一维配位聚合物2-巯基-5-甲基-1,3,4-噻重氮锌钴的合成、结构与性能

于中温混合溶剂热体系中合成出2种同构的一维配位聚合物[Zn(MMTT)2]n和[Co(MMTT)2]n(MMTT=2-巯基-5-甲基-1,3,4-噻重氮), 并进行了单晶结构解析、红外、热重、荧光及磁性等表征. 晶体同属单斜晶系, C2/c空间群. [Zn(MMTT)2]n的晶胞参数: a=1.40432(8) nm, b=1.13824(5) nm, c=0.72378(4) nm, β=101.425(3)°, V=1.13400(10) nm3; [Co(MMTT)2]n的晶胞参数: a=1.4001(9) nm, b=1.1142(9) nm, c=0.7403(3) nm, β=107.84(6)°, V=1.0994(12) nm3. 化合物中金属原子采取四面体构型, 与MMTT配体分子相互连接形成无限一维链; 链与链之间通过配体间弱的C-H···S 氢键连接而形成三维超分子网络结构.     

配位-均匀沉淀法合成Cd（OH）2和CdO纳米带

以硝酸镉为前驱物、氨水(25-28 wt%)为沉淀剂,在无模板的条件下,采用配位-均匀沉淀法成功地合成了Cd(OH)2纳米带。将Cd(OH)2纳米带在350℃下煅烧4 h得到形貌相似的CdO半导体纳米材料。X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、电子衍射(SAED)等测试结果表明,所制备的Cd(OH)2纳米带是由尺寸约25 nm的Cd(OH)2纳米粒子组成,其宽度为100-200 nm、长度达1.5 um、厚度约为30 nm;Cd(OH)2为六方晶系结构;CdO纳米带由更小的CdO纳米粒子组成,CdO为面心立方晶型。本文还初步探讨了Cd(OH)2纳米带的形成过程。     

化学气相沉积法制备Sn2S3一维纳米结构阵列

运用化学气相沉积法(CVD), 直接以Sn和S为原料分区加热蒸发, 通过控制温度分布、气压、载气流量和金属铅纳米颗粒分布等宏观实验条件, 成功制备大面积Sn₂S₃一维纳米结构阵列. 扫描电子显微镜(SEM)图片显示: Sn₂S₃一维纳米结构的横向尺度在100 nm左右, 长约几个微米. X射线衍射（XRD）谱显示: 所制备样品的晶体结构属于正交晶系, 沿[002]方向生长. 紫外-可见漫反射谱表明Sn₂S₃一维纳米结构是带隙为2.0 eV的直接带隙半导体. 讨论了温度分布和金属铅纳米颗粒对Sn₂S₃一维纳米结构生长的影响, 并指出其生长可能遵循气-固(V-S)生长机理.     

铝热反应法制备双股类螺旋Zn2SnO4单晶纳米带

综合利用化学气相沉积、铝热反应法、汽-液-固生长法、极性面融合和稳态湍流动力学控制来大量制备双股类螺旋Zn₂SnO₄单晶纳米带. 该材料属于面心立方尖晶石型透明半导体, 在光伏器件和湿度与可燃气体传感器中有着广泛的应用. 扫描电镜、透射电镜、电子衍射、X射线衍射、拉曼光谱以及光发射等技术分析表明所得的双股类螺旋纳米带是由两个独立的Zn₂SnO₄纳米带通过扭曲纠缠和融合而成. 该双股类螺旋纳米带实际上是在轴向具有周期性的超晶格材料. 光致发光测量表明该纳米带在326.1 nm处出现强发射峰, 线宽约为1.5nm. 本研究所采用的综合制备法中的铝热反应法和稳态湍流微扰法可能有助于类似材料的控制制备.     

溶胶-凝胶法制备ZrO2/SiO2纳米复合材料的研究

利用溶胶-凝胶法制备了ZrO2/SiO2纳米复合物室温磷光材料,通过各条件的优化,最终确定溶剂为异丙醇、Zr摩尔掺杂百分含量为15%、550℃下煅烧3h得到的纳米ZrO2/SiO2复合物的室温磷光发光性能较好,其最大激发波长为280nm、发射波长为460nm,且磷光寿命为0.56s。     

1,4-双(4′-N,N-二甲基氨基苯乙烯基)萘的合成及荧光性质

利用Wittig反应合成了一个以萘为π-Center的对称型“D-π-D”有机绿色发光化合物1,4 双(4′-N,N-二甲基氨基苯乙烯基)萘(BDASN),并测试了其在不同环境中的光谱性质.在378nm激发波长的激发下,BDASN显示出很强的荧光发射峰,峰位在521nm(CH₂Cl₂).随着溶剂极性增大,最大发射波长红移且荧光强度降低,与“D-π-A”分子具有相似的分子内电荷转移(TICT)行为.在β-环糊精(β-CD)中BDASN的绿色发光带被猝灭,同时在450nm附近蓝发光带的荧光强度骤增.     

利用离子型Cd源制备ZnSe/CdSe核-壳结构纳米晶

在有机相体系中利用ZnSe前驱体纳米晶制备过程中的富Se环境,以引入Cd2+的方式在相对温和的环境下通过控制Cd2+离子的加入量及调节反应时间,成功制备了ZnSe/CdSe核-壳复合结构纳米晶.利用X射线衍射(XRD)、透射电镜(TEM)、紫外-可见吸收光谱(UV-vis)和荧光光谱(FL)对其结构形貌以及光学性质进行表征和分析的结果表明,CdSe以外延生长的方式包覆在ZnSe纳米晶表面从而形成具有良好结晶性的核-壳复合结构,其荧光发射始终保持良好单色性,同时实现了在500～620nm可见光范围内的连续可调.     

氧化锌纳米带的低温无催化热蒸发制备及其表征

通过纯锌粉蒸发，在600 ℃无催化条件下成功制备了高质量的不同形貌的ZnO纳米带.该制备方法中控制产物形貌和尺寸的关键是氧、氩及锌蒸气的流速及分压.扫描电镜及高分辩透射电镜观察显示，氧化锌纳米带具有规整光滑及齿状等不同形貌，且皆为单晶，其生长由固-气机理控制.室温光致发光谱表明，齿状氧化锌纳米带在390 nm附近形成紫外发射峰；在455～495 nm时，形成绿光发射峰，该处由4个次级发射峰组成.     

纳米结构ZnO在TiO_2薄膜上的电化学沉积及其表征

在三电极体系中,以硝酸锌水溶液作为电解液,采用阴极还原电沉积法成功实现了一维纳米结构ZnO阵列在TiO2纳米粒子/ITO导电玻璃薄膜基底上的沉积,并通过XRD、SEM、EDS和PL光谱等方法对样品进行了表征.重点研究了薄膜基底、电解液浓度、沉积时间、六次亚甲基四胺(HMT)的引入对ZnO沉积及其发光性质的影响.结果显示:与ITO玻璃基底相比,ZnO更易于在TiO2纳米粒子薄膜上实现电化学沉积.ZnO属于六方晶系的铅锌矿结构,并且沿着c-轴方向表现出明显的择优化生长,以形成垂直于基底的ZnO纳米棒阵列.延长沉积时间、增加电解液浓度和引入一定量的HMT等均对ZnO的生长有促进作用,进而使其纳米棒的结晶度和取向程度提高,进而解释了所得的薄膜分别约在375和520nm处表现出ZnO的强而窄的带边紫外光发射峰和弱而宽的表面态绿光发射带.     

Sn掺杂ZnO半导体纳米带的制备、结构和性能

在无催化剂的条件下, 利用碳热还原反应气相沉积法制备出了高产率单晶Sn掺杂ZnO纳米带. XRD和TEM研究表明纳米带为结晶完好的纤锌矿结构, 生长方向沿[0001], EDS分析表明纳米带中Sn元素含量约为1.9%. 室温光致发光谱(PL)显示掺锡氧化锌纳米带存在强的绿光发射峰和较弱的紫外发射峰, 谱峰峰位中心分别位于494.8 nm和398.4 nm处, 并对发光机制进行了分析. 这种掺杂纳米带有望作为理想的结构单元应用于纳米尺度光电器件领域.     

Novel bulk synthesis of magnesium oxide nanobelts networks by microwave hydrothermal route

Novel magnesium oxide (MgO) nanobelt structures were successfully synthesized on a large scale, low cost and catalyst free by a microwave hydrothermal route using the magnesium metal and potassium hydroxide precursors at 200 °C for 10 min. The synthesized MgO nanobelts were systemically characterized by power X-ray diffraction (XRD), scanning electron microscopy, energy dispersion spectroscopy and transmission-high resolution electron microscopy. The XRD results indicate that the MgO nanobelts have the well-crystalline cubic phase. The detailed morphological studies revealed that the synthesized products were nanobelts and were grown in large quantity. The optical energy gap of MgO nanobelts was found to be 3.1 eV. The photoluminescence spectra of the MgO nanobelts show a strong and broad green emission band, a weak ultraviolet emission band, and a weak red emission band. This novel method will open new dimensions for synthesized 1-D metal oxide and can be easily extended to the synthesis and assembly of other inorganic nanocrystals.     

Surface-enhanced Raman scattering and polarized photoluminescence from catalytically grown CdSe nanobelts and sheets

We have successfully fabricated single-crystalline CdSe nanowires, nanobelts, and sheets by a chemical vapor deposition (CVD) method assisted with laser ablation. The synthesized CdSe nanostructures have hexagonal wurtzite phase as characterized by X-ray diffraction (XRD). CdSe nanobelts can range in length from several tens to a hundred micrometers, in thickness from 40 to 70 nm, and a tapered width which is approximately 3 microm at one end and tapers off to approximately 100 nm at a catalytic gold particle. Both selected area electron diffraction (SAED) and high-resolution transmission electron microscopic (HRTEM) measurements show that the single-crystalline hexagonal belts and sheets grew along the [0.1-1.0] direction with side surface of +/-(0 0 0 1) and top surface of +/-(2 -1 -1 0). While the growth mechanism of nanobelts complies with a combination of vapor-liquid-solid (VLS) and vapor-solid (VS) processes, the formation of sheets is primarily based on the VS mechanism. For comparison, the phonon modes of CdSe nanobelts and bulk powder have been measured by surface-enhanced Raman scattering (SERS) and normal Raman scattering (NRS) spectroscopies with off- and near-resonant excitations. A blue-shift of 2.4 cm(-1) for the longitudinal optical (LO) phonon of CdSe nanobelts, relative to bulk CdSe, is attributed to a lattice contraction in the belt structure, which is confirmed by the XRD measurement. Room-temperature microphotoluminescence (PL) at approximately 1.74 eV from single CdSe nanobelts shows a 3-fold enhancement compared to that from bulk CdSe powder and displays a partial polarization dependence of emission angles.     

高分子自组装Mn2O3花瓣状纳米带、纳米线的研究

通过控制热处理工艺条件, 利用Mn(CH3COO)2和具有特殊空间构型的聚乙烯醇(PVA), 在600 ℃合成了类花瓣状Mn2O3纳米带和纳米线结构. SEM, XRD表征分析证明Mn2O3纳米带结构为方铁锰矿晶型结构, 沿(222)方向择优生长. 分析了热处理工艺对一维纳米结构的影响机制. 初步探讨了Mn2O3一维纳米结构的生长机理.     

Facile Preparation and Visible-light Photocatalysis Enhancement of N-Doped β-TiO2 Nanobelts

A facile preparation of nitrogen-doped β-TiO₂(N-doped β-TiO₂) nanobelts and their visible-light photocatalytic activity were reported. The preparation of N-doped β-TiO₂ nanobelts consisted of cation-exchange between layered sodium titanate nanobelts and NH₄⁺ in aqueous solution at room temperature and subsequent calcination in air. Such a calcination treatment is beneficial to the formation of monoclinic N-doped β-TiO₂ nanobelts. Various measurement results indicate that not only were the nitrogen atoms doped into the lattice of β-TiO₂ nanobelts resulting in a strong visible-light absorption, but also a large number of defects were caused by them in the lattice, increasing the stability of β-TiO₂. The photocatalysis enhancement of N-doped β-TiO₂ nanobelts for the photodegradation of Rhodamine B was demonstrated.     

Large-scale growth of millimeter-long single-crystalline ZnS nanobelts

Millimeter-long single-crystalline hexagonal ZnS nanobelts were grown on specific locations on a wafer scale. This is the first time that the millimeter-scale ZnS nanobelt has been synthesized. The longest nanobelts are about 3 mm. The as-grown nanobelts were characterized by means of field emission scanning electron microscopy, X-ray powder diffraction, high-resolution transmission electron microscopy, and selected area electron diffraction. The results indicate that the ultra-long nanobelts are pure single-crystalline hexagonal ZnS. There are two kinds of ZnS nanobelts existing in the products. One is the nanobelts that have two smooth sides and grow along the [0 0 1] longitudinal direction, and the other is the nanobelts that have one smooth side and one saw-teeth-like side, namely nanosaws, and grow along the [2 1 0] longitudinal direction. A vapor-liquid-solid mechanism is suggested for the lengthwise growth of the ZnS nanobelts (nanosaws) and a vapor-solid mechanism for the side direction growth of the saw-teeth of the nanosaws.     

由钛酸盐纳米带水热制备锐钛矿型TiO2纳米带

研究了水热处理具有层状结构的钛酸钠纳米带或钛酸纳米带转化为锐钛矿型TiO₂的制备过程、难易程度和相转化机理. 实验结果表明, 当水热反应温度和时间分别在160 ℃ 和24 h以内, 钛酸钠纳米带很难完全转化为锐钛矿型TiO₂, 若升高反应温度并延长反应时间, 则可制得纯的锐钛矿型TiO₂, 但纳米带形貌被严重破坏; 当水热反应温度和时间分别为160 ℃ 和16 h时, 1次酸洗的钛酸纳米带能够完全转化为锐钛矿型TiO₂, 若钛酸纳米带经过3次强酸浸泡, 则在160 ℃下相转化时间就会缩短到12 h, 所有钛酸纳米带在转化为TiO₂后的形貌仍为纳米带, 但经3次酸浸后生成的TiO₂纳米带表面更光滑. 讨论了钛酸钠纳米带或钛酸纳米带转化为锐钛矿型TiO₂的相转化机理.     

Ag@AgI等离子体负载TiO2酸蚀纳米带的制备及可见光光催化性能的研究

采用沉积-沉淀法将AgI分散到TiO2酸蚀纳米带上,然后通过光照进而分解出Ag颗粒,最终获得了Ag@AgI等离子体负载的TiO2酸蚀纳米带(AIST)。利用UV-Vis吸收光谱、XRD、SEM对产物进行表征,并研究了可见光下对甲基橙(MO)的光催化降解性能。结果表明,纳米带酸蚀后利于AgI的沉积,Ag的表面等离子体共振效应可以增强催化剂对于可见光的吸收,使可见光下AIST的光催化降解性能显著提高。     

图案化锥形氧化锌纳米带的原位热氧化法制备与发光性质

采用光刻技术制备出图案的锌膜,所得锌膜与纯氧在700℃氧化反应10 min,在锌膜的表面上原位生长出具有图案的锥形ZnO纳米带阵列,实现了ZnO纳米带生长位置的可控生长。锌膜上得到的锥形ZnO纳米带为单晶六方纤锌矿结构,长度在1～4μm,纳米带根部和顶部的宽度分别在300～700 nm和100～300 nm。提出了锥形ZnO纳米带的可能生长机理。在波长为300nm光的激发下,发现了锌膜上锥形ZnO纳米带具有发光峰位于395 nm弱的紫外光发光和510 nm强的蓝绿光发光,它们分别起源于ZnO宽带隙的激子发射以及表面上离子化氧空位中的电子与价带中光激发的空穴之间的复合。     

Controlled growth of large-area, uniform, vertically aligned arrays of alpha-Fe2O3 nanobelts and nanowires

Vertically aligned iron oxide nanobelt and nanowire arrays have been synthesized on a large-area surface by direct thermal oxidation of iron substrates under the flow of O(2). The effects of reactive gas pressure, composition, and temperature have been systematically studied. It was found that nanobelts (width, tens of nanometers; thickness, a few nanometers) are produced in the low-temperature region (approximately 700 degrees C) whereas cylindrical nanowires tens of nanometers thick are formed at relatively higher temperatures (approximately 800 degrees C). Both nanobelts and nanowires are mostly bicrystallites with a length of tens of micrometers which grow uniquely along the [110] direction. The growth habits of the nanobelts and nanowires in the two temperature regions indicate the role of growth rate anisotropy and surface energy in dictating the ultimate nanomorphologies.     

Catalyst-assisted vapor-liquid-solid growth of single-crystal Ga2O3 nanobelts

Mass production of quasi-one-dimensional gallium oxide nanobelts is accomplished through graphite-thermal reduction of a mixture of gallium oxide powders and SnO2 nanopowders under controlled experimental conditions. Sn nanoparticles are located at or close to the tips of the nanobelts and served as the catalyst for the nanobelt growth by a vapor-liquid-solid mechanism. The morphology and microstructure of the nanobelts were characterized by scanning electron microscopy and high-resolution transmission electron microscopy. The Ga2O3 nanobelts grow along the [104] direction, the widths ranged from several tens to several hundreds of nanometers, and the lengths ranged from several tens to several hundreds of micrometers. The growth of Ga2O3 nanobelts is initiated by Sn nanoparticles via a catalyst-assisted vapor-liquid-solid process, which makes it possible to control the sizes of Ga2O3 nanobelts.