为中国“强起来”聚合磅礴力量

中华民族要实现伟大飞跃,就要聚合磅礴的力量。而中国共产党是一个特别善于"聚""合"的政党。中华民族要持续伟大飞跃,就要增添特殊的"核动力"。这种能够持续发展、取之不竭用之不尽的"核动力",来自坚定不移的改革开放政策和中华传统文化中的优秀基因。中国共产党由此探索出了一条与世界各国共商、共建、共享,遵循平等、追求互利的新路——"一带一路"。

复配乳液聚合物水泥防水涂料防护效果研究

本文以丙烯酸酯乳液和氯丁橡胶乳液复配的方法制备聚合物水泥防水涂料,以解决单一聚合物乳液水泥防水涂料在应用过程中易开裂、柔性不足等问题。将其涂覆于水泥砂浆试块表面,探讨了涂层对氯盐侵蚀、硫酸盐侵蚀、冻融循环、自然环境侵蚀下水泥砂浆试块质量、抗压强度的影响,分析了涂层对试块的防护效果。结果显示涂层水泥砂浆试块均无开裂、剥落现象,试块的质量损失率、抗压强度损失率均较小。采用复配乳液并添加外加剂制得涂层对水泥砂浆试块的防护效果最优,试块在氯盐、硫酸盐侵蚀180天、冻融循环100次后的抗压强度损失率分别为9.45%、10.84%、12.16%,自然环境侵蚀120天后,试块抗压强度可保持为29.80MPa远高于无涂层试块。还以其中防护效果最优配方制备聚合物水泥防水涂料,探讨了涂层涂覆方法对自然环境侵蚀下涂层水泥砂浆试块抗压强度的影响。结果显示固定涂层厚度,分多次涂覆制得涂层更致密,交叉涂覆方法制得涂层厚度更均匀,沿十字交叉方向分三次涂覆制得涂层对水泥砂浆试块的防护效果更优。

Preparation and interface state of phosphate tailing-based geopolymers

The long-term storage of phosphate tailings will occupy a large amount of land,pollute soil and groundwater,thus,it is crucial to achieve the harmless disposal of phosphate tailings.In this study,high-performance geopolymers with compressive strength of 38.8 MPa were prepared by using phosphate tailings as the main raw material,fly ash as the active silicon-aluminum material,and water glass as the alkaline activator.The solid content of phosphate tailings and fly ash was 60% and 40%,respectively,and the water-cement ratio was 0.22.The results of XRD,FTIR,SEM-EDS and XPS show that the reactivity of phosphate tailings with alkaline activator is weak,and the silicon-aluminum material can react with alkaline activator to form zeolite and gel,and encapsulate/cover the phosphate tailings to form a dense phosphate tailings-based geopolymer.During the formation of geopolymers,part of the aluminum-oxygen tetrahedron replaced the silicon-oxygen tetrahedron,causing the polycondensation reaction between geopolymers and increasing the strength of geopolymers.The leaching toxicity test results show that the geopolymer has a good solid sealing effect on heavy metal ions.The preparation of geopolymer from phosphate tailings is an important way to alleviate the storage pressure and realize the resource utilization of phosphate tailings.

Syntheses and catalytic performances of three coordination polymers with tetracarboxylate ligands

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.

Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

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.

Syntheses,crystal structures,and catalytic properties of three zinc(Ⅱ),cobalt(Ⅱ)and nickel(Ⅱ)coordination polymers constructed from 5⁃(4⁃carboxyphenoxy)nicotinic acid

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.

Syntheses,crystal structures,and quantum chemistry calculation of two Ni(Ⅱ)coordination polymers

Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.

Transition metal coordination polymers with flexible dicarboxylate ligand:Synthesis,characterization,and photoluminescence property

Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.

Compressive performance of innovative reinforced pillars in closed/abandoned mines

Pillar is closely related to the stability and reliability of underground spaces in closed/abandoned mines.The present research introduced a new technique to strengthen square cement mortar columns via fiber-reinforced polymer(FRP)strips to verify the strengthening effect of FRP on pillars.Compared to a fully wrapped FRP jacket,the advantages of FRP strip are cost-effective and easy-to-construct.A series of compression tests as well as theoretical analysis were carried out to explore the mechanical behavior of square cement mortar specimens partially strengthened with FRP strips.The results verified the effectiveness of FRP strips in enhancing the stress and strain of cement mortar.Different from unconfined cement mortar specimens,these FRP-strengthened cement mortar specimens are featured with the double-peaked behaviors,mainly attributed to the stress state transformation from a one-dimensional to a three-dimensional stress state.It also indicated that the enhancement of stress increased with the FRP strip width.Moreover,the brittle-ductile transition ductile failure characteristics were also observed in FRP-confined cement mortar specimens.The ultimate ductility of the cement mortar specimen decreases gradually with the growth of the FRP strip width.The main contribution of this research is to enrich the strengthening techniques for residual pillars.

Identification of origin of insulating polymer maneuvered photoredox catalysis

Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.

Syntheses,structures,and properties of three coordination polymers based on 5⁃ethylpyridine⁃2,3⁃dicarboxylic acid and N⁃containing ligands

Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.

Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity

Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2)) is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2) interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.

Experimental study on the properties of CMTs-incorporated geopolymers prepared at low temperatures

Considering that copper mine tailings(CMTs)are commonly mixed with ordinary Portland cement,fly ash(FA),and kaolin to produce geopolymers,to make full use of CMTs,the properties of geopolymers manufactured under different material mass ratios and curing methods(standard curing,water bath curing,and 60℃curing)are evaluated with significantly increased dosage of CMTs.Porosity and unconfined compressive strength tests,X-ray diffraction,field emission scanning electron microscopy,and energy dispersive spectroscopy are used to determine the physical and mechanical properties,microstructure,and mineral composition of geopolymers.Finally,costs and CO 2 emissions of specimens with different material mass ratios during the preparation processes are compared.The results show that during the geopolymerization of low-calcium materials,various geopolymer gels,including calcium silicate,calcium silicoaluminate,and mainly sodium silicoaluminate gels,coexist.The solid waste,cost,and carbon dioxide emission reductions can reach 100%,166.3 yuan/t,and 73.3 kg/t,respectively.Under a curing condition of 60℃,the sample with a CMTs mass fraction of 70%and an FA mass fraction of 30%meets the requirements of porosity,compressive strength.The resource utilization of CMT and FA is realized in a more economical way.

Supported Ziegler-Natta catalysts from MgCl_(2)·nROH precursors and its catalytic behaviors for diene copolymerization

Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.

Influence of external nitrogen-containing donors on polymerization behavior of neodymium-based cis-1,4-polybutadiene rubber

Neodymium(Nd)-based catalyst in butadiene(Bd)polymerization has drawn interests due to its availability in affording higher cis-1,4-unit selectivity than transition metal(Ti,Co,Ni,etc.)-based catalysts[1-2].Such outstanding high cis-1,4-unit selecti-vity is hypothetically originated from the presence of 4 f orbitals,that can participate in monomer coordination and thereby govern subsequent enchainment manners.This unique characteristic also renders the active species highly susceptible to Lewis bases,and may impact the overall selectivity as well as polyme-rization behavior after coordination.Nevertheless,it is still a virgin area in such a field,and the influence of Lewis bases on Nd-based diene polymerizations is still a black box.Based on this consideration,how nitrogen-containing donors(D)impacts the overall behaviors of Nd-mediated Bd polymerizations is disclosed.

Efficient in-situ end-functionalization of polydienes by isothiocyanate via neodymium mediated coordinative chain transfer polymerization system

End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.

Cardo poly (ether sulfone) toughened E51/DETDA epoxy resin and its carbon fiber composites

A toughener that can effectively improve the interlaminar toughness in carbon fiber composites is crucial for various applications.We investigated,the toughening effects of phenolphthalein-based cardo poly(ether sulfone)(PES-C)on E51/DETDA epoxy and its carbon fiber composites(CFCs).Scanning electron microscopy showed that the phase structures of PES-C/epoxy blends change from island(of dispersed phase)structures to bi-continuous structures(of the matrix)as the PES-C content increased,which is associated with reaction-induced phase separation.After adding 15 phr PES-C,the glass transition temperature(T_(g))of the blends increased by 51.5℃,and the flexural strength,impact strength and fracture toughness of the blends were improved by 41.1%,186.2%and 42.7%,respectively.These improvements could be attributed to the phase separation structure of the PES-C/epoxy sys-tem.A PES-C film was used to improve the mode-II fracture toughness(G_(IIC))of CFCs.The G_(IIC) value of the 7μm PES-C film toughened laminate was improved by 80.3%compared to that of the control laminate.The increase in G_(IIC) was attributed to cohesive failure and plastic deformation in the interleaving region.

Ballistic Penetration Damage of Hybrid Thermoplastic Composites Reinforced with Kevlar and UHMWPE Fabrics

Polymer matrix types of fiber hybrid composites are key factors to improve ballistic impact damage tolerances.Here we report ballistic penetration damages of Kevlar/ultra-high molecular weight polyethylene(UHMWPE)hybrid composites with thermoplastic polyurethane(PU)matrix.The hybrid composites were penetrated by fragment-simulating projectiles(FSPs)using an air gun impact system.The effects of stacking sequences on the ballistic performance of hybrid composites were analyzed.Two types of specific energy absorption(the energy absorption per unit area density and the energy absorption per unit thickness)were investigated.It was found that the main damage modes of PU hybrid composites were fiber breakage,matrix damage,fiber pullout and interlayer delamination.The instantaneous deformation could not be used as a reference index for evaluating the ballistic performance of the target plate.The energy absorption process of the PU hybrid composites showed a nonlinear pattern.The hybrid structure affected the specific energy absorption of the materials.

Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by acidithiobacillus ferrooxidans

The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.