymerization （SI-ATRP）. Energy disperse spectroscopy （EDS） and atomic force microscopy （AFM） confirmed that PMMA brushes were successfully prepared on the silicon wafers, and the surface became more hydrophobic according to the contact angle of 69~. It is found that CuCI/1, 1, 4, 7, 10, 10-hexamethyl triethylenetetramine （HMTETA） system is more suitable than CuBr/N, N, N′, N″, N′″-pentamethyl diethylenetriamine （PMDETA） system to control the free radical polymerization of MMA in solution. Nevertheless, better control on the thickness of PMMA brushes was achieved in CuBr/PMDETA than in CuC1/HMTETA due to higher activity and better reversibility of the former system.
文摘Polyesters,such as polylactide(PLA),are a class of biodegra-dable and biocompatible polymers that have received increasing attention in biomedicine,agriculture,and commodity thermoplastics[1-2].However,the lack of pendant functionality of conventional polyesters makes it difficult to modify and modulate the physicochemical properties in subsequent applications[3-4].Since 2006[5],the ring-opening polymerization(ROP)of O-carbox-yanhydrides(OCAs),which can be readily synthesized from amino acid or hydroxyl acid precursors,has been recognized as a promising route to functionalized polyesters[3-4].However,due to the increased methine C-H acidity,significant racemization of the stereogenic center and decreased stereoregularity have been identified for most OCAs,for instance,ManOCA[6](OCA from mandelic acid)and SerOCA[7](OCA from serine),when using typical 4-(dimethylamino)pyridine(DMAP)as catalyst.To minimize epimerization,some classical metal-based catalysts of coordination polymerization have been introduced to mediate ROP of OCAs,furnishing isotactic polyesters[8].
基金Project(G199906490 2) supported by the National Key Fundamental Research and Development Program of China
文摘The redox initiation system for polyacrylate sodium of high molecular mass was designed and its effect with varying component dosage on the degree of polymerization was investigated. The results show that the proper type and amount of inorganic salt, as well as amine initiator, are conductive to the increase of degree of polymerization. The fine ingredient of the initiation system is as follows:the dosages of amine, persulphate and inorganic salt are 0.75%, 0.10% and 1.00% by mass based on acryl acid respectively, the molar ratio of sulphite to the persulphate is 1:1. Under such conditions the degree of polyacrylate can reach 7.43×107 with a acceptable polymerization time for industrial production.
基金TheNaturalScienceFoundationofHunanProvince (No .98JJY2 0 6 0 )
文摘The emulsion polymerization of aniline in three phase system of xylene functionalized protonic acid water was carried out using (NH 4) 2S 2O 4 as oxidant. The influences of water phase concentration on the viscosity, conductivity, transmittance of polyaniline(PAN) latex and its powders were studied. The results show that the properties of PAN prepared through the emulsion polymerization are influenced by the amount of water used in the polymerization. The morphology of PAN varies with the water phase concentration used in the polymerization, which may result in the change of properties of PAN latex and its powders. When the volume fraction of water (φ) is about 20% 30%, the prepared PAN powder has higher conductivity, and the PAN latex has appropriate viscosity and particle size. The consumption of xylene was reduced at high φ value.
文摘In this work,by combining the specific selectivity of molecularly imprinted polymer(MIP)with a simple and sensitive electrochemiluminescence(ECL)detection method,a molecularly imprinted ECL sensor for kanamycin(KA)was developed.The MIP film was synthesized on the surface of gold electrode via electrochemical polymerization,using pyrrole(PY)as the functional monomer and KA as the template molecule.The commonly used luminescent reagent Ru(bpy)32+was employed as the ECL probe,and its co-reagent tripropylamine(TPA)was added to enhance the detection sensitivity of the sensor.Quantitative analysis of KA was performed by evaluating the difference in ECL responses between MIP film electrodes after KA removal and KA rebinding.The sensor exhibited high selectivity,good reproducibility,and stability toward KA,with a linear range of 5.00×10^(-8) to 1.00×10^(-5) mol·L^(-1) and a limit of detection of 1.67×10^(-8) mol·L^(-1)(S/N=3).This work would provide a new idea for the development of simple and sensitive molecularly imprinted ECL sensors.
文摘Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubricant additives,their macromolecular analogs have been rarely considered yet to develop environmentally friendly lubricant additives.In this work,a series of boron-containing copolymers have been synthesized by free-radical copolymerization of stearyl methacrylate and isopropenyl boronic acid pinacol ester with different feeding ratios(S_(n)-r-B_(m),n=1,m=1/3,1,2,3,5,9).The resulting copolymers of S_(n)-r-B_(m)(n=1,m=1/3,1,2,3,5)are readily dispersed in the PAO-10 base oil and form micelle-like aggregates with hydrodynamic diameters ranging from 9.7 to 52 nm.SRV-IV oscillating reciprocating tribological tests on ball-on-flat steel pairs show that compared with the base oil of PAO-10,the friction coefficients and wear volumes of the base oil solutions of S_(n)-r-B_(m)decrease considerably up to 62%and 97%,respectively.Moreover,the base oil solution of S_(1)-r-B_(1)exhibits an excellent load-bearing capacity of(850±100)N.These superior lubricating properties are due to the formation of protective tribofilms comprising S_(n)-r-B_(m),boron oxide,and iron oxide compounds on the lubricated steel surface.Therefore,the boron-containing copolymers can be regarded as a novel class of environmentally friendly lubricating oil macroadditives for efficient friction and wear reduction without sulfur and phosphorus elements.
文摘Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.
文摘Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.
文摘A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been designed and synthesized through solvothermal reaction.Structural analysis shows that Cd(Ⅱ)is connected by H4L and 1,4-bimb to form a 2D network,and 1,4-bimb further expands the 2D network into a 3D framework.CP 1 can be used as an excellent fluorescence sensor for Fe^(3+)and 4-nitrophenol(4-NP),with low detection limits and good anti-interference.The detection limits of Fe^(3+)and 4-NP were 0.034 and 0.031μmol·L^(-1),respectively.In addition,the fluorescence quenching mechanism was studied.1 was successfully applied to determine Fe^(3+)and 4-NP content in the Yanhe River water sample.CCDC:2351092.
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
基金The project was supported by Natural Science Foundation of Shandong Province(ZR2021MB104)National Natural Science Foundation of China(22078174).
文摘This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal method,demonstrating a significant improvement in photocatalytic NO removal under visible light irradiation.For high-flux simulated flue gas,the composite with 10%SnS_(2)(denoted as SNCN-10)showed exceptional NO removal efficiency,reaching up to 66.8%,along with excellent reusability over five consecutive cycles.Detailed band structure and density of states(DOS)calculations confirmed the formation of a characteristic heterojunction.Spin-trapping ESR spectroscopy identified·O_(2)^(-)−as the key reactive species driving NO oxidation.Additionally,in situ DRIFT spectroscopy revealed that SNCN-10 facilitated the conversion of NO to nitrate through intermediate species,including bridging nitrite and cis-nitrite(N_(2)O_(2)^(2-)).Kinetic studies further indicated that NO oxidation followed the Langmuir-Hinshelwood(L-H)mechanism.Based on density functional theory(DFT)calculations of free energy changes,a comprehensive reaction pathway for NO oxidation was proposed.These findings provide valuable insights for the development of efficient photocatalytic strategies for NO removal.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
文摘A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.
基金Project(2022YFC3801000)supported by the National Key Research and Development Program of ChinaProject(232300421064)supported by the Natural Science Foundation of Henan Province,China+1 种基金Project(241111322700)supported by the Key Research and Development Projects in Henan Province,ChinaProject(52008379)supported by the National Natural Science Foundation of China。
文摘Recently,foamed polymers have been widely used in the repair of underground engineering disasters by grouting(trenchless technology)due to controllable gelation time and self-expansion.However,the grouting process becomes more complicated due to the complex geological conditions and the self-expansion of slurry.Therefore,this paper adopts a self-made visual experimental device with peripheral pressure and water plugging rate(WPR)monitoring functions to study the influence of main influencing parameters(particle size distribution,grouting amount and dynamic water pump pressure(DWPP))on the spatiotemporal distribution of slurry WPR and diffusion dynamic response(peripheral pressure).The results show that:When grouting amount is 563 g and DWPP is 0.013 MPa,the expansion force of the slurry in the diffusion process is dominant and can significantly change the local sand and gravel skeleton structure.When grouting amount is 563 g,DWPP is 0.013 MPa,and particle size distribution type isⅢ,the flow time of the polymer is shortened,the pores of the gravel are rapidly blocked.Then,the peripheral pressure decreases rapidly with the increase of the distance,and the time to reach the inflection point WPR is shortened.The instantaneous blockage of the pores leads to the delayed transmission of flow field blockage information.
文摘This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Applications(CEA),software.ABS was selected as the base fuel due to its thermoplastic nature,which allows for the creation of complex fuel geometries through 3D printing,offering significant flexibility in fuel design.Hybrid rockets,which combine a solid fuel with a liquid oxidiser,offer advantages in terms of operational simplicity and safety.However,conventional polymer fuels often exhibit low regression rates and suboptimal combustion efficiencies.In this research,we evaluated a range of metal additives-aluminium(Al),boron(B),nickel(Ni),copper(Cu),and iron(Fe)-at chamber pressures ranging from 1 to 30 bar and oxidiser-to-fuel(O/F)ratios between 1.1 and 12,resulting in 1800 unique test conditions.The main performance parameters used to assess each formulation were characteristic velocity(C^(*))and adiabatic flame temperature.The results revealed that each test produced a different optimum O/F ratio,with most ratios falling between 4 and 6.The highest performance was achieved at a chamber pressure of 30 bar across all formulations.Among the additives,Al and B demonstrated significant potential for improved combustion performance with increasing metal loadings.In contrast,Fe,Cu,and Ni reached optimal performance at a minimum loading of 1%.Future work includes investigating B-Al metal composites as additives into the ABS base polymer fuel,and doing experimental validation tests where the metallised ABS polymer fuel is 3D printed.
