Pt/Ni/Fe三金属纳米颗粒的制备及催化制氢活性

采用化学共还原方法制备了聚乙烯吡咯烷酮(PVP)保护的Pt/Ni/Fe三金属纳米颗粒,对所合成的纳米颗粒进行了表征,研究了三金属纳米颗粒的化学组成对其催化NaBH4制氢的影响.研究结果表明,Pt/Ni/Fe三金属纳米颗粒的平均粒径在2 nm左右,Pt/Ni/Fe三金属纳米颗粒催化活性高于Pt,Ni或Fe单金属纳米颗粒和Pt/Ni,Pt/Fe或Ni/Fe双金属纳米颗粒的催化活性,其中Pt10Ni78.75Fe11.25三金属纳米颗粒的催化活性最高,30℃时,其催化活性可达63.920×103molH2/(molPt·h).Pt/Ni/Fe三金属纳米溶胶催化剂具有很好的催化稳定性,10次重复催化实验后,该催化剂依然可以保持较高的催化活性.该三金属纳米溶胶催化NaBH4水解反应的活化能为52 kJ/mol.     

基于氧化铁颗粒与聚合物的纳米复合材料磁电容特性研究

对由Fe3O4纳米颗粒-聚二甲基硅烷(PDMS)聚合物材料所组成纳米复合材料磁电容特性进行了研究,提出了该复合材料的制备方法,并对其进行了表征、磁化特性测试以及零磁场环境下介电特性测试;分析了该复合材料的相对介电常数随环境磁场的变化关系以及具有不同含量、粒径纳米颗粒的复合材料磁电容特性差异.实验结果显示,该复合材料的相对介电常数随环境磁场的增大而增大,其变化曲线有一定的滞后特性;复合材料的相对介电常数变化量随材料中纳米颗粒粒径以及含量的增大而增大,但含有较大颗粒复合材料的相对介电常数变化曲线具有较大的滞后性.研究表明,该复合材料在环境磁场中能够产生磁电容效应,其相对介电常数随环境磁场的变化率、饱和值以及滞后性都会受到材料中包含的纳米颗粒的含量以及磁化特性(磁导率、饱和磁化强度、矫顽力)所影响.     

《化学通报》网络版(Chemistry Online)2005年第10期论文摘要

[w110]磁性Fe3O4纳米颗粒**Fe3O4Magnetic Nanoparticle赵朝辉姚素薇*张卫国(天津大学化工学院天津300072)介绍了机械球磨法、水热法、微乳液法、超声沉淀法、水解法制备磁性纳米Fe3O4颗粒的工艺,归纳了各种制备方法的特点。针对当前纳米Fe3O4颗粒的两大研究热点———Fe3O4复合纳米颗粒和磁流体进行了综述,并展望了Fe3O4纳米颗粒的研究前景。Various preparation methods of Fe3O4nanoparticle,such as mechanical milling,hydrothermal method,micro-emulsionmethod,sonochemical synthesis and hydrolytic method,are introduced,…     

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.     

超级铝热剂Al/Fe2O3的制备、表征及对环三亚甲基三硝胺热分解的影响

采用水热法制备了中空短棒状纳米Fe2O3,并用超声分散法将其与纳米Al颗粒复合为单金属氧化基超级铝热剂.利用X射线粉末衍射(XRD)、傅里叶变换红外(FTIR)光谱、扫描电镜及能量散射光谱仪(SEM-EDS)对样品进行表征.并运用差示扫描量热法(DSC)对比研究了超级铝热剂Al/Fe2O3、Al粉和纳米Fe2O3对环三亚甲基三硝胺(RDX)热分解特性的影响.结果表明:超级铝热剂的加入改变了RDX的热分解过程,并加剧了RDX的二次气相反应;随着超级铝热剂含量的增加,RDX的分解峰峰形发生了明显的改变;Al/Fe2O3、Al粉和Fe2O3对RDX热分解的作用主要表现为二次分解峰逐渐明显且峰温降低.     

单质铁纳米颗粒的液相还原制备

采用水合肼作还原剂, 在有柠檬酸存在的情况下, 以FeCl2为铁源, 通过液相化学还原制备粒径为15~50 nm的单质铁纳米颗粒. 采用X射线衍射(XRD)、X射线能谱仪(EDS)和场发射扫描电镜(FESEM)对制备的Fe纳米粒子的结构、组成和形貌进行了表征, 并使用超导量子干涉仪(SQUID)对制备的Fe纳米粒子的磁学性能进行了表征. 研究结果表明, 在柠檬酸存在下, 可以用肼在常温常压下液相还原亚铁离子制备出单质铁纳米颗粒, 改变络合剂后还原无法进行, 并对可能的反应机理进行了讨论.     

新型磁性纳米金修饰过氧化氢生物传感器的研制

利用共沉淀法合成纳米Fe3O4颗粒,将半胱氨酸吸附到纳米Fe3O4微粒表面,借助半胱氨酸的巯基(-SH)对纳米金的强烈吸附,使纳米金自组装到磁性颗粒上,再通过静电吸附作用自组装辣根过氧化酶(HRP),合成了Fe3O4/Cys/Au/HRP纳米复合粒子,最后通过磁力将其修饰到固体石蜡碳糊电极表面,制得新型过氧化氢生物传感器.以对苯二酚作为电子媒介,用计时电流法对H2O2进行测定,线性范围为2.4 X10-3～6.0×10-6mol/L,检出限(S/N=3)为2.5 X 10-6mol/L,响应时间小于10 s.磁性纳米微粒Fe3O4/Cys/Au能够高效地保持HRP的生物活性.该新型传感器已用于实际样品测定.     

纳米金属铁降解有机卤化物的研究进展

有机卤化物是一种毒性强、难生物降解的环境污染物,传统处理技术存在着降解不完全、效率低等不足。纳米技术的发展给有机卤化物的处理带来了一种新的颇具潜力的方法,即应用纳米金属/双金属颗粒对有机卤化物进行脱卤。目前,以Fe(Ⅱ) 和 Fe(Ⅲ)等常见原料合成纳米铁颗粒的技术已经成熟,纳米颗粒对有机卤化物也显示出高效的降解性能。更重要的是,其可灵活应用于地下水和土壤的原位和异位修复,尤其适用于原位修复。本文综述了纳米铁颗粒降解有机卤化物的研究进展,包括纳米铁颗粒的合成与修饰, 降解效能、降解机理、降解动力学、示范工程等,以及发展前景和今后的研究方向。     

纳米Fe3O4/聚苯乙烯均匀分散体系的制备及结构

用化学共沉淀法制备了Fe3O4纳米颗粒,以油酸为表面活性剂,苯乙烯为载液,制备了稳定的纳米Fe3O4可聚合磁流体,将可聚合磁流体经自由基引发聚合制成纳米Fe3O4/聚苯乙烯均匀分散体系,用WAXRD研究了Fe3O4纳米粒子的结晶情况;用FTIR研究了油酸表面改性前后Fe3O4粒子表面官能团的变化;用TEM研究了Fe3O4颗粒的粒径大小及其在苯乙烯单体和聚苯乙烯中的分散情况;用DSC和TGA研究了纳米Fe3O4/聚苯乙烯均匀分散体系的玻璃化转变温度(Tg)和热稳定性,结果表明,合成的纳米Fe3O4为立方晶型,平均粒径在10nm左右,油酸分子在Fe3O4表面是化学吸附,经表面处理的Fe3O4超细颗粒在苯乙烯和聚苯乙烯基体中分散较均匀.界面粘结较好,含1.8％Fe3O4纳米颗粒的聚苯乙烯的最大热失重温度比聚苯乙烯提高了13K,Fe3O4/聚苯乙烯复合体系的饱和磁化强度σs为17.43emu/g.     

基于Pickering乳液的磁性高强水凝胶的制备及性能表征

合成了一种磁性Fe3O4纳米颗粒稳定的水包油(O/W)Pickering乳液并以其作为交联剂,在适宜条件下引发单体丙烯酰胺聚合来制备了一种新型的磁性高强复合水凝胶.采用X射线衍射(XRD)及场发射扫描电子显微镜(SEM)分别对磁性Fe3O4纳米颗粒和复合水凝胶的结构进行了表征,结果表明Pickering乳胶粒子较均匀地分布在复合凝胶网络中.溶胀性能测试及溶胀动力学分析表明复合水凝胶具有良好的溶胀性能,能够吸收自身干重100倍左右的水,其溶胀过程不遵循Fickian扩散模型;拉伸测试表明该水凝胶具有优异的力学性能,其拉伸强度能够达到150 kPa左右,断裂伸长率能够达到300%左右,并且当其承受的应力释放后能快速地恢复到初始形态.磁性能测试的结果显示该水凝胶具有良好的磁性.     

高稳定性普鲁士蓝修饰电极的制备和研究

采用恒电流电解方法,使用FeCl_3-K_3Fe(CN)_6和Fe~(?)L_(?) -K_3Fe(CN)_6(L,邻菲绕啉,EDTA,5-磺基水杨酸等)两体系,在玻碳和铂基体上均制得高稳定性普鲁士蓝膜。用循环伏安法在lmol·dm~(-3)KCl(pH4)溶液中,重点地在0.6--1.1V(vs.Ag/AgCl)区间研究了膜的电化学稳定性。在玻碳基体上FeCl_3,-K_3Fe(CN)_6和Pe~(?)·L_(?) -K_3Fe(CN)_6体系电积膜分别可经受10~(?)周和2×10~(?)周扫描。在铂基体上则可分别经受2×10~(?)和7×10~(?)周扫描。红外和X-射线衍射证明两体系制得的膜均为普鲁士蓝膜,稳定性的明显差异是由于普鲁士蓝晶粒度的不同和在基体表面的相对取向不同引起的。对影响膜的稳定性的因素作了较系统的研究。     

Characterization of an Inclusion Complex of 5,10,15,20-Tetrakis(4-sulfonatophenyl)-porphinato Iron and an O-Methylated β-Cyclodextrin Dimer Having a Pyridine Linker and Its Related Complexes in Aqueous Solution

The structure of a carbon monoxide adduct (CO-hemoCD) of a 1:1 complex of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinato iron(II) (Fe(II)TPPS) and an O-methylated β-cyclodextrin dimer having a pyridine linker (1) has been determined by means of NMR spectroscopy and molecular mechanics (MM) calculation. The results indicate the structure as that the sulfonatophenyl groups at the 5- and 15-positions of Fe(II)TPPS are incorporated into two cyclodextrin cavities of 1 to form a 1:1 inclusion complex (hemoCD), whose Fe(II) center is coordinated by a carbon monoxide (CO) molecule. CO-hemoCD possesses a C _2v symmetrical nature that is supported by MM calculation. The energy minimized structure of CO-hemoCD suggests that the CO–Fe(II) part is significantly covered by two cyclodextrin moieties resulting in a cage effect in CO binding phenomenon. Other spectroscopic results of relating complexes also support the structure of hemoCD deduced from the results concerning CO-hemoCD.     

Infrared multiphoton dissociation of the siderophore enterobactin and its Fe(III) complex. Influence of Fe(III) binding on dissociation kinetics and relative energetics

The dissociation pathways of the siderophore enterobactin and its complex with Fe(III) were examined using infrared multiphoton dissociation (IRMPD). Under experimental conditions (pH = 3.5), both compounds' electrospray spectra exhibited exclusively singly-charged anions. The compositions of the dissociation products were characterized by accurate mass measurements using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The primary dissociation channel for both species was determined to be the loss of one serine group from the precursor molecules. To further investigate the influence of Fe(III) binding on the intramolecular interactions, dissociation kinetics and relative energetics for the loss of this serine group were determined using the focused radiation for gaseous multiphoton energy-transfer (FRAGMENT) method. From the kinetic data, it was found that enterobactin was approximately seven times more reactive than its Fe(III) complex over the range of laser intensities investigated. The relative activation energies, however, exhibited similar values, approximately 7 kcal.mol(-1). These results suggest that at pH = 3.5, Fe(III) interacts with only two of the three serine groups. The results from the present work are believed to be valuable for the characterization of novel siderophores as well as their associated metabolites and synthetic analogues.     

Binding and photodissociation of CO in iron(II) complexes for application in positron emission tomography (PET) radiolabelling

(R-DAB)FeI(2) complexes containing bidentate diimide ligands (R-DAB = RN=CH-CH=NR; R = (i)Pr, c-C(6)H(11)) have been investigated for their ability to react with carbon monoxide to form iron(II) dicarbonyl complexes, (R-DAB)FeI(2)(CO)(2). Solution IR spectroscopy revealed two νCO stretches between 2000 and 2040 cm(-1) corresponding to a cis-arrangement of the carbonyl ligands around the iron. Photochemical decarbonylation was achieved by UV irradiation (365 nm), which occurred within 5 min as evidenced by solution IR spectroscopy. (c-C(6)H(11)-DAB)FeI(2) has been characterised by X-ray crystallography. Reactions using (11)C-labelled carbon monoxide were investigated and revealed that both (R-DAB)FeI(2) species were not effective as trapping complexes due to the low concentrations of [(11)C]CO used in these experiments. A Fe(TPP)(THF)(x) (TPP = tetraphenylporphyrin) complex was investigated with unlabelled CO and the monocarbonyl adduct Fe(TPP)(THF)CO was formed in situ as identified by IR spectroscopy (νCO = 1966 cm(-1)) yet was stable to CO loss upon UV irradiation. Carbonylation reactions of in situ-generated Fe(TPP)(THF)(x) using [(11)C]CO revealed that 97% of the [(11)C]CO stream could be trapped in one pass of the gas at room temperature and at atmospheric pressure.     

Iron and copper complexes of tetraphenyl-m-benziporphyrin: reactivity of the internal C-H bond

Iron and copper complexes of tetraphenyl-m-benziporphyrin (TPmBPH)H have been prepared and structurally characterized. The iron system, (TPmBPH)Fe(II)Br, contains a high-spin Fe(II) center. In the solid state the complex forms dimeric units linked by weak CH.Br hydrogen bonds. The Cu complex contains a tetrameric copper cluster with a Cu(2)Cl(4)(2)(-) unit bridging two [(TPmBPCl)Cu(II)](+) fragments. The formation of (TPmBPCl)H represents an example of copper-catalyzed chlorination on the internal carbon atom of (TPmBPH)H.     

Mechanism of dioxygen activation in 2-oxoglutarate-dependent enzymes: a hybrid DFT study

The reaction mechanism for dioxygen activation in 2-oxoglutarate-dependent enzymes has been studied by means of hybrid density functional theory. The results reported here support a mechanism in which all chemical transformations take place on a quintet potential-energy surface. More specifically, the activated dioxygen species attacks the carbonyl group of the co-substrate producing the Fe(II)-persuccinate-CO(2) complex, which readily releases the carbon dioxide molecule. The step in which the Fe(II)-peracid-CO(2) complex is formed is found to be rate-limiting and irreversible. Subsequent heterolysis of the Obond;O bond in the Fe(II)-persuccinate complex proceeds in two one-electron steps and produces the high-valent iron-oxo species Fe(IV)dbond;O, which is most likely to be responsible for oxidative reactions catalyzed by 2-oxoglutarate-dependent enzymes. The concerted pathway for simultaneous Obond;O and Cbond;C bond cleavage on the septet potential-energy surface is found to be less favorable. The relative stability of different forms of the active iron-oxo species is assessed, and the quintet five-coordinate complex is found to be most stable.     

基于氮掺杂碳量子点荧光猝灭效应检测Fe3+

碳量子点光致发光性质取决于尺寸大小和表面官能团的性质.本研究以还原冶炼过程产生的生物质焦油为前驱体,采用小分子乙二胺进行氮掺杂,通过一步水热法合成荧光产率高、分散性能好的氮掺杂碳量子点,基于Fe3+对氮掺杂碳量子点选择性荧光猝灭效应,实现了对Fe3+快速准确检测.合成的氮掺杂碳量子点为规则的球形,尺寸均一,平均粒径为2.64 nm,晶面间距为0.25 nm,具备石墨碳晶格(100)晶格结构,其荧光量子产率为26.1%;Fe3+与N-CQDs表面官能团配位络合致使N-CQDs荧光猝灭,Fe3+浓度在0.23~600μmol/L范围内,与氮掺杂碳量子点荧光猝灭程度呈良好的线性关系,Fe3+的检出限为230 nmol/L.     

中空结构聚苯胺/Fe_3O_4/炭黑复合材料的制备及吸波性能

采用界面聚合和Pickering乳液聚合相结合的方法制备了具有微米尺寸的中空聚苯胺/Fe_3O_4/炭黑微球复合材料,研究了其形貌、电磁性能和吸波性能.结果表明,中空聚苯胺/Fe_3O_4/炭黑微球的平均粒径约为2.0μm;在2~4 GHz范围内的磁损耗主要是自然共振和交换共振,而在4~18 GHz范围内的磁损耗主要是涡流损耗;在2~18 GHz范围内,随着涂层厚度增加,反射损耗峰向低频方向移动,当涂层厚度增大到5.0mm时,反射损耗曲线出现2个反射损耗峰,分别位于C波段(4~8 GHz)和Ku波段(12~18 GHz),说明中空聚苯胺/Fe_3O_4/炭黑微球复合材料可作为特定频段的吸波材料.     

聚苯胺/Co_(0.5)Zn_(0.5)Fe_2O_4纳米复合材料的制备及电磁性能

采用高分子凝胶法制备尖晶石型Co0.5Zn0.5Fe2O4,原位聚合法制备纯聚苯胺和聚苯胺/Co0.5Zn0.5-Fe2O4纳米复合材料.使用傅立叶红外光谱(FTIR)、紫外可见吸收光谱(UV-Vis)、X射线衍射仪(XRD)和透射电子显微镜(TEM)对复合材料进行了表征.FTIR和XRD的结果表明样品为纯聚苯胺和聚苯胺/Co0.5Zn0.5-Fe2O4.UV-Vis光谱表明聚苯胺/Co0.5Zn0.5Fe2O4苯环上的π-π*和n-π*分别红移了23nm和5nm.TEM照片可知,聚苯胺和聚苯胺/Co0.5Zn0.5Fe2O4粒子的平均粒径分别约为50nm和70nm.在8.2～12.4GHz测试频率范围内,聚苯胺/Co0.5Zn0.5Fe2O4的ε″数值在9.2～12.3之间,u″数值在0.15～0.16之间;聚苯胺/Co0.5-Zn0.5Fe2O4介电损耗低于纯聚苯胺,而磁损耗高于纯聚苯胺.