多孔碳海绵封装Na2SO4·10H2O/Na2HPO4·12H2O复合相变材料及其热性能

碳海绵具有低密度、大孔体积、高导热系数等优点,可作为相变材料的良好载体。采用脱脂棉及MgO为原料,合成了具有一定石墨化特性、孔隙率达到96.3%的碳海绵为载体,以Na2SO4·10H2O/Na2HPO4·12H2O为相变介质,制备出多孔碳海绵封装的复合相变材料。结果表明：在700、800℃和900℃制得的碳海绵对相变材料的吸附量分别达到了自身质量的60、75倍和102倍。同时探讨了在不同温度下制得碳海绵封装的材料在5～60℃之间固液相变循环性能,经5 000次循环后,该相变材料的潜热仍在200 J·g–1以上,下降值均在13%以内,导热系数提升率均大于50%。该多孔碳海绵封装的复合相变材料在太阳能储能等领域具有很好的应用前景。     

Crystal Structure and Magnetic Properties of a Novel Helical Coordination Polymer [Cu2(pda)2(phen)2(H2O)2]·6H2O

A novel coordination polymer of Cu^II with flexible ligands, namely, [Cu ₂ (pda) ₂ (phen) ₂ (H ₂ O) ₂ ]·6H ₂ O (1) (H₂pda = 1,3-phenylenediacetic acid, phen = 1,10-phenanthroline), was synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, elemental analysis and IR spectroscopy. In complex 1, the Cu^II ions are linked by pda ligands to form 1D helical chains. The adjacent chains are related by the π–π stacking interactions and exhibit opposite chirality, which result in extended 2D heterochiral helical-layers. Furthermore, the 2D helical-layers are assembled into 3D supramolecular edifices through heterochiral helical hydrogen bonding. In addition, the thermal stability and magnetic properties of 1 are reported.     

NaFexCry(SO4)2(OH)6的合成及电化学性能研究

随着国内外能源的过度消耗和环境污染,寻求高效、清洁、可持续的能源已成为当前的首要任务。关于易合成的黄钠铁矾在析氧反应(OER)方面的研究较少。因此,通过水热法合成了4种不同铁铬物质的量比的铬掺杂黄钠铁矾[Na Fe_x Cr_y(SO₄)₂(OH)₆]催化材料。利用SEM、XRD、Raman和电化学方法对其结构和性能进行表征。结果表明,Cr³⁺成功地掺入到黄钠铁矾晶格中,随着Cr³⁺掺杂量的增加,黄钠铁矾颗粒尺寸逐渐减小;在1 mol/L KOH的电解液中,n(Fe³⁺)/n(Cr³⁺)为1∶1的样品的OER催化性能最佳;当电流密度为10 m A/cm²时,其过电位为370 m V,塔菲尔斜率为92.99 mV/dec,电化学双层电容(C_dl)为10.94 mF/cm²。     

Nd2（C7H4NO4）2(SiW12O40)·18H2O的合成及其光电性能的研究

以硅钨酸和2,3-吡啶二羧酸为配体合成了一种新型的配合物Nd2(C7H4NO4)2(SiW12O40)·18H2O,并对其进行了元素分析、红外光谱、紫外光谱、荧光光谱、热重分析和电化学分析等一系列表征。结果表明:配合物在261nm处具有较强的紫外吸收;在361nm处进行荧光激发,分别在431nm和480nm处得到两个强度不同的荧光发射峰;具有较好的热稳定性;在-0.3~0.3V的电势范围具有电化学活性。     

Hydrothermal Synthesis and Crystal Structures of Cd(II)-Based 1D Coordination Polymer and Mn(II) Coordination Complex with Mixed N- and O-donor Ligands: [Cd2(4-4′-bpy)2(pa)4]n·0.25(H2O) and [Mn(4-4′-bpy)2(pa)(H2O)3]ClO4·2(H2O)

Two new complexes, [Cd₂(4-4′-bpy)₂(pa)₄] _n ·0.25H₂O (1) (pa = phenylacetate), and [Mn(4-4′-bpy)₂(pa)(H₂O)₃]ClO₄·2H₂O, (2), have been obtained from hydrothermal reaction of Cd(NO₃)₂·4H₂O and Mn(ClO₄)₂·6H₂O with a mixture of the ligands, 2-phenylmalonic acid (2-phmalH₂) and 4-4′-bipyridine (4-4′-bpy). The pa is formed in situ by decarboxylation of phenylmalonic acid. These complexes have been characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis and single-crystal X-Ray diffraction. The Cd(II) center is seven-coordinate and linked via pa ligands to form a binuclear complex in the asymmetric unit of 1. A ladder-like 1D chain of binuclear units is formed by Cd(II)–N coordination bond through 4-4′-bpy ligands. Complex 2 consists of a mononuclear manganese center based on a distorted octahedral geometry and exhibits a supramolecular structure containing hydrogen bonds and extensive π···π and C–H···π interactions.     

A Ladder-like Coordination Polymer [Sr(H2O)4(CuL)2]·(CuL)·2.25H2O Constructed From Metallo-Ligand Na[CuL] and Sr(NO3)2: Crystal Structure and ESR Study

Ligand L (H₃L = Glycylglycine, N-[1-(2-hydroxy,5-bromophenyl)propylidene]) has been prepared which contain flexible dipeptide group and substituted phenol group. The ligand react with Cu(NO₃)₂ to give the metallo-ligand [CuL]⁻, in which L acting as quadridentate ONNO chelate, coordinate to Cu(II) ion. The metallo-ligand [CuL]⁻ is rigid and has multifunctional groups. Reaction of metallo-ligand with Sr(NO₃)₂ leads to the formation of the title complexes [Sr(H₂O)₄(CuL)₂]· (CuL)·2.25H₂O (1). This heteronuclear compound has been characterized by elemental analyses, spectroscopic analyses, and single crystal diffraction. Structural analyses reveal that the complex was crystallized in triclinic space group P-1 and has intricate 2D net-structure, which contain an infinite 1D [Sr(H₂O)₄(CuL)₂]⁺ ladder-like structure. In addition ESR (electron spin resonance) property and thermogravimetric analysis of 1 are discussed in detail.     

糖精铜水合物[Cu（C7H4NO3S）2（H2O）4]·2H2O的合成及晶体结构

首次以糖精钠、丙氨酸和硫酸铜为原料合成得到糖精铜蓝色块状晶体,采用红外光谱、X-射线单晶衍射对配合物的晶体结构进行了表征。证明该晶体属单斜晶系,空间群为P21/c,晶胞参数为:a=8.4012(19),b=16.3605(18),c=7.3479(16),α=90°,β=100.84(2)°,V=991.49(15)3,Z=2,Dc=1.794g.cm-3,F(000)=550,R=0.0309。结构分析表明,中心Cu2+与4个O原子和2个N原子配位,处于四角双锥八面体配位环境中,4个水分子在赤道平面上与Cu2+配位,晶胞中还包含有2个游离的结晶水,形成了含6个水分子的结晶物。     

新型镍配合物[Ni(C14H12N2)（H2O）（HCO2）2]·H2O合成及结构

溶解2,9’-二甲基邻菲咯啉的15ml乙醇水溶液中(v/v=2:1)加入新制备NiCO3沉淀,搅拌下再滴加入1.0mol/L的甲酸液,该溶液室温下静置缓慢蒸发5天,得到绿色块状的[Ni(C14H12N2)(H2O)(HCO2)2].H2O晶体。单晶X-射线衍射分析表明,该配合物晶体属三斜晶系,P-1空间群,晶胞参数为:a=7.399(2),b=10.373(2),c=11.442(2),α=82.42(3)°,β=81.77(3)°,γ=76.10(3)°,V=839.3(3)3,Z=2,C16H18NiN2O6,Mr=393.01。最后残差因子R1=0.0353,wR2=0.0835。中心金属离子Ni与邻菲咯啉配体的2个N原子及一个甲酸根中的2个O原子螯合形成八面体赤道面,轴向与结晶H2O与另一个甲酸根中的2个O原子与形成NiN2O4畸变八面体配位结构。     

均苯三酸配合物Co3（BTC）2·12H2O和Mn3（BTC）2·10H2O用于染料废水脱色的研究

通过水热法合成出了两个均苯三酸配合物Co3(BTC)2·12H2O和Mn3(BTC)2·10H2O,经红外光谱、元素分析进行了结构表征。将其用于催化过氧化氢脱色活性艳兰KN-R,研究了双氧水浓度、催化剂浓度和温度对脱色率的影响。由结果可知,Co3(BTC)2·12H2O和Mn3(BTC)2·10H2O表现出优异的催化脱色性能,在废水处理方面具有广阔的应用前景。     

H2SO4和Al2（SO4）3改性中孔分子筛Al-MCM-41及其催化性能

用SO24-物质的量相同的H2SO4和Al2(SO4)3分别对Al-MCM-41进行改性,得到样品SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41。采用X射线多晶衍射(XRD)、红外光谱(FTIR)、N2吸附-脱附和NH3程序升温脱附(NH3-TPD)等测试技术对样品进行表征。分别用H2SO4、MCM-41、Al-MCM-41、SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41催化合成丙酸香叶酯,比较了它们的催化性能。结果表明,H2SO4和Al2(SO4)3改性对Al-MCM-41中孔分子筛结构影响不明显,都可提高其酸性,改性后中孔分子筛的骨架仍保持着六方介孔结构,孔径、孔容和比表面积有所降低,但用Al2(SO4)3改性的分子筛酸性和催化性能更强;SO42-/Al-MCM-41的酸催化活性主要源于SO42-与分子筛表面硅羟基作用形成的双齿螯合配位结构,而Al/SO42-/Al-MCM-41的酸催化活性一方面来自SO24-与分子筛表面硅羟基作用形成的双齿螯合配位结构,另一方面,也来自与分子筛骨架接枝的铝,使其产生了更多的Brnsted酸中心。     

纳米FePO4·2H2O的制备与表征

以六水三氯化铁和磷酸为原料,十六烷基三甲基溴化铵为表面活性剂,水浴法合成,在一定温度下反应一段时间,得到白色沉淀。用X-射线粉末衍射、电镜、热分析、红外光谱等对产物的组成、大小、形貌进行表征。结果表明,产物二水磷酸铁为厚度为30 nm左右的纳米薄片。以此薄片为原料合成的磷酸铁锂具有较好的电化学性能。     

二聚物[Ni2（phen）2（BTC）（H2O）6]·2H2O的水热合成和晶体结构

在水热条件下,成功合成出一例新型镍配位聚合物(CPs),[Ni2(phen)2(BTC)(H2O)6]·2H2O(化合物1,phen=1,10-菲罗啉,BTC=1,2,4,5-均苯四甲酸)。X-射线单晶衍射分析表明,化合物1属于三斜晶系,P1空间群,晶胞参数为ɑ=7.3604(5),b=10.9871(7),c=12.1984(8),α=66.787(6)°,β=76.531(6)°,γ=70.716(6)°,Z=2。结构分析显示化合物1是一个二聚物,并且通过配位水分子和均苯四甲酸配体上的配位原子形成的氢键进一步形成3D的超分子结构。     

Na2CO3?10H2O-Na2HPO4.12H2O/SiO2复合定形相变材料的制备及应用研究

以十水合碳酸钠(SCD)、十二水合磷酸氢二钠(DHPD)为相变主体,制备了低过冷度,无相分离的共晶水合盐(EHS),以九水合硅酸钠为成核剂。进一步使用气相SiO₂为支撑材料,采用浸渍法制备了相变前后形状稳定的 EHS/SiO₂定形相变储能材料(SSPCM)。所得SSPCM的相变温度为 24.08 ℃,焓值为 146.6 J/g,过冷度为 0.55 ℃,热导率为 0.5454 W/m?K。同保温泡沫相比,其可将模拟房内部中心温度的升温时间延长 3.26 倍,降温时间延长 1.39 倍,具有优异的“热缓冲”性能,在建筑节能领域具有广阔的应用前景。     

[CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O (L=3,10-Bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane): A Novel Three-Dimensional Coordination Polymer via H-Bonded Linkages of One-Dimensional Zigzag Chain

A complex with the formula [CuL(H₂O)₂]{[CuL][Fe(CN)₆]}₂·2H₂O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of units, and [CuL(H₂O)₂]²⁺ units. The one-dimensional zigzag chain extents through linkages. The adjacent two polymer chains are linked by the hydrogen bonding between [CuL(H₂O)₂]²⁺ and [Fe(CN)₆]^3–, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer (axial) bond length.     

60%(CH3)2Si(OEt)2/40%Si(OEt)4有机-无机 复合醇盐水解聚合过程的研究

研究了有机-无机复合醇盐60%二甲基二乙氧基硅烷(DDS)/40%正硅酸乙酯(TEOS)的水解聚合过程.通过测定不同水解时间后形成产物的结构及含量变化,分析了这种有机-无机复合材料水解聚合过程中有机与无机组分的相互作用机制及各种产物的形成规律.指出DDS的添加抑制TEOS的自聚合,使得体系中形成了大量的TEOS和DDS的共聚合分子,有机与无机组分通过化学键合连接起来而成为一种凝胶网络组成体.同时还检测到许多DDS的自聚合环状分子［（CH     

Z型g-C3N4/WO3·H2O的制备及其光催化CO2还原性能

以石墨相氮化碳(g-C₃N₄)和二水合钨酸钠为原料,采用水热合成法制备了复合材料g-C₃N₄/WO₃·H₂O(CNW-1),通过XRD、XPS、SEM、TEM对其进行了表征,探究了298 K、0.1 MPa条件下其对CO₂的可见光催化还原性能,并提出了可能的反应机理。通过调控WO₃结晶水含量可以实现CO和CH₄的产率调节,在反应10 h后,CNW-1具有最高的CH₄产率(0.33μmol/g),而g-C₃N₄/WO₃(CNW)具有最高的CO产率(0.67μmol/g)。该研究为CO₂选择性还原为C1化合物提供了一种有效策略,同时突出了以g-C₃N₄作为半导体构建Z型光催化体系在催化领域的应用潜力。     

Structure of a catalytically active octanuclear cobalt complex [Co(II)4Co(III)4(μ4-O)4(μ-O2CPh)12(PhCOOH)4]

The structure of a catalytically active octanuclear mixed-valence cobalt complex [Co(II)₄Co(III)₄(μ₄-O)₄(μ-O₂CPh)₁₂(PhCOOH)₄] (Ph = phenyl, C₆H₅) has been determined using an X-ray diffraction analysis. The presence of 16 ligands containing phenyl rings in each complex gives rise to strong steric stresses and leads to a disordering of terminal groups. The compound crystallizes in the monoclinic crystal system, space group of symmetry P2₁/n, with the unit cell parameters a = 18.076(5) ?, b = 26.371(3) ?, c = 22.791(5) ? β = 92.48(1)°, V = 10853(4) ?³, Z = 4, and ρ = 1.516 g/cm³. The final values of the discrepancy factors are R1 = 0.0441 for 4005 symmetrically nonequivalent reflections with I ≥ 2σ(I), wR2 = 0.1131, and GooF = 0.943.     

复合无机盐CuSO4/Fe2(SO4)3催化合成乙酸异戊酯

乙酸异戊酯通常在浓硫酸催化下由乙酸和异戊醇酯化制得,由于浓硫酸的氧化和脱水作用存在产品纯度低和色泽深等缺点,开发性能更加优良的酯化催化剂以代替硫酸成为研究热点。为考察复合无机盐催化剂CuSO₄/Fe₂(SO₄)₃合成乙酸异戊酯的催化性能,研究乙酸和异戊醇为原料在复合无机盐CuSO₄/Fe₂(SO₄)₃催化下的酯化反应,并考察催化剂用量、反应时间和乙酸与异戊醇物质的量比对乙酸酯化率的影响。结果表明,在乙酸用量0.1 mol、异戊醇用量0.2 mol、催化剂用量0.8 g、反应时间2.0 h和带水剂环己烷用量10 mL条件下,酯化率高于93%。催化剂具有催化活性高、操作简单和不污染环境等优点。     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构.该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为a=9.836(2)(A),b=5.2256(10)(A),c=14.611(3)(A),Mr=381.64,β=90.01(3)°,V=751.0(3)(A)3,Z=2,Dc=1.688Mg·m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612.共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I＞2σ(I)).结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2·(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系.