氨硼烷同分异构体H_2B(NH_3)_2BH_4的制备

本文以NaBH_4为硼源、氨基络合物为氨源制备出了能缩短氨硼烷热分解放氢诱导期的氨硼烷同分异构体H_2B(NH_3)_2BH_4。研究了反应温度、时间和溶剂等因素对H_2B(NH_3)_2BH_4产率的影响。实验结果表明:在温度为25℃,物质的量Cu(NH_3)_6Cl_2∶NaBH_4=1∶2,反应时间为10h的条件下,制得的H_2B(NH_3)_2BH_4产率高达74%。XRD检测到反应产物中有金属Cu,经超景深显微镜观测,其粒径大小约为20μm。     

自石灰石矿粉中直接提取CaCO3晶须的碳化-分解法研究

提出一种自石灰石矿粉中直接提取CaCO_3晶须的碳化-分解方法。该方法能够以天然石灰石矿粉为原料,通过水溶性碳酸的作用溶解出Ca(HCO_3)_2,进而在升温条件下通过Ca(HCO_3)_2的分解反应得到形貌规整的棱锥状CaCO_3晶须。扫描电镜观测与X射线衍射分析显示,Ca(HCO_3)_2分解温度对CaCO_3晶须微观形貌的影响显著,晶须长度与长径比随分解温度的升高均呈上升趋势,但分解温度超过80℃会导致文石晶相向方解石晶相转化。实验结果表明,80℃、2h条件下,Ca(HCO_3)_2分解产物中文石晶相含量较高,晶须几何形貌更为合理,其平均长度为14.61 μm、长径比为8.10。     

氨基酸对水热合成羟基磷灰石纤维形貌的影响

以Ca(NO_3)_2·4H_2O和(NH_4)_2HPO_4的水溶液为前驱体,基于生物矿化的基本原理,利用水热法制备结晶度较高的羟基磷灰石(HA)纤维,重点研究酸性氨基酸L-谷氨酸(Glu)、中性氨基酸L-苯丙氨酸(Phe)和碱性氨基酸L-赖氨酸(Lys)的添加对产物物相和形貌的影响。结果表明:添加这3种氨基酸均对产物的物相影响不大,制得样品的主要组成相都是HA,部分样品含有少量碳酸钙。3种氨基酸的加入均改变纤维沿c轴生长的趋势:加入Glu后得到球状形貌的HA,Lys的加入使得产物形貌变得不均匀,而加入Phe后得到分散性较好的棒状纤维。     

柠檬酸钠对球形NaGd(MoO4)2∶Eu3+纳米晶的溶剂热合成与发光性能影响

采用以乙醇为溶剂的溶剂热法,以三氧化二钆(Gd_2O_3)和钼酸钠(Na_2MoO_4)为原料,柠檬酸钠(Na_3Cit)为表面活性剂,在pH=5,180℃条件下合成出铕离子(Eu~(3+))掺杂的球形双金属钼酸盐纳米粉体[NaGd(MoO_4)_2∶Eu~(3+)],并对制备的产物的物相、形貌以及荧光性质进行表征,探讨了表面活性剂量对产物形貌及发光性能的影响。结果表明,在393nm激发条件下,不同形貌的NaGd(MoO_4)_2∶Eu~(3+)纳米晶在612nm处均有很强发射峰,在Na_3Cit∶Gd_2O_3体积配合比为1∶3,Na_3Cit添加量为1mL,Eu~(3+)用量为5%(wt,质量分数)条件下,合成的球形NaGd(MoO_4)_2∶Eu~(3+)纳米晶颗粒均匀,荧光性较好。由此,表面活性剂Na_3Cit的添加量对产物的形貌及发光性能起到重要作用。     

单分散γ-Al_2O_3纳米颗粒制备工艺参数的调控

采用均相沉淀法,在950℃煅烧碱式硫酸铝(Al(SO_4)_x(OH)_y)纳米颗粒2h,制备出单分散的γ-Al_2O_3纳米颗粒。研究了阴离子、浓度和沉淀剂/铝盐摩尔比对Al(SO_4)_x(OH)_y颗粒的形貌、尺寸和分散性的影响。结果表明,Al(SO_4)_x(OH)_y颗粒的最佳制备条件为:二甲胺硼烷(DMAB)作沉淀剂、Al_2(SO_4)_3.18H_2O作铝源、[Al~(3+)]=0.0005mol/L、n(DMAB)/n(Al_2(SO_4)_3·18H_2O)=40。制备出的Al(SO_4)_x(OH)_y具有球形、平均颗粒尺寸为98nm、粒径分布为75~130nm、单分散性的特点;获得了球形、平均颗粒尺寸为90nm、粒径分布范围为50~105nm、单分散的γ-Al_2O_3颗粒。     

不同工艺条件对球形纳米硫酸钙制备的影响

制备纳米硫酸钙(CaSO4)颗粒的关键在于采用适宜的制备工艺条件配制反相微乳液,使CaSO4晶体在理想的环境中生长。采用AOT、OP-10复合表面活性剂/环己烷/正戊醇/水溶液反相微乳液反应体系,在水与表面活性剂的摩尔比(水表比)ω=20、反应物浓度n([Ca2+])/n([SO24-])=0.125mol/L、陈化时间t=10min的条件下,制备出了形貌均一,平均粒径为70nm的球形CaSO4颗粒。用扫描电子显微镜(SEM)对产物形貌和大小进行了表征。实验分析了水表比ω、反应物浓度n([Ca2+])/n([SO24-])值、陈化时间t等因素对纳米CaSO4颗粒粒径的影响。     

氟磷灰石的微乳液法制备及其表征

在OP乳化剂/异辛烷/正葵醇/((NH4)2HPO4溶液、Ca(NO3)2溶液及KF溶液)四元微乳液体系下合成氟磷灰石,采用扫描电镜(SEM),X射线衍射(XRD),红外光谱分析(FT-IR),电子能谱(EDS)等研究方法对不同pH条件下合成的氟磷灰石样品进行表征。结果表明:在弱碱条件下更利于氟磷灰石的合成,同时结晶程度更高;在pH=7.5条件下所制备氟磷灰石的Ca/P比约为1.62,与理论值(1.67)较为接近。     

Na(La_(0.97)Yb_(0.02)Tm_(0.01))(WO_4)_2荧光粉的自牺牲模板合成及纯净近红外发光

本文以一种稀土层状化合物(La_(0.97)Yb_(0.02)Tm_(0.01))_2(OH)_4SO_4·2H_2O为新型模板通过自牺牲模板反应成功制备出Na(La_(0.97)Yb_(0.02)Tm_(0.01))(WO_4)_2上转换荧光粉。在该荧光粉的制备过程中不需要后续煅烧经自牺牲反应后可直接获得目标产物。采用X射线衍射(XRD),场发射扫描电子显微镜(FE-SEM)和荧光光谱(PL/PLE)对模板及产物进行表征。结果表明在200℃,WO_4~(2-)/RE~(3+)摩尔比为10的条件下反应24 h可获得纯相荧光粉。利用模板良好的导向作用在不添加任何有机溶剂的条件下获得了尺寸均匀分散性良好的圆盘状形貌,直径约为4.6μm。在978 nm激光激发下,Na(La_(0.97)Yb_(0.02)Tm_(0.01))(WO_4)_2荧光粉于约796 nm处可发射出近乎纯净的近红外光,归属于Tm~(3+)离子的~3H_4→~3H_6的跃迁,蓝光处的发射峰近乎完全淬灭,近红外处发射峰的强度为蓝光发射峰强度的约260倍。根据泵浦功率与发光强度的关系得出上转换发射过程为双光子过程。     

TiO_2/Ni_3[Si_2O_5][OH]_2复合光催化材料对盐酸四环素的光降解研究

以Ni_3[Si_2O_5][OH]_2纳米管(NNTs)为载体,利用氟钛酸氨((NH_4)_2TiF_6)与硼酸(H_3BO_3)混合液相沉积法制备TiO_2/NNTs复合纳米管。通过TEM、Raman和UV-Vis等手段对样品的形貌、物相和光吸收性能进行了分析表征,探讨了沉积温度对复合效果的影响。以TiO_2/NNTs复合纳米管作为催化剂对水体中盐酸四环素进行降解研究,探究了沉积温度、水体环境(pH值条件)对催化效果的影响。并通过质谱对催化降解产物进行了初步的推断。结果表明,NNTs表面被TiO_2均匀包覆,包覆的TiO_2为锐钛矿相。制备的TiO_2/NNTs在紫外和可见光区有较强吸收,相对TiO_2光吸收范围红移。当溶液pH值为6.5时降解率最佳;降解产物为小分子物质。     

纳米Co3O4/ZnO复合材料的制备及其光催化性能的研究

以Co(NO_3)_2为原料,CO(NH_2)_2为沉淀剂,H_2O_2为氧化剂,通过水热-煅烧制备Co_3O_4和Co_3O_4/ZnO纳米颗粒。通过XRD、FT-IR、SEM对样品的结构和形貌进行了表征。结果表明,所制备出的Co_3O_4呈现多片层组成的不规则颗粒结构,Co_3O_4/ZnO的形貌为片层堆叠的球状结构。在紫外光照条件下降解甲基橙溶液研究了Co_3O_4与Co_3O_4/ZnO复合材料的光催化性,发现Co_3O_4/ZnO复合材料比Co_3O_4颗粒具有更好的光催化性能活性,其对甲基橙的降解率在72 h可达99%。     

Hydrothermal synthesis of calcium hydroxyapatite nanorods in the presence of PVP

Calcium hydroxyphosphate (Ca₁₀(PO₄)₆(OH)₂, HAP) nanorods have been successfully synthesized by a simple and mild hydrothermal treatment in the presence of polyvinylpyrrolidone (PVP). A complex of calcium nitrate (Ca(NO₃)₂) and Na₂HPO₄ was used to supply the calcium and phosphate ions during the reactions. The synthesis of pure HAP nanorods was under near neutral condition. The morphology and structure of the samples were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy analysis. The nanorods were uniform with diameter of 20–25 nm and length ranging from several hundreds of nanometers to several micrometers. The influence of different experiment conditions, i.e., the PVP concentration, molar ratio of Ca²⁺ to HPO₄ ²⁻, reaction time, and temperature, on the morphology of the nanorods was investigated. The formation mechanism of rod-like HAP and effects of PVP on the crystal nucleation and growth have also been discussed.     

Formation of calcium phosphate nanoparticles in reverse microemulsions

Nanosized calcium phosphate powder had been synthesized via an inverse microemulsion processing route, which used cyclohexane as the oil phases, octaethylene glycol monododecyl ether (C₁₂EO₈) as surfactant phase, and an aqueous Ca(NO₃)₂ and (NH₄)₂HPO₄ solution as the water phase. A wide variety of morphologies were encountered in synthesis which produced nanosphere (25–40 nm in diameter), sheet-like (3–16 nm in width and 50–300 nm in length), rod-like (10–17 nm in diameter and 24–50 nm in length) and needle-like (4–8 nm in diameter and 80–100 nm in length). The great structural diversity was resulted from the different value of the molar ratio of water to surfactant, W₀. Particles were visualized by transmission electron microscopy (TEM) and the identities of powder confirmed by FT-IR and X-ray diffraction (XRD).     

Fibrous hydroxyapatite grown in the gel system: effects of pH of the solution on the growth rate and morphology

In the preparation of fibrous hydroxyapatite (HAp), using the gel system consisting of agar gel containing calcium nitrate and over-layered (NH₄)₂HPO₄ solution, the pH of the solution was found to greatly influence the growth rate and morphology of the resultant products. In particular, a pH value of about 9–10 produced straight fibrous HAp in the shortest time. Also, the Ca/P molar ratio of the product increased with the pH value of the starting solution. The growth rate and morphology of the product were correlated to the ion species present in the solution at different pHs.     

Effect of key parameters on the morphology transformation of three-dimensional TiO2 solid microspheres

Three-dimensional (3D) TiO₂ solid microspheres with different morphologies have been synthesized on a large scale by a simple hydrothermal method using titanium tetrachloride (TiCl₄) as the titanium source and ammonium fluoride (NH₄F) as the etchant. X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) studies show that the 3D solid microspheres, with an average diameter from hundreds of nanometers to several micrometers, are composed of numerous anatase TiO₂ particles. In addition, the morphologies of the as-prepared 3D solid microspheres can be controlled by adjusting the dosage of NH₄F and the reaction temperatures. The present study has enlarged the family of 3D solid microspheres, and offers a possible route for the synthesis of other inorganic hierarchical structures.     

N-Lauroyl sarcosine sodium salt mediated formation of hydroxyapatite microspheres via a hydrothermal route

Dandelion-like hydroxyapatite (HA) microspheres were successfully prepared using Ca(NO₃)₂·4H₂O and (NH₄)₃PO₄·3H₂O as raw materials and N-Lauroyl sarcosine sodium salt (Sar-Na) as template via a hydrothermal route. The chemical composition, structure, morphology and thermal properties of the samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), Scanning electron microscope (SEM) and Thermal gravimetric analysis (TG), respectively. The results demonstrate that, Sar-Na has great impact on the morphology of HA. With increasing the amount of Sar-Na, the morphology of HA varies from nanograins to nanorods, finally grows into dandelion-like microstructure. The obtained dandelion-like HA microspheres about 6 μm in diameter are composed of radially oriented nanorods. Furthermore, the possible formation mechanism of morphology change is also discussed.     

Template-free hydrothermal synthesis of macroporous TiO2 microspheres on a large scale

Macroporous TiO₂ microspheres have been synthesized on a large scale by a facile hydrothermal process using titanium tetrachloride (TiCl₄) as the titanium source, ammonium fluoride (NH₄F) and hydrogen peroxide (H₂O₂) as the etchant. X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) studies show that the anatase TiO₂ microspheres are well-crystalline with an average diameter of 5.43 μm. N₂ adsorption–desorption and mercury intrusion porosimetry analysis reveal that the as-prepared TiO₂ microspheres are composed of numerous pore networks with an average pore diameter of 274 nm and porosity of 39.8%. In addition, the formation mechanisms of macroporous TiO₂ microspheres were also investigated.     

Controllable growth of zinc oxide nanosheets and sunflower structures by anodization method

Large scale of ZnO nanosheets and sunflower structures were fabricated by anodization of zinc in (NH₄)₂SO₄ and NH₄Cl aqueous electrolytes. The products were characterized via scanning electron microscope, transmission electron microscope and X-ray diffraction analysis. Results show that the sheets are about 20–50 μm in dimension and 20 nm in thickness. The sunflower microstructures are about 400–500 μm in dimension. The possible growth mechanism is suggested on the basis of experimental results.     

Structural characterization of zinc-substituted hydroxyapatite prepared by hydrothermal method

Zinc-substituted hydroxyapatite (Zn-HA) powders were prepared by hydrothermal method using Ca(NO₃)₂, (NH₄)₃PO₄ and Zn(NO₃)₂ as reagents. X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the crystalline phase, microstructure, chemical composition, morphology and thermal stability of Zn-HA. The results show that the substitution content of zinc (Zn) in Zn-HA powders prepared in NaOH solution is higher than that prepared in NH₃ solution, and is lower than that of the corresponding amount of starting materials. The substitution of the Zn ion for calcium ion causes a lower crystallinity of Zn-HA and changes the lattice parameters of Zn-HA, since the ionic radius is smaller in Zn²⁺ (0.074 nm) than in Ca²⁺ (0.099 nm). Furthermore, the substitution of the Zn ions restrains the growth of Zn-HA crystal and decreases the thermal stability of Zn-HA. Zn-HA powder prepared in NH₃ solution starts to decompose at 800 °C when the Zn fraction increases to 15 mol%, while that prepared in NaOH solution start to decompose at 5 mol% Zn. The substitution content of Zn significantly influences the thermal stability, microstructure and morphology of Zn-HA.     

钯纳米颗粒的形貌控制合成

为优化钯纳米颗粒的化学还原法制备工艺,本文以氯钯酸(H₂PdCl₄)为前驱体,抗坏血酸(C₆H₈O₆)为还原剂,聚丙烯酸钠(PAAS)为表面活性剂制备钯纳米颗粒。采用正交实验探究不同工艺参数对钯纳米颗粒粒径和形貌的影响。通过 X射线粉末衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)及电化学工作站对制备产物的结构、物相、形貌、电催化性能进行了表征。结果表明:在相同的工艺体系下,通过温度的改变,40 ℃条件下可以得到粒径大小为64.5 nm,球形度较好,分散性高的钯纳米颗粒;90 ℃条件下可以得到粒径大小为45.9 nm的立方体钯纳米颗粒。所制备的球形和立方体钯纳米颗粒对甲酸的电氧化催化活性分别为商业钯黑的1.57倍和1.49倍,在催化剂制备领域有广泛的应用前景。     

溶剂热法合成粒径可控的Fe3O4磁性介孔/空心球

采用简便的溶剂热法合成粒径可控的Fe3O4磁性介孔/空心球(mesoporous/hollow spheres of magne-tite,MHSM),粒径从80 nm至400 nm可调.通过调节反应时间、NH4HCO3与NH4Ac的摩尔比来控制MHSM的形貌、粒径以及介孔-空心的程度.采用XRD、SEM、TEM、VSM多种表征手段对MHSM进行了表征,结果表明NH4HCO3和NH4Ac的摩尔比对MHSM结构的形成、形貌、粒径起关键性的作用;NH4+的浓度对MHSM的粒径和磁性有决定性的影响;保持NH4HCO3和NH4Ac的摩尔比不变,延长反应时间对MHSM的结构与空腔生长有一定的影响.