Synthesis and characterization of aminophenolate-ligated rare-earth metal amide complexes and their catalytic activity for lactides polymerization

Amine elimination of Ln[N(SiMe_3)_2]_3(μ-Cl)Li(THF)_3 with aminophenol H[ON] {H[ON]=2-(CH_2 NC_5 H_(10))-4,6-~tBu_2-C_6 H_3OH} in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]_2 LnN(SiMe_3)_2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5)) in 57%-73% isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.     

Synthesis, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.     

Alternating copolymerization of CO2 and cyclohexene oxide initiated by rare-earth metal complexes stabilized by o-phenylenediamine-bridged tris(phenolate) ligand

A series of o-phenylenediamine bridged tris(phenolate) ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^tBu),and yttrium(complex 3) complexes stabilized by ligand of buiky tert-butyl substituents are mononuclear,whereas neodymium complexes 2^Me and 2^C1 bearing smaller methyl and chloro substituents are dinuclear,respectively.They were applied in the alternating copolymerization of CO₂     

Synthesis,characterization and thermolysis of lanthanide metal nitrate complexes with 1, 10-phenanthroline,Part-95

The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline(phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3(where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry(TG) and differential thermal analysis(DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay(Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: NdPrCe.     

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu（Ⅲ）, β-diketones and 1,10-phenanthroline

Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.     

X-CTS制备及对水中重金属去除的研究

为了处理水中重金属离子,制备了系列壳聚糖修饰物(x-CTS):戊二醛交联壳聚糖(GC)、邻苯二甲酸二丁酯致壳聚糖多孔膜(DBP-C)、壳聚糖凝胶珠(CHD),对目标产物进行了表征,并将目标产物对水环境中的重金属离子Cr(VI),Cd2 ,Pb2 进行了吸附研究.试验表明,在试验条件下,GC对相同质量浓度Cr(Ⅵ)和Pb2 的吸附率可达到99.6%以上,远大于对Cd2 的吸附;CHD的饱和吸附量为:Pb2 》Cr(Ⅵ)》Cd2 ;DBP-C的配比为1:4时,吸附效果最好.同时,研究了1:4配比DBP-C对Cd 2的静、动态吸附,以及pH、温度、浓度等试验条件对Cd2 吸附的影响,确定了最佳吸附条件.     

Synthesis,crystal structure,and fluorescence of two dimeric europium（Ⅲ） complexes with 2-（trifluoromethyl）benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.     

钴取代的硅钼钨四元多金属含氧簇合物的合成及其性质研究

合成了钴取代的硅钼钨四元多金属含氧簇合物,根据元素分析的结果及电荷平衡推算,其组成为K4H2[Co(OH2)SiMo7W4O39]·21H2O,并通过IR、UV、TG-DTA及XRD对其性质进行了表征。     

Synthesis, Crystal Structure of [ （MeC5H4）2Ln（μ-OCH2 CH2NMe2 ） ]2 （Ln = Sm, Y, Nd） and Their Catalytic Activity for Ring-Opening Polymerization of ε-Caprolactone

Reaction of (MeC5H4)3Ln with HOCH2CH2NMe2 in tetrahydrofuran (THF) gives the new complexes [ (MeC5H4)2Ln(μ-OCH2CH2NMe2)]2(Ln = Sm, Y, Nd) with nitrogen functionalized μ-alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [ (MeC5H4)2Sm(μ-OCH2CH2NMe2)]2 was structurally characterized by the X-ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm- N bonds via intmmoleeular coordination of OCH2CH2NMe2. The coordination number of the central metal Sm is nine. The tide complexes show good catalytic activity for ring-opening polymerization of ε-capmlactone.     

萘甲酰三氟丙酮-2,2'-联吡啶钐配合物的合成、表征及荧光性能研究

以氯化钐与β-萘甲酰三氟丙酮(TFNB)和2,2'-联吡啶(bpy)反应,合成了钐及掺杂钐配合物。经C、H、N元素分析和稀土络合滴定及差热-热重分析,推测配合物的组成分别为Sm(TFNB)3bpy.H2O和Sm0.5RE0.5(TFNB)3bpy.H2O(RE3+=Y3+、La3+、Gd3+),配合物在500℃以下稳定。摩尔电导率表明,所有配合物均为非电解质。红外光谱及核磁共振氢谱表明,TFNB通过烯醇式氧负离子与稀土离子螯合配位,bpy的两个氮原子也与稀土离子的配位成键。荧光光谱和荧光寿命测定表明,该类配合物激发波长接近可见光,均可发出钐的特征荧光,荧光寿命也比较长,Y3+、La3+、Gd3+对Sm3+的敏化作用不强。     

Synthesis of novel europium complexes and their photoluminescence properties

Two novel luminescent Eu(III) complexes with the formulas(NIP)Eu(DBM)3 1 and(ENIP)Eu(DBM)3 2(NIP=2-(naphtha-len-1-yl)-1H-imidazo [4,5-f] [1,10] phenanthroline,ENIP=1-ethyl-2-(naphthalen-1-yl)-1H-imidazo [4,5-f] [1,10] phenanthroline,DBM= dibenzoylmethanato) were successfully synthesized and characterized by IR and elemental analysis.The UV-vis absorption spectra and pho-toluminescence properties of the complexes were investigated,and the irradiation at the absorption band between 300-400 nm of europium complexes either in solution or in the solid state led to the emission of a sharp red band at ~610 nm,a characteristic Eu3+ emission due to the transition of 5D0→7F2.Furthermore,the weak emission bands around 587 and 595 nm attributed to 5D0→7F0 and 5D0→7F1 transition were also displayed in the emission spectra.These results demonstrated that the Eu(III) ion was sensitized efficiently by the ligand and displayed photoluminescence with high intensity,narrow half-peak width,and monochromic light.The excited-state lifetimes of 1 and 2 were in the microsecond time scale,but the photoluminescence quantum yield of 2(0.03) was two times higher than that of 1(0.01) which should be at-tributed to the effect of the ethyl substituting in ENIP.     

氯化钕丙酰胺配合物的合成、表征及催化性能

合成了丙酰胺氯化钕配合物并对其催化 4 -乙烯吡啶极性单体聚合反应进行了研究。考察了 Al/Nd摩尔比、催化剂浓度、反应时间和温度对聚合的影响     

阳离子聚丙烯酰胺的合成:丙烯酰胺与甲基丙烯酰氧乙基三甲基氯化铵的共聚合

利用复合引发体系制备阳离子聚丙烯酰胺,讨论了影响聚合反应的因素。试验结果表明,反应时间、聚合单体浓度、引发温度等影响聚合物的相对分子质量。试验合成了相对分子质量较高、溶解性良好的阳离子聚丙烯酰胺。     

Synthesis and characterization of yttrium-aluminum-iron and yttrium-cerium-iron citric complexes

Fe-, Y-Fe-Al- and Y-Ce-Fe- citrates were synthesized in ethylene glycol （EG） medium under conditions similar to those used in the polymerized complex method. Their elemental composition, IR,^ 13C and ^1H NMR, X-ray photoelectron and Mossbauer spectra were studied, and formulae describing their composition were proposed. The complexes contained EG bonded as adduct and ester with citric acid ligand and did not contain ligands with deprotonated alcoholic groups. The complexes consisted of agglomerated spheres, 0.7-3 μm in diameter. The local composition of the products was established by energy dispersive X-ray microanalysis. The comparison of the number of the ligands, their average electrical charge and the esterification degree of mono-, di- and trimetallic complexes proved the mixed-metal nature of the species studied. The thermal decomposition of the complexes was studied and a general scheme of the processes taking place was proposed. Highly crystalline, phase homogeneous YaFe4AlO12 was produced after heating the respective complex at 1000 ℃. Ce-doped yttrium-iron garnet, similarly prepared, contained traces of CeO2.     

Extraction of rare earth elements from their oxides using organophosphorus reagent complexes with HNO3 and H2O in supercritical CO2

Direct extraction of metals from solids with complexing agents in supercritical CO2(SC-CO2) has recently attracted interests in separation,purification,recovery,and analysis of metals.In the present study,the static/dynamic extraction of rare earth elements(Nd,Ce) from their oxides(Nd2O3,CeO2) with organophosphorus complexes with HNO3 and H2O in SC-CO2 was investigated.The static extraction efficiency of Nd from Nd2O3 with the tri-n-butylphosphate(TBP)-HNO3 complex could reach 95% under optimized experiment...     

金属增材制造技术在核工业领域的应用与发展

增材制造能够制备任意复杂形状的零件,具有快速、高效、经济、全智能化和全柔性化制造的优势.本文总结了国内外典型的金属增材制造技术,介绍了金属增材制造技术在核工业领域的应用,梳理了增材制造核材料产品的性能表现,并以实际案例证明了金属增材制造技术在核工业领域的优势.本文结合革新性反应堆技术在核材料中的应用背景,展望了增材制造...     

Mid-Temperature Synthesis of CeO2-TiO2 Complex Compound and Its XRD Structure Study

TiO2 andCeO2 aresemiconductormaterials .TiO2hasthepropertiesofphoto catalysis[1] whileCeO2 hastheabilityofoxygenstorageandcanpromotethedispersionofprecionsmetalsonthesupporter[2 ] .CeO2 TiO2 com plexcompoundwasusedascatalystandspecialfunction almaterial[3～ 5] .ThetraditionalsynthesisofCeO2 TiO2complexcompoundisbyceramicmethodthatusesoxidesasrawmaterialsanditiscalcinedabove 130 0℃[6～ 8] .However ,thestructureandmicrostructureofthecomplexcompoundarenotsuitableforcatalystandfunctionalm…     

底吹氮工艺在KR法铁水脱硫工序的应用

介绍了在选择CaO为脱硫剂的情况下,KR法脱硫技术增加铁水罐(包)底吹N工艺,对提高搅拌头寿命,改善扒渣效果、降低扒渣铁损,提高转炉冶炼低硫钢(w(S)≤0.008%)的终点硫控制合格率等方面取得的成效。     

碱添加量对金属离子的分布和pH变化的影响

提出了一种计算公式,定量地计算了既有氢氧化物沉淀又有氢氧配离子形成的化学反应体系中的金属离子的分布,考察了影响沉淀和配离子形成的各种因素.基于提出的公式,计算了锌、镉、铜、镍、铁(Ⅲ)、铁(Ⅱ)、铝、钙、镁的沉淀率,理论计算与实验结果一致.     

生物医用纯钛的粉末微注射成形工艺研究

钛材料作为目前生物医用性能最好的材料,具有一系列的优良性能,如高比强度、低弹性模量、优良的耐磨耐蚀性和优异的生物相容性。金属粉末微注射成形(Micro MIM)技术作为一种新兴的微加工技术,为钛材料在生物医用微型植入物领域的应用提供了一种低成本、大批量、近净成形途径。利用微注射成形技术制备了纯钛微型试样,并对试样进行了脱粘和烧结。通过调整脱粘和烧结工艺参数,制得整体性能如下的试样:氧质量分数0.240%,氮质量分数0.028%,屈服强度450 MPa,极限抗拉强度565 MPa,伸长率18.0%,相对密度97.3%。试样的整体性能满足ASTM F2989-13外科植入用金属微注射成形纯钛构件要求。