氮掺杂有序介孔碳-Ni纳米复合材料的制备及电化学性能

以F₁₂₇为模板剂,NiCl₂为镍源,尿素为氮源,间苯二酚甲醛原位聚合树脂为碳源,分别采用均相法和两相法制备Ni-N-OMC-1,Ni-N-OMC-2纳米复合材料.X射线衍射(XRD)、激光拉曼以及透射电子显微镜(TEM)等测试结果表明,复合材料具有有序介孔结构,Ni以金属微粒形式嵌于碳骨架中,提高了有序介孔碳的石墨化程度.X射线光电子能谱测试(XPS)表明尿素热解后以4种形式存在:sp³杂化与C结合的N原子,吡啶N原子,sp²杂化与C结合的N原子以及quaternary-N原子.Ni-N的共改性改变了碳载体的理化性质,有利于Pt纳米粒子的负载与分散.均相法制备的Ni-N-OMC-1复合材料微波负载Pt后,氧还原极限电流密度为5.32mA·cm^-2,氢氧化电化学活性面积高达138.53m²·g^-1,电化学催化活性优于商业20%Pt/C材料(4.49mA·cm^-2,96.98m²·g^-1).     

功能化有序介孔碳对重金属离子Cu(II)、Cr(VI)的选择性吸附行为

以三嵌段共聚物F127为模板剂, 酚醛树脂为碳源, 正硅酸乙酯为硅源, 三组分共组装合成介孔碳?氧化 硅纳米复合物, 再经HF去除氧化硅, 得到有序介孔碳(OMC). X射线衍射(XRD)、透射电子显微镜(TEM)、低温 N2吸脱附(BET)等测试表明, 所得样品具有高度有序的介孔结构, 比表面积和孔容分别为1330 m²·g^-1和2.13 cm³·g^-1, 平均孔径6.4 nm. 对其先氧化、后氯化、再胺化, 得到不同胺基接枝量的胺化介孔碳(C-NH₂(m), m为加入的乙二胺的质量(g)). 傅里叶变换红外(FT-IR)光谱表征结果证实, 胺基官能团成功接枝到有序介孔碳表面.TEM测试表明介孔碳的有序孔道结构得到了较好的保持. 以有序介孔碳、胺化介孔碳作吸附剂对Cu(II)、Cr(VI)进行选择性吸附研究. 结果表明: 功能化修饰前, 样品对Cu(II)、Cr(VI)饱和吸附量分别为213.33、241.55 mg·g^-1; 修饰后饱和吸附量可分别达到495.05、68.21 mg·g^-1. 功能化介孔碳表现了较强的选择性吸附Cu(II)的能力.     

三维有序大孔-介孔二氧化硅的可控制备及表征

以聚甲基丙烯酸甲酯(PMMA)胶晶为大孔模板、嵌段共聚物P123为介孔模板,利用双模板剂法进行了三维有序大孔-介孔二氧化硅材料的制备研究。采用SEM、TEM、低角XRD以及N₂吸脱附技术对样品进行了表征。结果表明,通过简单的调控PMMA胶晶模板的组装过程,就可以调变合成材料中的大孔结构,从而轻松地实现可控的制备出具有网状或者层状结构的三维有序大孔-介孔二氧化硅材料,并提出了其可能的形成机理。此外,所制备的三维有序大孔-介孔二氧化硅样品均具有较大的BET比表面积(>550m₂·g^-1),大孔孔径200nm左右,介孔孔径分布集中于3.5nm左右。     

水溶性壳聚糖制备多孔碳/氧化镍复合材料及其电化学电容行为

将水溶性壳聚糖碳化得到多孔碳材料, 然后制备了多孔碳/NiO复合材料. 透射电子显微镜(TEM), X射线衍射(XRD)和N₂吸-脱附实验等结构表征显示, 材料具有富含介孔的孔道结构. 循环伏安(CV), 恒流充放电等电化学测试表明, 复合材料具有良好的电化学电容性能. 其中Ni/C质量比为2:20时, 复合材料在0.1 A·g^-1电流密度下比容量可达355 F·g^-1, 而且经过1500次循环比容量仍保持99%左右, 表现出良好的循环稳定性.     

水热纳米浇筑HNTs模板法制备碳纳米棒

以埃洛石纳米管（HNTs）为模板和聚乙烯醇（PVA）为碳源,采用水热纳米浇筑法成功制备出碳纳米棒。方法涉及3步,即在HNTs中浇筑PVA,碳化和模板移除。采用一系列表征手段如XRD、FT-IR、SEM、TEM、Raman、XPS、SAED和N₂吸附-脱附等表征碳纳米棒的形成和结构。具有一维棒状结构的碳纳米棒具有高的比表面积（408 m²·g^-1）和典型的介孔特征。     

水热纳米浇筑HNTs模板法制备碳纳米棒

以埃洛石纳米管（HNTs）为模板和聚乙烯醇（PVA）为碳源,采用水热纳米浇筑法成功制备出碳纳米棒。方法涉及3步,即在HNTs中浇筑PVA,碳化和模板移除。采用一系列表征手段如XRD、FT-IR、SEM、TEM、Raman、XPS、SAED和N₂吸附-脱附等表征碳纳米棒的形成和结构。具有一维棒状结构的碳纳米棒具有高的比表面积（409 m²·g^-1）和典型的介孔特征。     

具有双孔径分布的介孔C-Al2O3-TiO2纳米复合材料的合成及其红外发射率

以嵌段共聚物F127 (PEO₁₀₆PPO₇₀PEO₁₀₆, M_W=12600)为模板剂, 异丙醇铝和钛酸四丁酯为金属源, 低分子量的酚醛树脂为碳源, 通过溶胶-凝胶三元共组装法合成了具有双孔径分布的C-Al₂O₃-TiO₂纳米复合材料.用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)及N₂吸附-脱附对该复合材料进行结构表征. 结果显示, 当铝钛原子的摩尔比为1:10 时, 对应的纳米复合材料具有较好的有序介孔结构, 其双孔径分别为3.9和6.5 nm, 比表面积可达259 m²·g^-1, 孔容0.37 cm³·g^-1. 以三元乙丙橡胶(EPDM)为粘结剂, 与介孔纳米复合材料混合制备涂层. 通过调节复合材料中铝钛摩尔比和涂层厚度, 红外发射率在0.450-0.617之间可调.     

MCM-41介孔材料负载金属的一步法合成及其对酯化反应的催化作用

以增溶了茂金属的十六烷基三甲基溴化铵(CTAB)胶束为模板, 采用一步法合成了介孔表面负载有金属(铁、钛和锆)的介孔材料MCM-41, 通过等离子体电感耦合发射光谱仪(ICP-AES)测定铁、钛和锆负载量(质量分数)分别为1.71%、0.95%和0.81%. 通过X射线衍射(XRD)图谱和N₂吸脱附等温线可知, 负载金属的介孔材料M-MCM-41(T) 仍具有较高的比表面以及规整的六方有序孔道结构, 去除模板剂的焙烧温度对孔道结构有一定影响. 由一步法合成的金属负载介孔材料对乙酸正丁酯的酯化反应具有很高的催化活性, 其中Fe-MCM-41在单位时间单位金属催化生成的产物量(TOF)为55643 g·h^-1·g^-1, 而Zr-MCM-41的TOF高达125320 g·h^-1·g^-1. 与纯茂金属相比, 由茂金属合成的金属负载介孔材料可显著提高酯化反应的催化活性.     

SBA-15负载CeO2纳米晶的溶胶-凝胶一步合成

以P123为模板剂, 正硅酸乙酯和硝酸铈为前驱体, 通过溶胶-凝胶路线在酸性条件下合成了SBA-15负载氧化铈(CeO2与SiO2质量比为28.7%)有序介孔材料. 采用热重/差热分析(TGA/DTA)、X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明, 合成的材料具有类似于SBA-15的结构, 孔径、孔容和比表面积分别为38.7 Å, 0.46 cm3/g和570 m2/g. X射线衍射(XRD)、透射电镜(TEM)、X射线能谱(EDS)和选区电子衍射花样联合表征证实了铈物种以高分散的CeO2纳米晶的形式分布在介孔基体中.     

具有锐钛矿骨架结构TiO2介孔分子筛的合成

在“酸-碱对”合成高度有序TiO₂介孔分子筛的基础上, 引入具有促进质子转移作用的硝基甲烷作为晶化助剂, 增强了合成体系中无机-无机之间相互作用力. XRD, TEM, BET, UV-Vis表征表明, 成功合成了骨架为锐钛矿的高度有序TiO₂介孔分子筛. 研究发现, 适量晶化助剂是成功合成的关键.     

Fe, Co, Ni-聚合物-C复合催化剂的制备及对乙醇电催化氧化性能研究

采用模板聚合物与金属离子配位-碳粉负载-还原方法得到的纳米复合材料P-M-C (P为聚合物, M为Fe, Co, Ni金属纳米颗粒, C为碳粉XC72). 利用红外光谱(IR)对中间产物进行了表征, 结果表明所制物质为目标产物P; 透射电镜(TEM)结果表明Fe, Co, Ni纳米粒子粒径多数为20～30 nm, 部分在10 nm左右, 纳米粒子均匀地分散在聚合物P上; 扫描电镜的能谱(SEM-EDS)分析结果证实了Fe, Co, Ni三种元素的存在. 通过循环伏安和计时电流法研究表明, 碱性介质中P-M-C复合催化剂对乙醇电化学氧化具有高催化活性和稳定性; 反向高效液相色谱(HPLC)结果表明乙醇氧化后的产物部分为乙醛和乙酸的混合物.     

Effects of a 10 T external magnetic field on the thermal decomposition of Fe, Ni, and Co acetyl acetonates

The current investigation is centered on the thermal decomposition (700 degrees C) of acetyl acetonates of Ni, Co, and Fe in a closed reactor that was conducted by employing an external magnetic field (MF) of 10T. Interestingly, reactions of Co and Ni acetyl acetonates under a 10T MF produce Co and Ni nanoparticles (NPs) coated with carbon, while Fe acetyl acetonate produces Fe3O4 uncoated with carbon. Additionally, it is observed that all the as-formed magnetic particles tend to align in one dimension along applied MF; thus, this process can be used to fabricate large arrays of magnetic nanoparticles. The effect of an applied MF to synthesize morphologically and compositionally different products from corresponding precursors with their mesoscopic organization is the key theme of the present paper, explained with a plausible mechanism.     

Heterometallic bismuth-transition metal homoleptic beta-diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(beta-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials.     

催化反应制备碳化硅纳米粉体的密度泛函理论计算及实验研究

以Si_(55),Si_(43)M_(12)和Si_(37)M_(18)(M=Fe,Co或Ni)团簇为模型,采用密度泛函理论(DFT)研究了Fe,Co及Ni纳米团簇催化硅粉转化为SiC的机理.计算结果表明,Fe,Co及Ni纳米催化剂先与Si形成合金,拉长并弱化Si—Si键的强度,起到活化Si粉的作用;合金的形成有利于C原子的吸附及Si原子和C原子间的反应;Fe的催化能力强于Co和Ni.在此基础上,以Si粉和酚醛树脂为原料,以Fe,Co及Ni硝酸盐为催化剂前驱体,通过微波加热反应制备了3C-SiC纳米粉体.研究了催化剂种类、反应温度、催化剂用量和反应时间等对制备3C-SiC纳米粉体的影响.结果表明,催化剂Fe,Co和Ni的加入均可显著降低3C-SiC的合成温度.当以2.0%(质量分数)的Fe为催化剂时,Si粉在1100℃下反应30 min后即可全部转化为3C-SiC纳米粉体;而在相同条件下,无催化剂时Si粉的完全转化温度为1250℃;Fe的催化效果优于Co和Ni,与DFT计算结果吻合.     

Low-temperature solution synthesis of the non-equilibrium ordered intermetallic compounds Au3Fe, Au3Co, and Au3Ni as nanocrystals

Alloys and intermetallic compounds of Au with the 3d transition metals Fe, Co, and Ni are nonequilibrium phases that have many useful potential applications as catalytic, magnetic, optic, and multifunctional magneto-optic materials. However, the atomically ordered Au-M (M = Fe, Co, Ni) intermetallics are particularly elusive from a synthetic standpoint. Here we report the low-temperature solution synthesis of the L12 (Cu3Au-type) intermetallic compounds Au3Fe, Au3Co, and Au3Ni using n-butyllithium as a reducing agent. Reaction pathway studies for the Au3Co system indicate that Au nucleates first, followed by Co incorporation to form the intermetallic. The nonequilibrium intermetallic nanocrystals have been characterized by powder XRD, TEM, EDS, selected area electron diffraction, and nanobeam electron diffraction, which collectively confirm the compositions and superlattice structures.     

Electrochemical properties of ordered mesoporous carbon and its electroanalytical application for selective determination of dopamine

The electrochemical properties of one novel carbon material, ordered mesoporous carbons (OMC), synthesized by templating SBA-15 mesoporous silica materials and the electrocatalytic behaviors of OMC modified electrode towards the oxidation of dopamine (DA) and ascorbic acid (AA) were studied. Cyclic voltammetry was used to evaluate the electrochemical behaviors of OMC in 5 mM K₃Fe(CN)₆/0.1 M KCl solution. OMC showed a faster electron transfer rate, as compared with glass carbon (GC) electrode. The higher electron transfer kinetics can be attributed to the existence of a large amount of edge plane defect sites in the OMC materials, which was verified by Raman spectroscopy. The cyclic voltammetric studies also showed the presence of oxygen-containing functional groups on the surface of OMC. Furthermore, the OMC modified electrode showed high electrocatalytic activities toward the oxidation of DA and AA, and resolved their voltammetric responses into two well-defined peaks with peak separation of ca. 0.210 V. The OMC modified electrode could be effectively used for the selective electrochemical determination of DA in the presence of AA.     

Formation of CO(x)-free H2 and cup-stacked carbon nanotubes over nano-Ni dispersed single wall carbon nanohorns

Transitional metals (M) were dispersed on single-wall carbon nanohorns (M/SWCNHs, M = Fe, Co, Ni, Cu) by simple thermal treatment of the deposited metal nitrate without H(2) reduction. Nanometallic Ni particles on SWCNH were evidenced by high-resolution transmission electron microscopic observation and X-ray photoelectron spectroscopy. The nano-Ni dispersed on SWCNH showed the highest CH(4) decomposition activity; the activity of used transitional metals decreases in the order Ni ? Co > Fe ? Cu. On the other hand, the reaction rate over Ni/SWCNH was much larger than that over Ni/Al(2)O(3), and the former provided CO(x)-free H(2) and cup-stacked carbon nanotubes, while Ni/Al(2)O(3) produced CO(x) in addition to H(2). SWCNH was superior to Al(2)O(3) as the catalyst support of Ni for the CH(4) decomposition reaction.     

多硫化钠/溴液流储能电池负极材料的研究

在常规玻璃三电极池中用稳态极化法研究了铁、钴、镍、铅及石墨在 1. 3mol·L-1Na2S4水溶液中的极化行为, 测定了不同材料的交换电流密度.以泡沫镍、镀镍或镀钴碳毡为负极,聚丙腈碳毡为正极组成电池测试了常温下电池的能量效率及循环性能.结果表明:泡沫镍及镀镍或钴的碳毡可做电池负极材料;充放电电流密度为30mA/cm2时,电池的能量效率约 80 %;电池循环性能较好.     

磁性有序介孔炭的制备及药物吸附行为研究

采用纳米共铸法将磁性纳米粒子包埋到有序介孔炭的骨架中, 制成含有磁性纳米粒子的有序介孔炭(Fe/OMCs). 实验通过氮气吸附、扫描电镜、X射线衍射、磁性测试等手段对Fe/OMCs进行了系统的表征. 研究表明, Fe/OMCs基本保持了有序介孔结构, 磁性粒子在材料中以纳米α-Fe粒子的形式存在, 并且具有超顺磁特性. 盐酸四环素(TH)在Fe/OMCs上的吸附研究表明, Fe/OMCs的介孔表面积和介孔孔容是决定TH吸附量的关键因素. 脱附动力学研究表明, Fe/OMCs的孔尺寸是影响脱附速率的关键因素, 孔径越大, TH的脱附速率就越大.     

Sc6MTe2 (M = Mn, Fe, Co, Ni): members of the flexible Zr6CoAl2-type family of compounds

The compounds Sc6MTe2 (M = Mn, Fe, Co, Ni) have been prepared by high-temperature solid-state techniques and their structures determined to be hexagonal P62m (No. 189), Z = 1, a = 7.662(1) A, 7.6795(2) A, 7.6977(4) A, 7.7235(4) A and c = 3.9041(9) A, 3.8368(2) A, 3.7855(3) A, 3.7656(3) A for M = Mn, Fe, Co, and Ni, respectively. Crystal structures were refined for M = Fe and Ni, while M = Mn and Co were assigned as isostructural on the basis of powder diffraction data. The Sc6MTe2 compounds belong to a large family with the Zr6CoAl2-type structure, an ordered variant of the Fe2P structure. The structure contains confacial tricapped trigonal prisms of scandium centered alternately by the late transition metal or tellurium atoms. The Sc6MTe2 compounds are the electron-poorest examples of this structure type. Extended Hückel band calculations for M = Fe and Ni show that both compounds exhibit largely 1D metal-metal bonding and are predicted to be metallic.